EP1629703A1 - Method for the structured metal-coating of polymeric and ceramic support materials, and compound that can be activated and is used in said method - Google Patents
Method for the structured metal-coating of polymeric and ceramic support materials, and compound that can be activated and is used in said methodInfo
- Publication number
- EP1629703A1 EP1629703A1 EP04738625A EP04738625A EP1629703A1 EP 1629703 A1 EP1629703 A1 EP 1629703A1 EP 04738625 A EP04738625 A EP 04738625A EP 04738625 A EP04738625 A EP 04738625A EP 1629703 A1 EP1629703 A1 EP 1629703A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- carrier
- weight
- parts
- activating compound
- 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- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 239000000919 ceramic Substances 0.000 title claims description 11
- 238000000576 coating method Methods 0.000 title claims description 7
- 239000011248 coating agent Substances 0.000 title claims description 5
- 239000000463 material Substances 0.000 title claims description 3
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000001465 metallisation Methods 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000012876 carrier material Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 230000005855 radiation Effects 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 8
- 239000004640 Melamine resin Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- -1 argon ion Chemical class 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 3
- 238000007788 roughening Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 8
- 239000000969 carrier Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
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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
- C23C18/18—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
- C23C18/1813—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by radiant energy
- C23C18/182—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
- C23C18/1803—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
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
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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
- C23C18/1803—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
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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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
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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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
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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
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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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
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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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
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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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
-
- 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
- H05K2203/12—Using specific substances
- H05K2203/121—Metallo-organic compounds
Definitions
- the invention relates to a method for structured metallization of a carrier made of a polymeric or ceramic material for the production of conductive structures for microelectronic applications. It includes the application of a layer of an optically activatable compound to the carrier material, which can be done by spin coating, a doctor blade process, spraying, a printing technique, dipping or another suitable process, the selective irradiation with laser or another suitable light source and the subsequent adhesive metallization in the area of the conductive structures to be produced. Depending on the carrier material used, a pretreatment to improve the adhesive strength can be advantageous.
- the invention also relates to the composition of an optically activatable compound.
- EP 0965656 Al a method for producing a surface activation a palladium compound, which contains a photo-labile group as ligands, described on a substrate, 'which consists of an alumina ceramic wafer with a surface roughness of 0.8 microns.
- This compound is photochemically active so that it decomposes to the metal when it is exposed to UV radiation of a suitable wavelength.
- An excimer lamp is specified as the UV source; Compound absorbs in the 210-260 nm and 290-330 nm range
- DE 4124686 AI discloses a process on a carrier material using laser radiation energy, in which copper is deposited from the gas phase, which contains an organic Cu-metal complex. disadvantage This method is that the structured deposition of copper has to be carried out in a vacuum chamber under an inert gas atmosphere. The high costs for equipment and technical workload are an obstacle to the extensive use of this method within normal production processes.
- US Pat. No. 6,319,564 B1 describes a method for producing conductive structures on a non-conductive carrier material.
- the heavy metal complex is applied to the entire microporous surface of the carrier material and covers the surface of the carrier material in the area of the conductive structures.
- the conductive structures are easier to manufacture than conventional conductive structures. But the application of this method is limited to microporous surfaces and to the use of a KrF excimer laser (248 nm).
- a method for the selective metallization of non-conductive polymeric or ceramic carrier materials comprises the process steps, coating with an optically activatable transition metal complex compound, excitation of this compound with light (e.g. laser) in order to achieve activation on the surfaces to be metallized, and subsequent electroless metallization.
- the coating can be a spin coating, a doctor blade process, spraying, a printing technique, dipping or another suitable method.
- the function of the surface-activating compound is to prepare a surface ⁇ for activation by radiation and the subsequent electroless metallization with a desired conductive material.
- the activated areas are provided with an adhesive metallization by the electroless metallization process.
- Ceramic materials such as aluminum oxide ceramic,
- Barium titanate ceramics and lead zirconate titanate ceramics as well as plastics such as polyester (PET, PBT), polyimide, polyamide, PMMA, ABS, polycarbonate, liquid crystalline polyester (LCP), polyphenylene sulfide as well as mixtures of these plastics with other plastics in question.
- the method according to the invention enables the production of firmly adhering fine conductive structures of uniform layer thickness with a minimum width of up to 20 ⁇ m and good conductivity with short exposure times and is simple and convenient to use.
- the surface-activating compound consists of a non-conductive transition metal complex based on palladium, platinum, gold, copper or silver as an activating compound (actually an active substance on which chemical metallization takes place) and a dicarboxylic acid derivative (i.e. a compound from the group of unsaturated carboxylic acid derivatives), e.g. Methacrylic anhydride, preferably maleic anhydride, as crosslinking agent and melamine resins as complexing agents.
- Palladium diacetate in solution forms a palladium complex with an organic complexing agent. This is indicated by a shift in the absorption band in the UV / Vis spectrum as a result of charge transfer from the ligand to the metal. It is known that stable polyfunctional chelating agents with several ligand atoms such as N, O, S, P are used as organic complexing agents.
- an etherified melamine / formaldehyde resin melamine resin is the organic complexing agent.
- the crosslinker In the structuring process under the influence of light (laser), the crosslinker has the task of crosslinking the reactive components with one another and / or with the substrate material in order to ensure adhesion to the support.
- the surface-activating compound is photochemically active in such a way that it decomposes in the presence of light of suitable wavelength and intensity at room temperature to form the metal, which is the electroless metallization initiated. However, it does not decompose in normal ambient light.
- the metal-ligand bonds are weakened by the laser radiation, which enables the subsequent cleavage or decomposition of the connection to the metal in the region of the conductive structures to be produced. It is further assumed that the irradiated areas of the surface-activating layer form a network in the form of a polymer coating into which palladium cores are incorporated by the addition of maleic anhydride. It is possible to perform the cleavage without heating the complex. This avoids the melting of the carrier material in the work area
- the surface-activating compound has a complex compound with palladium as the metal.
- the irradiation is carried out with an Nd: YAG laser at a wavelength of 355 nm and the subsequently electrolessly deposited metal is copper.
- the surface activation can be carried out at atmospheric air pressure.
- the activation with excimer laser can take place at a wavelength of 248 nm.
- the selective radiation for splitting off the transition metal core from the metal complex only in the areas to be metallized can be done by means of flat applied laser radiation and mask technology as well as by means of focused laser beam.
- pretreatment can be carried out in a known manner, e.g. Etching with chromic sulfuric acid, etc., can be advantageous for achieving the desired adhesive strength.
- Laser radiation with short wavelengths e.g. with excimer laser
- the metallization takes place without wild growth, with the formation of very sharp contours of the conductor tracks. It is particularly suitable for the production of two- or three-dimensional circuit board structures.
- a Kapton® 500H polyimide film is to be used as the carrier material.
- a suitable amount of Kapton® 500H polyimide film is poured into 10% hydrochloric acid and kept at higher temperatures for 10-15 minutes (boiled if necessary). After washing with distilled water and drying in air, the carriers are ready for the next step. The intermediate storage of the beams until the next work step is possible for up to 1 month.
- a polyester film with a rough surface (average roughness 0.7 ⁇ m) or other carrier materials with a porous surface do not require this pretreatment.
- the surface-activating compound 0.8-2.0 parts by weight, preferably 1.0-1.3 parts by weight, of palladium diacetate are dissolved in 80 parts by weight of tetrahydrofuran, and 0.5-1.5 parts by weight, preferably 1.0-1.2 parts by weight of the organic complexing agent
- Melamine resin made from etherified melamine / formaldehyde resins is simply dissolved in 20 parts by weight of tetrahydrofuran.
- the two solutions are then mixed and 0.2-0.5 parts by weight of maleic anhydride are added. The mixture is ready for further processing.
- the resulting surface-activating compound is spin-coated onto a support at a speed of 1500 min "1, a layer of 80 - 100 nm to produce thickness.
- the coated supports are irradiated through a mask with a KrF excimer laser at a wavelength of 248 nm.
- the surface activated in this way can be used directly for electroless copper metallization.
- the coated and selectively irradiated carriers are placed in a MACDermid XD-6157-T copper solution for 2-10 min. Thereafter, the supports are rinsed under running deionized water to remove the remaining copper bath residues to be removed and then dried at 80 ° C in an inert atmosphere for about an hour.
- the tape test (according to US standard: ASTM B 905, edition: 2000 Standard Test Method for Assessing the Adhesion of Metallic and Inorganic Coatings by the Mechanized Tape Test) was successful for the applied copper structure, i.e. good adhesion of the metal structure to the substrate was demonstrated.
- 0.8-2.0 parts by weight, preferably 0.8-1.0 parts by weight of palladium diacetate, are dissolved in 50 parts by weight of tetrahydrofuran to produce the surface-activating compound.
- 0.5 to 15 parts by weight, preferably 8 to 10 parts by weight of the organic complexing agent melamine resin from etherified melamine / formaldehyde resins are dissolved in 50 parts by weight of tetrahydrofuran.
- the two solutions are then mixed and 0.2-0.5 parts by weight of maleic anhydride are added. The mixture is ready for further processing.
- the resulting surface-activating compound is spun onto the carrier, here made of aluminum oxide, at a speed of 350 min -1 and then dried at 60 ° C. for 15 min.
- the coated carriers are irradiated in a focused manner by means of frequency-doubled Nd: YAG lasers at a wavelength of 532 nm and structured directly.
- the laser power is 5 W and the writing speed is 20 - 50 mm / s.
- the surface activated in this way can be used directly for electroless copper metallization. However, it may also be necessary to swivel the surface for 1 min by removing residues from non-irradiated areas in a solvent (tetrahydrofuran).
- the coated and selectively irradiated carriers are placed in a MACDermid XD-6157-T copper solution for 10-20 min and metallized at 70 ° C. without current.
- the supports are then rinsed under running deionized water to remove the remaining copper bath residues and then dried at 80 ° C. in an inert atmosphere for 45 minutes.
- 0.8-2.0 parts by weight of palladium diacetate, preferably 1.0-1.3 parts by weight, in 50 parts by weight of a solvent mixture of PGMEA are used to prepare the surface-activating compound
- Melamine resin from etherified melamine / formaldehyde resins preferably 8-10 parts by weight, dissolved in 50 parts by weight of the solvent mixture.
- the two solutions are then mixed and 0.2-0.5 parts by weight of methacrylic anhydride are added.
- the mixture is ready for further processing.
- the surface-activating compound formed is spun onto the support, here made of polybutylene terephthalate, at a speed of 350 min -1 and then dried at 60 ° C. for 15 min.
- the coated supports are irradiated using an argon ion laser at a wavelength of 488 nm.
- the surface activated in this way can be used directly for electroless copper metallization. However, it may also be necessary to clean the surface for 1 min by removing residues from unexposed areas using solvent (tetrahydrofuran).
- the coated and selectively irradiated carriers are placed in a MACDermid XD-6157-T copper solution for 10-20 min and metallized at 70 ° C. without current.
- the supports are then rinsed under running deionized water to remove the remaining copper bath residues and then dried at 80 ° C. in an inert atmosphere for 45 minutes.
- the tape test was successful for the applied copper structure, i.e. good adhesion of the metal structure to the substrate was demonstrated.
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Abstract
The invention relates to a method for producing highly adhesive conductive structures on non-conductive supports, especially for use in electric circuits, and a surface activating compound which is used in said method. The inventive method comprises the following steps: a surface activating compound is applied and is selectively irradiated; and the irradiated areas are then metal-coated in a currentless manner so as to form metallic structures.
Description
Verfahren zur strukturierten Metallisierung von polymeren und keramischen Trägermaterialien und aktivierbare Verbindung zur Verwendung in diesem VerfahrenProcess for the structured metallization of polymeric and ceramic carrier materials and activatable compound for use in this process
Die Erfindung betrifft ein Verfahren zur strukturierten Metallisierung eines Trägers aus einem polymeren oder keramischen Material zur Herstellung von leitfähigen Strukturen für mikroelektronische Anwendungen. Es umfasst das Aufbringen einer Schicht, aus einer optisch aktivierbaren Verbindung, auf das Trägermaterial, welches durch eine Schleuderbeschichtung (Spin-coating) , einen Rakelprozess, ein Besprühen, eine Drucktechnik, Tauchen oder ein anderes geeignetes Verfahren erfolgen kann, die selektive Bestrahlung mit Laser oder einer anderen geeigneten Lichtquelle und die anschließende haftfeste Metallisierung im Bereich der herzustellenden leitfähigen Strukturen. In Abhängigkeit des verwendeten Trägermaterials kann eine Vorbehandlung zur Verbesserung der Haftfestigkeit vorteilhaft sein.The invention relates to a method for structured metallization of a carrier made of a polymeric or ceramic material for the production of conductive structures for microelectronic applications. It includes the application of a layer of an optically activatable compound to the carrier material, which can be done by spin coating, a doctor blade process, spraying, a printing technique, dipping or another suitable process, the selective irradiation with laser or another suitable light source and the subsequent adhesive metallization in the area of the conductive structures to be produced. Depending on the carrier material used, a pretreatment to improve the adhesive strength can be advantageous.
Die Erfindung betrifft auch die Zusammensetzung einer optisch aktivierbaren Verbindung.The invention also relates to the composition of an optically activatable compound.
Es ist bekannt, dass dünne Palladium-Acetat-Filme durch Lasereinwirkung zur Ablagerung von Palladium und damit als Katalysatoren für nachfolgende stromlose Beschichtung mit anderen Metallen, vor allem Kupfer, verwendet werden können. Gemäß Artikel „VUV Synchrotron radiation processing of thin palladium acetate spin-on films for metallic surface patterning" aus V.46 (1990), S. 153-157 Applied Surface Science, kann dieser sogenannte Palladiumablagerungsprozess unter Nutzung verschiedener Lichtquellen durchgeführt werden.
Im Artikel „LAD - ein neuartiges lasergestütztes Beschichtungsverfahren für Feinstleitermetallisierungen" Nr. 10, V81 (1990), S.3661 „Galvanotechnik" wurde gefunden, dass bei der oben beschriebenen Methode (Nutzung eines dünnen Filmes aus Palladiumacetatlösung und nachfolgende Belichtung mit Excimerlaser bei λ = 248 nm und nachfolgende selektive stromlose Metallisierung) sehr feine Leiterstrukturen erzeugt werden können. Jedoch können keine ausreichenden Haftfestigkeiten erzielt werden (siehe hierzu auchIt is known that thin palladium-acetate films can be used by laser exposure to deposit palladium and thus as catalysts for subsequent electroless plating with other metals, especially copper. According to the article "VUV Synchrotron radiation processing of thin palladium acetate spin-on films for metallic surface patterning" from V.46 (1990), pp. 153-157 Applied Surface Science, this so-called palladium deposition process can be carried out using different light sources. In the article "LAD - a new type of laser-assisted coating process for ultra-fine metallization" No. 10, V81 (1990), p.3661 "Galvanotechnik" it was found that with the method described above (use of a thin film of palladium acetate solution and subsequent exposure with excimer laser at λ = 248 nm and subsequent selective currentless metallization) very fine conductor structures can be generated. However, sufficient adhesive strengths cannot be achieved (see also
WO 99/05895) , bzw. nur mit sehr hohen Keimdichten, die wiederum Wildwuchs in den unbelichteten Bereichen fördern. Letzterem muss mit aufwendigen Spülprozessen, bei denen die unbelichteten Schichten entfernt werden, entgegen gewirkt werden.WO 99/05895), or only with very high germ densities, which in turn promote wild growth in the unexposed areas. The latter must be counteracted with complex rinsing processes in which the unexposed layers are removed.
In der EP 0965656 AI ist eine Methode zur Herstellung einer Oberflächenaktivierung mit einer Palladiumverbindung, welche eine photolabile Gruppe als Liganden enthält, auf einem Substrat beschrieben, ' welches aus einem Aluminiumoxid-Keramik-Wafer mit einer Oberflächenrauigkeit von 0,8 μm besteht. Diese Verbindung ist photochemisch aktiv, so dass sie sich zum Metall zersetzt, wenn sie UV- Strahlung geeigneter Wellenlänge ausgesetzt wird. - Als UV-Quelle wird eine Excimerlampe angegeben; Verbindung absorbiert im Bereich 210-260 nm und 290- 330 nmIs disclosed in EP 0965656 Al a method for producing a surface activation a palladium compound, which contains a photo-labile group as ligands, described on a substrate, 'which consists of an alumina ceramic wafer with a surface roughness of 0.8 microns. This compound is photochemically active so that it decomposes to the metal when it is exposed to UV radiation of a suitable wavelength. - An excimer lamp is specified as the UV source; Compound absorbs in the 210-260 nm and 290-330 nm range
Nachteil: lange Bestrahlungszeiten (5 bis 20 min) und Erwärmung des Substrates (bis 80°C nach 10 min)Disadvantage: long exposure times (5 to 20 min) and heating of the substrate (up to 80 ° C after 10 min)
Die DE 4124686 AI offenbart einen Prozess auf einem Trägermaterial unter Nutzung von Laserstrahlungsenergie, in welchem Kupfer aus der Gasphase, welche einen organischen Cu-Metallkomplex enthält, abgeschieden wird. Nachteil
dieser Methode ist, dass die strukturierte Abscheidung von Kupfer in einer Vakuumkammer unter Inertgas - Atmosphäre durchgeführt werden muss. Die hohen Kosten für Apparate und technischen Arbeitsaufwand sind ein Hindernis für eine ausgedehnte Nutzung dieser Methode innerhalb üblicher Produktionsabläufe.DE 4124686 AI discloses a process on a carrier material using laser radiation energy, in which copper is deposited from the gas phase, which contains an organic Cu-metal complex. disadvantage This method is that the structured deposition of copper has to be carried out in a vacuum chamber under an inert gas atmosphere. The high costs for equipment and technical workload are an obstacle to the extensive use of this method within normal production processes.
In der US 6,319,564 Bl ist eine Methode zur- Herstellung leitfähiger Strukturen auf einem nichtleitfähigen Trägermaterial beschrieben. Der Schwermetallkomplex wird auf die gesamte mikroporöse Oberfläche des Trägermaterials aufgebracht und bedeckt die Oberfläche des Trägermaterials im Bereich der leitfähigen Strukturen. Die leitfähigen Strukturen sind gemäß dieser Erfindung leichter herzustellen als herkömmliche leitfähige Strukturen. Aber die Anwendung dieser Methode ist auf mikroporöse Oberflächen sowie auf die Verwendung eines KrF-Excimerlaser (248 nm) begrenzt.US Pat. No. 6,319,564 B1 describes a method for producing conductive structures on a non-conductive carrier material. The heavy metal complex is applied to the entire microporous surface of the carrier material and covers the surface of the carrier material in the area of the conductive structures. According to this invention, the conductive structures are easier to manufacture than conventional conductive structures. But the application of this method is limited to microporous surfaces and to the use of a KrF excimer laser (248 nm).
Es ist Aufgabe der Erfindung, ein Verfahren zur selektiven Metallisierung von polymeren und keramischen Trägermaterialien zu entwickeln, welches eine verbesserte Haftung der abgelagerten metallischen Strukturen gewährleistet und das zugleich kostengünstig ist und damit ausgedehnt genutzt werden kann.It is an object of the invention to develop a method for the selective metallization of polymeric and ceramic carrier materials, which ensures improved adhesion of the deposited metallic structures and which is also inexpensive and can therefore be used extensively.
Es ist auch Aufgabe der Erfindung eine verbesserte Verbindung zur Anwendung in einem erfindungsgemäßen Verfahren zu finden.It is also an object of the invention to find an improved compound for use in a method according to the invention.
Diese Aufgabe wird für ein Verfahren zur strukturierten Metallisierung von polymeren und keramischen Trägermaterialien gemäß dem Hauptanspruch 1 und für eine Verbindung zur Verwendung in diesem Verfahren gemäß Hauptanspruch 13 gelöst.
Vorteilhafte Ausführungen sind in den Unteransprüchen beschrieben.This object is achieved for a method for structured metallization of polymeric and ceramic carrier materials according to main claim 1 and for a connection for use in this method according to main claim 13. Advantageous designs are described in the subclaims.
Ein erfindungsgemäßes Verfahren zur selektiven Metallisierung von nichtleitenden polymeren oder keramischen Trägermaterialien umfasst die Verfahrensschritte, Beschichtung mit einer optisch aktivierbaren Übergangsmetallkomplexverbindung, Anregung dieser Verbindung mit Licht (z.B. Laser), um die Aktivierung auf den zu metallisierenden Flächen zu erreichen, und nachfolgende stromlose Metallisierung. Die Beschichtung kann eine Schleuderbeschichtung (Spin- coating) , ein Rakelprozeß, ein Besprühen, eine Drucktechnik, Tauchen oder ein anderes geeignetes Verfahren sein.A method according to the invention for the selective metallization of non-conductive polymeric or ceramic carrier materials comprises the process steps, coating with an optically activatable transition metal complex compound, excitation of this compound with light (e.g. laser) in order to achieve activation on the surfaces to be metallized, and subsequent electroless metallization. The coating can be a spin coating, a doctor blade process, spraying, a printing technique, dipping or another suitable method.
Die oberflächenaktivierende Verbindung hat die Aufgabe, eine Oberfläche ■ für die Aktivierung durch Strahlung und die anschließende stromlose Metallisierung mit einem gewünschten leitfähigen Material aufzubereiten. Die aktivierten Bereiche werden durch den stromlosen Metallisierungsprozess mit einer haftfesten Metallisierung versehen. Als nichtleitende Trägermaterialien kommen keramische Materialien wie Aluminiumoxidkeramik,The function of the surface-activating compound is to prepare a surface ■ for activation by radiation and the subsequent electroless metallization with a desired conductive material. The activated areas are provided with an adhesive metallization by the electroless metallization process. Ceramic materials such as aluminum oxide ceramic,
Siliziumnitridkeramik, Aluminiumnitridkeramik,Silicon nitride ceramic, aluminum nitride ceramic,
Bariumtitanatkeramik und Blei-Zirkonat-Titanat-Keramik sowie Kunststoffe wie Polyester (PET, PBT) , Polyimid, Polyamid, PMMA, ABS, Polycarbonat, flüssigkristalline Polyester (LCP) , Polyphenylensulfid sowie Mischungen dieser Kunststoffe mit anderen Kunststoffen in Frage.
Das erfindungsgemäße Verfahren ermöglicht die Herstellung festhaftender feiner leitfähiger Strukturen gleichmäßiger Schichtdicke mit einer minimalen Breite bis zu 20 μm und guter Leitfähigkeit bei geringen Belichtungszeiten und ist einfach und bequem in der Anwendung.Barium titanate ceramics and lead zirconate titanate ceramics as well as plastics such as polyester (PET, PBT), polyimide, polyamide, PMMA, ABS, polycarbonate, liquid crystalline polyester (LCP), polyphenylene sulfide as well as mixtures of these plastics with other plastics in question. The method according to the invention enables the production of firmly adhering fine conductive structures of uniform layer thickness with a minimum width of up to 20 μm and good conductivity with short exposure times and is simple and convenient to use.
Die oberflächenaktivierende Verbindung besteht aus einem nichtleitenden Übergangsmetallkomplex auf der Basis von Palladium, Platin, Gold, Kupfer oder Silber als Aktivierungsverbindung (eigentlich wirksame Substanz an der die chemische Metallisierung stattfindet) und einem Dicarbonsäureabkömmling (d.h. eine Verbindung aus der Gruppe der ungesättigten Karbonsäurederivate), z.B. Methacrylsäureanhydrid, bevorzugt Maleinsäureanhydrid, als Vernetzer sowie Melaminharzen als Komplexbildner.The surface-activating compound consists of a non-conductive transition metal complex based on palladium, platinum, gold, copper or silver as an activating compound (actually an active substance on which chemical metallization takes place) and a dicarboxylic acid derivative (i.e. a compound from the group of unsaturated carboxylic acid derivatives), e.g. Methacrylic anhydride, preferably maleic anhydride, as crosslinking agent and melamine resins as complexing agents.
Palladiumdiacetat in Lösung bildet mit einem organischen Komplexbildner einen Palladiumkomplex. Darauf weist eine Verschiebung der Absorptionsbande im UV/Vis-Spektrum hin, als Resultat eines Ladungstransfers vom Liganden zum Metall. Es ist bekannt, dass stabile polyfunktionelle Chelatbildner mit mehreren Ligantoratomen wie N, O, S, P als organische Komplexbildner verwendet werden. In der vorliegenden Erfindung ist ein Melaminharz aus veräthertem Melamin/Formaldehydharz der organische Komplexbildner. Der Vernetzer hat die Aufgabe im Prozess der Strukturierung unter Einfluss von Licht (Laser) die Reaktivkomponenten untereinander und/oder mit dem Substratmaterial zu vernetzen, um die Haftung auf dem Träger sicherzustellen.Palladium diacetate in solution forms a palladium complex with an organic complexing agent. This is indicated by a shift in the absorption band in the UV / Vis spectrum as a result of charge transfer from the ligand to the metal. It is known that stable polyfunctional chelating agents with several ligand atoms such as N, O, S, P are used as organic complexing agents. In the present invention, an etherified melamine / formaldehyde resin melamine resin is the organic complexing agent. In the structuring process under the influence of light (laser), the crosslinker has the task of crosslinking the reactive components with one another and / or with the substrate material in order to ensure adhesion to the support.
Die oberflächenaktivierende Verbindung ist photochemisch aktiv derart, dass sie sich in Gegenwart von Licht geeigneter Wellenlänge und Intensität bei Raumtemperatur zum Metall zersetzt, welches die stromlose Metallisierung
initiiert. Sie zersetzt sich aber nicht bei normalem Umgebungslicht .The surface-activating compound is photochemically active in such a way that it decomposes in the presence of light of suitable wavelength and intensity at room temperature to form the metal, which is the electroless metallization initiated. However, it does not decompose in normal ambient light.
Durch die Laserbestrahlung werden die Metall-Ligand- Bindungen geschwächt, was die nachfolgende Spaltung oder Zersetzung der Verbindung zum Metall im Bereich der zu erzeugenden leitfahigen Strukturen ermöglicht. Es wird weiterhin angenommen, dass die bestrahlten Flachen der oberflachenaktivierenden Schicht durch die Zugabe von Maleinsaureanhydrid ein Netzwerk bilden in Form einer Polymerbeschichtung, in die Palladiumkerne eingebaut sind. Es ist möglich, die Spaltung ohne Erwärmung des Komplexes durchzufuhren. So wird das Aufschmelzen des Tragermaterials im Arbeitsbereich vermiedenThe metal-ligand bonds are weakened by the laser radiation, which enables the subsequent cleavage or decomposition of the connection to the metal in the region of the conductive structures to be produced. It is further assumed that the irradiated areas of the surface-activating layer form a network in the form of a polymer coating into which palladium cores are incorporated by the addition of maleic anhydride. It is possible to perform the cleavage without heating the complex. This avoids the melting of the carrier material in the work area
Bei einer besonders bevorzugten Methode weißt die oberflachenaktivierende Verbindung eine Komplexverbindung mit Palladium als Metall auf. Die Bestrahlung erfolgt mit einem Nd:YAG-Laser bei einer Wellenlange von 355 nm und das nachfolgend stromlos abgeschiedene Metall ist Kupfer. Die Oberflachenaktivierung kann bei atmosphärischem Luftdruck durchgeführt werden.In a particularly preferred method, the surface-activating compound has a complex compound with palladium as the metal. The irradiation is carried out with an Nd: YAG laser at a wavelength of 355 nm and the subsequently electrolessly deposited metal is copper. The surface activation can be carried out at atmospheric air pressure.
In einer anderen Ausgestaltungsvariante kann die Aktivierung mit Excimerlaser bei einer Wellenlange von 248 nm erfolgen.In another embodiment variant, the activation with excimer laser can take place at a wavelength of 248 nm.
Vergleichbare Ergebnisse werden auch mit einem Argonionenlaser bei einer Wellenlange von 488 nm erzielt.Comparable results are also achieved with an argon ion laser at a wavelength of 488 nm.
Die selektive Bestrahlung zur Abspaltung des Ubergangsmetallkerns vom Metallkomplex nur in den zu metallisierenden Bereichen kann sowohl mittels flachig
aufgebrachter Laserstrahlung und Maskentechnik als auch mittels fokussiertem Laserstrahl erfolgen.The selective radiation for splitting off the transition metal core from the metal complex only in the areas to be metallized can be done by means of flat applied laser radiation and mask technology as well as by means of focused laser beam.
Mit dem erfindungsgemäßen Verfahren können auf gebräuchlichen KunststoffOberflächen, wieWith the method according to the invention, conventional plastic surfaces such as
Spritzgussartikeln oder Folien, haftfeste Metallisierungen erzeugt werden.Injection molded articles or foils, adhesive metallizations are generated.
Bei Verwendung von Trägermaterialien mit nicht ausreichender Haftung kann eine Vorbehandlung in bekannter Weise, z.B. Ätzen mit Chromschwefelsäure etc., für das Erreichen der gewünschten Haftfestigkeit von Vorteil sein.When using carrier materials with insufficient adhesion, pretreatment can be carried out in a known manner, e.g. Etching with chromic sulfuric acid, etc., can be advantageous for achieving the desired adhesive strength.
Die Laserbestrahlung mit kurzen Wellenlängen, z.B. mit Excimerlaser, ermöglicht sehr feine, scharfe Strukturen. In diesem Fall findet die Metallisierung ohne wildes Wachstum unter Ausbildung sehr scharfer Konturen der Leiterbahnen statt. Es ist besonders geeignet zur Herstellung von zwei- oder dreidimensionalen Leiterplattenstrukturen.Laser radiation with short wavelengths, e.g. with excimer laser, enables very fine, sharp structures. In this case, the metallization takes place without wild growth, with the formation of very sharp contours of the conductor tracks. It is particularly suitable for the production of two- or three-dimensional circuit board structures.
Die Erfindung soll nachfolgend anhand von Ausführungsbeispielen näher erläutert werden.The invention will be explained in more detail below using exemplary embodiments.
In einem ersten Ausführungsbeispiel soll eine Polyimidfolie Kapton® 500H als Trägermaterial verwendet werden. Zur Vorbehandlung wird eine geeignete Menge der Polyimidfolie Kapton® 500H, in 10%-ige Salzsäure gegeben und 10-15 min bei höheren Temperaturen gehalten (ggf. gekocht) . Nach dem Waschen mit destilliertem Wasser und Trocknen an Luft sind die Träger für den nächsten Schritt vorbereitet. Die Zwischenlagerung der Träger bis zum nächsten Arbeitsgang ist bis zu 1 Monat möglich.
Eine Polyesterfolie mit rauer Oberfläche (mittlere Rauhigkeit 0,7 μm) oder andere Trägermaterialien mit poröser Oberfläche benötigen diese Vorbehandlung nicht.In a first embodiment, a Kapton® 500H polyimide film is to be used as the carrier material. For the pretreatment, a suitable amount of Kapton® 500H polyimide film is poured into 10% hydrochloric acid and kept at higher temperatures for 10-15 minutes (boiled if necessary). After washing with distilled water and drying in air, the carriers are ready for the next step. The intermediate storage of the beams until the next work step is possible for up to 1 month. A polyester film with a rough surface (average roughness 0.7 μm) or other carrier materials with a porous surface do not require this pretreatment.
Zur Herstellung der oberflachenaktivierenden Verbindung werden 0,8 - 2,0 Gewichtsanteile vorzugsweise 1,0 - 1,3 Gewichtsanteile Palladiumdiacetat in 80 Gewichtsanteilen Tetrahydrofuran gelöst und 0,5 - 1,5 Gewichtsanteile vorzugsweise 1,0 - 1,2 Gewichtsanteile des organischen Komplexbildners Melaminharz aus verätherten Melamin/Formaldehydharzen werden einfach in 20 Gewichtsanteile Tetrahydrofuran gelöst. Beide Lösungen werden dann gemischt und 0,2 - 0,5 Gewichtsanteile Maleinsaureanhydrid werden zugeben. Die Mischung ist zur Weiterverarbeitung bereit.To prepare the surface-activating compound, 0.8-2.0 parts by weight, preferably 1.0-1.3 parts by weight, of palladium diacetate are dissolved in 80 parts by weight of tetrahydrofuran, and 0.5-1.5 parts by weight, preferably 1.0-1.2 parts by weight of the organic complexing agent Melamine resin made from etherified melamine / formaldehyde resins is simply dissolved in 20 parts by weight of tetrahydrofuran. The two solutions are then mixed and 0.2-0.5 parts by weight of maleic anhydride are added. The mixture is ready for further processing.
Die entstandene oberflächenaktivierende Verbindung wird auf einen Träger mit einer Drehzahl von 1500 min"1 aufgeschleudert, um eine Schicht von 80 - 100 nm Dicke herzustellen.The resulting surface-activating compound is spin-coated onto a support at a speed of 1500 min "1, a layer of 80 - 100 nm to produce thickness.
Die beschichteten Träger werden durch eine Maske mit einem KrF-Excimerlaser bei einer Wellenlänge von 248 nm bestrahlt. Die in dieser Weise aktivierte Oberfläche kann direkt zur stromlosen Kupfermetallisierung verwendet werden. Es kann jedoch von Vorteil sein, die Oberfläche durch Waschen von Rückständen nicht bestrahlter Folie mittels Lösungsmittel z.B. Tetrahydrofuran, zu reinigen.The coated supports are irradiated through a mask with a KrF excimer laser at a wavelength of 248 nm. The surface activated in this way can be used directly for electroless copper metallization. However, it may be advantageous to remove the surface by washing residues of non-irradiated film with solvent e.g. Tetrahydrofuran, to clean.
Als nächstes werden die beschichteten und selektiv bestrahlten Träger für 2 - 10 min in eine MACDermid XD- 6157-T Kupferlösung gegeben. Danach werden die Träger unter fließendem deionisiertem Wasser gespült, um die
verbleibenden Kupferbadreste zu entfernen und anschließend bei 80°C in inerter Atmosphäre ca. eine Stunde getrocknet.Next, the coated and selectively irradiated carriers are placed in a MACDermid XD-6157-T copper solution for 2-10 min. Thereafter, the supports are rinsed under running deionized water to remove the remaining copper bath residues to be removed and then dried at 80 ° C in an inert atmosphere for about an hour.
Mit dem konkret beschriebenen Verfahrensablauf wurde eine 600 nm dicke Kupferschicht in den selektiv bestrahlten Bereichen ausgebildet.With the process sequence specifically described, a 600 nm thick copper layer was formed in the selectively irradiated areas.
Der Tape-Test (entsprechend US-Norm: ASTM B 905, Ausgabe:2000 Standard Test Methode for Assessing the Adhesion of Metallic and Inorganic Coatings by the Mechanized Tape Test) verlief für die aufgebrachte Kupferstruktur erfolgreich, d.h. es wurde eine gute Haftung der Metallstruktur auf dem Substrat nachgewiesen.The tape test (according to US standard: ASTM B 905, edition: 2000 Standard Test Method for Assessing the Adhesion of Metallic and Inorganic Coatings by the Mechanized Tape Test) was successful for the applied copper structure, i.e. good adhesion of the metal structure to the substrate was demonstrated.
In einem zweiten Ausführungsbeispiel werden zur Herstellung der oberflachenaktivierenden Verbindung 0,8 - 2,0 Gewichtsanteile vorzugsweise 0,8 - 1,0 Gewichtsanteile Palladiumdiacetat in 50 Gewichtsanteilen Tetrahydrofuran gelöst. Des weiteren werden 0,5 - 15 Gewichtsanteile vorzugsweise 8 - 10 Gewichtsanteile des organischen Komplexbildners Melaminharz aus veräthertem Melamin/Formaldehydharzen in 50 Gewichtsanteilen Tetrahydrofuran gelöst. Beide Lösungen werden dann gemischt und es werden 0,2 - 0,5 Gewichtsanteile Maleinsaureanhydrid zugeben. Die Mischung ist zur Weiterverarbeitung bereit.In a second exemplary embodiment, 0.8-2.0 parts by weight, preferably 0.8-1.0 parts by weight of palladium diacetate, are dissolved in 50 parts by weight of tetrahydrofuran to produce the surface-activating compound. Furthermore, 0.5 to 15 parts by weight, preferably 8 to 10 parts by weight of the organic complexing agent melamine resin from etherified melamine / formaldehyde resins are dissolved in 50 parts by weight of tetrahydrofuran. The two solutions are then mixed and 0.2-0.5 parts by weight of maleic anhydride are added. The mixture is ready for further processing.
Die entstandene oberflächenaktivierende Verbindung wird auf den Träger, hier aus Aluminiumoxid, mit einer Drehzahl von 350 min-1 aufgeschleudert und anschließend 15 min bei 60 °C getrocknet .The resulting surface-activating compound is spun onto the carrier, here made of aluminum oxide, at a speed of 350 min -1 and then dried at 60 ° C. for 15 min.
Die beschichteten Träger werden mittels frequenzverdoppelten Nd:YAG-Laser bei einer Wellenlänge von 532 nm fokussiert bestrahlt und dabei direkt strukturiert. Die Laserleistung beträgt hierbei 5 W und es wird mit einer Schreibgeschwindigkeit von 20 - 50 mm/s gearbeitet.
Die in dieser Weise aktivierte Oberfläche kann direkt zur stromlosen Kupfermetallisierung verwendet werden. Es kann jedoch auch nötig sein, die Oberfläche durch Entfernen von Rückständen von nicht bestrahlten Bereichen in einem Lösungsmittel { Tetrahydrofuran) für 1 min zur Reinigung geschwenkt .The coated carriers are irradiated in a focused manner by means of frequency-doubled Nd: YAG lasers at a wavelength of 532 nm and structured directly. The laser power is 5 W and the writing speed is 20 - 50 mm / s. The surface activated in this way can be used directly for electroless copper metallization. However, it may also be necessary to swivel the surface for 1 min by removing residues from non-irradiated areas in a solvent (tetrahydrofuran).
Als nächstes werden die beschichteten und selektiv bestrahlten Träger für 10 - 20 min in eine MACDermid XD- 6157-T Kupferlösung gegeben und bei 70°C stromlos metallisiert. Danach werden die Träger unter fließendem deionisiertem Wasser gespült, um die verbleibenden Kupferbadreste zu entfernen und anschließend bei 80 °C in inerter Atmosphäre 45 min getrocknet.Next, the coated and selectively irradiated carriers are placed in a MACDermid XD-6157-T copper solution for 10-20 min and metallized at 70 ° C. without current. The supports are then rinsed under running deionized water to remove the remaining copper bath residues and then dried at 80 ° C. in an inert atmosphere for 45 minutes.
Bei der Durchführung des Verfahrens gemäß dem zweiten Ausführungsbeispiel wurde eine 400 nm dicke Kupferschicht in den selektiv bestrahlten Bereichen ausgebildet.When the method according to the second exemplary embodiment was carried out, a 400 nm thick copper layer was formed in the selectively irradiated areas.
In einem dritten Ausführungsbeispiel werden zur Herstellung der oberflachenaktivierenden Verbindung 0,8 - 2,0 Gewichtsanteile Palladiumdiacetat, vorzugsweise 1,0 - 1,3 Gewichtsanteile, in 50 Gewichtsanteilen eines Lösungsmittelgemisches aus PGMEAIn a third exemplary embodiment, 0.8-2.0 parts by weight of palladium diacetate, preferably 1.0-1.3 parts by weight, in 50 parts by weight of a solvent mixture of PGMEA are used to prepare the surface-activating compound
(Propylenglycolmonomethyletheracetat) und NMP (N-Methyl-2- pyrrolidon) , im Verhältnis 3:1 gelöst. Des weiteren werden(Propylene glycol monomethyl ether acetate) and NMP (N-methyl-2-pyrrolidone), dissolved in a ratio of 3: 1. Be further
5 - 15 Gewichtsanteile des organischen Komplexbildners5 - 15 parts by weight of the organic complexing agent
Melaminharz aus verätherten Melamin/Formaldehydharzen, vorzugsweise 8 - 10 Gewichtsanteile, in 50 Gewichtsteilen des Lösungsmittelgemisches gelöst. Beide Lösungen werden dann gemischt und es werden 0,2 - 0,5 Gewichtsanteile Methacrylsäureanhydrid zugeben. Die Mischung ist zur Weiterverarbeitung bereit.
Die entstandene oberflächenaktivierende Verbindung wird auf den Träger, hier aus Polybutylentherephthalat, mit einer Drehzahl von 350 min-1 aufgeschleudert und anschließend 15 min bei 60°C getrocknet.Melamine resin from etherified melamine / formaldehyde resins, preferably 8-10 parts by weight, dissolved in 50 parts by weight of the solvent mixture. The two solutions are then mixed and 0.2-0.5 parts by weight of methacrylic anhydride are added. The mixture is ready for further processing. The surface-activating compound formed is spun onto the support, here made of polybutylene terephthalate, at a speed of 350 min -1 and then dried at 60 ° C. for 15 min.
Die beschichteten Träger werden mittels eines Argonionenlasers bei einer Wellenlänge von 488 nm bestrahlt. Die in dieser Weise aktivierte Oberfläche kann direkt zur stromlosen Kupfermetallisierung verwendet werden. Es kann jedoch auch nötig sein, die Oberfläche durch Entfernen von Rückständen nicht bestrahlter Bereiche mittels Lösungsmittel (Tetrahydrofuran) für 1 min zu reinigen.The coated supports are irradiated using an argon ion laser at a wavelength of 488 nm. The surface activated in this way can be used directly for electroless copper metallization. However, it may also be necessary to clean the surface for 1 min by removing residues from unexposed areas using solvent (tetrahydrofuran).
Als nächstes werden die beschichteten und selektiv bestrahlten Träger für 10 - 20 min in eine MACDermid XD- 6157-T Kupferlösung gegeben' und bei 70°C stromlos metallisiert. Danach werden die Träger unter fließendem deionisiertem Wasser gespült, um die verbleibenden Kupferbadreste zu entfernen und anschließend bei 80°C in inerter Atmosphäre 45 min getrocknet.Next, the coated and selectively irradiated carriers are placed in a MACDermid XD-6157-T copper solution for 10-20 min and metallized at 70 ° C. without current. The supports are then rinsed under running deionized water to remove the remaining copper bath residues and then dried at 80 ° C. in an inert atmosphere for 45 minutes.
Der Tape-Test verlief für die aufgebrachte Kupferstruktur erfolgreich, d.h. es wurde eine gute Haftung der Metallstruktur auf dem Substrat nachgewiesen.
The tape test was successful for the applied copper structure, i.e. good adhesion of the metal structure to the substrate was demonstrated.
Claims
1. Verfahren zur strukturierten Metallisierung von polymeren und keramischen Trägermaterialien bei dem - eine oberflächenaktivierbare Verbindung, welche einen nichtleitenden organischen Übergangsmetallkomplex als oberflächenaktivierende Verbindung, eine Dicarbonsäure als Vernetzer und Melaminharz als Komplexbildner enthält, auf das Trägermaterial mittels geeigneter Beschichtung aufgebracht wird,1. Process for the structured metallization of polymeric and ceramic carrier materials in which a surface-activatable compound which contains a non-conductive organic transition metal complex as surface-activating compound, a dicarboxylic acid as crosslinking agent and melamine resin as complexing agent is applied to the carrier material by means of a suitable coating,
- die oberflächenaktivierbare Verbindung selektiv mit Licht bestrahlt wird, und anschließend eine stromlose Metallisierung der bestrahlten Bereiche zur Ausbildung metallischer Strukturen in einem chemisch-reduktiven Bad durchgeführt wird.- The surface-activatable compound is selectively irradiated with light, and then an electroless metallization of the irradiated areas is carried out to form metallic structures in a chemical-reductive bath.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass zur Aufrauung der Oberfläche des Trägers aus einem polymeren Material diese chemisch, physikalisch oder thermisch vorbehandelt wird.2. The method according to claim 1, characterized in that for roughening the surface of the carrier made of a polymeric material, this is pretreated chemically, physically or thermally.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die Vorbehandlung des Trägers durch Atzen der Trägeroberfläche erfolgt.3. The method according to claim 2, characterized in that the pretreatment of the carrier is carried out by etching the carrier surface.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass die Ätzlösung in Wasser verdünnte Salzsäurelösung ist .4. The method according to claim 3, characterized in that the etching solution is hydrochloric acid solution diluted in water.
5. Verfahren nach Anspruch 3 oder 4, dadurch gekennzeichnet, dass der Ätzprozess durch Erhitzen der Ätzlösung stattfindet . 5. The method according to claim 3 or 4, characterized in that the etching process takes place by heating the etching solution.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Übergangsmetallkomplex Palladium enthält.6. The method according to claim 1, characterized in that the transition metal complex contains palladium.
7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die nichtleitende oberflächenaktivierbare Verbindung in einem Lösungsmittel gelöst ist und auf dem Träger in Form einer Flüssigkeit appliziert wird.7. The method according to claim 1, characterized in that the non-conductive surface-activatable compound is dissolved in a solvent and is applied to the carrier in the form of a liquid.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das Lösungsmittel Tetrahydrofuran ist.8. The method according to claim 7, characterized in that the solvent is tetrahydrofuran.
9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Licht eine Laserbestrahlung mit einer Wellenlänge kleiner 600 nm ist.9. The method according to claim 1, characterized in that the light is laser radiation with a wavelength less than 600 nm.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass die Laserstrahlung mit einem frequenzverdoppelnden oder verdreifachenden Nd:YAG-Laser (λ= 532 nm bzw. 355 nm) erzeugt wird.10. The method according to claim 9, characterized in that the laser radiation is generated with a frequency doubling or tripling Nd: YAG laser (λ = 532 nm or 355 nm).
11. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass die Laserstrahlung mit einem Argonionenlaser (λ = 488 nm) erzeugt wird.11. The method according to claim 9, characterized in that the laser radiation is generated with an argon ion laser (λ = 488 nm).
12. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Entfernung der nichtbestrahlten oberflachenaktivierenden Verbindung nach der Bestrahlung in Tetrahydrofuran vorgenommen wird.12. The method according to claim 1, characterized in that the removal of the non-irradiated surface-activating compound is carried out after the irradiation in tetrahydrofuran.
13. Oberflächenaktivierende Verbindung zur Aktivierung der13. Surface activating compound to activate the
Oberfläche eines polymeren oder keramischen Trägeres zur stromlosen Metallisierung mit einem nichtleitenden organischen Übergangsmetallkomplex als Aktivierungsverbindung, eine Dicarbonsäure als Vernetzer und Melaminharz als Komplexbildner.Surface of a polymer or ceramic Carrier for electroless metallization with a non-conductive organic transition metal complex as an activation compound, a dicarboxylic acid as a crosslinking agent and melamine resin as a complexing agent.
14. Oberflächenaktivierende Verbindung nach Anspruch 13, dadurch gekennzeichnet, dass die Aktivierungsverbindung ein Übergangsmetallkomplex auf der Basis von Palladium ist und die Dicarbonsäure als Vernetzer Maleinsaureanhydrid ist.14. Surface-activating compound according to claim 13, characterized in that the activating compound is a transition metal complex based on palladium and the dicarboxylic acid as crosslinking agent is maleic anhydride.
15. Oberflächenaktivierende Verbindung nach Anspruch 14, dadurch gekennzeichnet, dass die Verbindung bezogen auf eine Losungsmittelanteil von 100 Gewichtsanteile 0,8-2,0 Gewichtsanteile Palladiumdiacetat, 5-15 Gewichtsanteile Melaminharz und 0,2-0,5 Gewichtsanteile Maleinsaureanhydrid enthält. 15. Surface-activating compound according to claim 14, characterized in that the compound contains 0.8-2.0 parts by weight of palladium diacetate, 5-15 parts by weight of melamine resin and 0.2-0.5 parts by weight of maleic anhydride based on a solvent fraction of 100 parts by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10325520 | 2003-06-05 | ||
| PCT/DE2004/001171 WO2004110118A1 (en) | 2003-06-05 | 2004-06-04 | Method for the structured metal-coating of polymeric and ceramic support materials, and compound that can be activated and is used in said method |
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| Publication Number | Publication Date |
|---|---|
| EP1629703A1 true EP1629703A1 (en) | 2006-03-01 |
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| US (1) | US20070092638A1 (en) |
| EP (1) | EP1629703A1 (en) |
| JP (1) | JP2006526889A (en) |
| CN (1) | CN1799293A (en) |
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| US8974869B2 (en) * | 2010-01-26 | 2015-03-10 | Robert Hamilton | Method for improving plating on non-conductive substrates |
| US8703602B2 (en) * | 2010-12-02 | 2014-04-22 | Qualcomm Incorporated | Selective seed layer treatment for feature plating |
| TW201352095A (en) * | 2012-06-11 | 2013-12-16 | Unimicron Technology Corp | Circuit board and manufacturing method thereof |
| CN103517568B (en) * | 2012-06-19 | 2016-12-21 | 欣兴电子股份有限公司 | Circuit board and manufacturing method thereof |
| DE102014101522A1 (en) * | 2014-02-07 | 2015-08-13 | 3D Schilling Gmbh | Method and apparatus for selectively activating at least a portion of a surface of a dielectric substrate |
| WO2016031691A1 (en) * | 2014-08-29 | 2016-03-03 | 株式会社村田製作所 | Method for manufacturing multilayer circuit board, and multilayer circuit board |
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| DE3814506A1 (en) * | 1988-04-29 | 1989-11-09 | Bayer Ag | METHOD FOR METALLIZING SUBSTRATE SURFACES |
| KR100272739B1 (en) * | 1994-05-13 | 2000-11-15 | 기타지마 요시토시 | Multilayer printed wiring board and manufacturing method thereof, transfer disc and manufacturing method thereof |
| US6210537B1 (en) * | 1995-06-19 | 2001-04-03 | Lynntech, Inc. | Method of forming electronically conducting polymers on conducting and nonconducting substrates |
| DE19723734C2 (en) * | 1997-06-06 | 2002-02-07 | Gerhard Naundorf | Conductor structures on a non-conductive carrier material and method for their production |
| EP1062850B1 (en) * | 1998-12-10 | 2007-05-30 | LPKF Laser & Electronics Aktiengesellschaft | Method for producing printed conductor structures |
-
2004
- 2004-06-04 JP JP2006508122A patent/JP2006526889A/en active Pending
- 2004-06-04 US US10/559,112 patent/US20070092638A1/en not_active Abandoned
- 2004-06-04 DE DE112004001472T patent/DE112004001472D2/en not_active Expired - Fee Related
- 2004-06-04 CN CNA2004800151862A patent/CN1799293A/en active Pending
- 2004-06-04 EP EP04738625A patent/EP1629703A1/en not_active Withdrawn
- 2004-06-04 WO PCT/DE2004/001171 patent/WO2004110118A1/en not_active Ceased
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| CN1799293A (en) | 2006-07-05 |
| WO2004110118A1 (en) | 2004-12-16 |
| US20070092638A1 (en) | 2007-04-26 |
| DE112004001472D2 (en) | 2006-04-20 |
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