TWI530515B - 藉由電磁波的直接輻射而形成導電圖案的方法和在其上具有導電圖案之樹脂結構 - Google Patents
藉由電磁波的直接輻射而形成導電圖案的方法和在其上具有導電圖案之樹脂結構 Download PDFInfo
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- TWI530515B TWI530515B TW103127553A TW103127553A TWI530515B TW I530515 B TWI530515 B TW I530515B TW 103127553 A TW103127553 A TW 103127553A TW 103127553 A TW103127553 A TW 103127553A TW I530515 B TWI530515 B TW I530515B
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- Taiwan
- Prior art keywords
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- polymer resin
- resin substrate
- metal layer
- electromagnetic wave
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 82
- 229920005989 resin Polymers 0.000 title claims description 53
- 239000011347 resin Substances 0.000 title claims description 53
- 230000005855 radiation Effects 0.000 title claims description 41
- 239000000758 substrate Substances 0.000 claims description 130
- 239000002952 polymeric resin Substances 0.000 claims description 124
- 229920003002 synthetic resin Polymers 0.000 claims description 124
- 229910052751 metal Inorganic materials 0.000 claims description 104
- 239000002184 metal Substances 0.000 claims description 104
- 230000003746 surface roughness Effects 0.000 claims description 57
- 239000013078 crystal Substances 0.000 claims description 47
- 238000012360 testing method Methods 0.000 claims description 20
- -1 polypropylene Polymers 0.000 claims description 18
- 230000032798 delamination Effects 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000002082 metal nanoparticle Substances 0.000 claims description 7
- 238000010561 standard procedure Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002390 adhesive tape Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229920005668 polycarbonate resin Polymers 0.000 claims description 6
- 239000004431 polycarbonate resin Substances 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 2
- 239000004954 Polyphthalamide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001680 brushing effect Effects 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920006375 polyphtalamide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 claims 1
- 238000009713 electroplating Methods 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000000654 additive Substances 0.000 description 25
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- 230000003287 optical effect Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
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- 238000006116 polymerization reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
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- 101710134784 Agnoprotein Proteins 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
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- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 239000003017 thermal stabilizer Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000004380 Cholic acid Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
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- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
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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
-
- 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
- C23C18/1689—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
-
- 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
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Description
本發明關於一種藉由電磁波的直接輻射而形成導電圖案的方法，該電磁波能藉由簡單製程將精細導電圖案形成於不同種類的聚合物樹脂產物或樹脂層上，即使是該聚合物樹脂本身中沒有特定無機添加物；以及其上形成具有該導電圖案之樹脂結構。
近幾年，因為發展精細電子技術，所以對於精細導電圖案形成於不同樹脂產物或樹脂層等的聚合物樹脂基材(或產物)表面上之結構的需求提高。在該聚合物樹脂基材表面和該結構上的導電圖案可用以將不同標的如天線整併於手機外殼、不同種類的感測器、MEMS結構和RFID標籤等中。
特別是，最近的可攜式裝置如智慧式手機等不像現有
的手機等，必須同時安裝局部網路功能如通訊、藍芽、Wi-Fi和電子付款等，且由於此原因，其必需同時安裝不同天線於一個智慧式手機中。然而，除了那個之外，因為得強調該可攜式裝置如智慧式手機等的審美設計態樣，所以持續提議且研究能擔任該聚合物樹脂基材表面上的不同天線如該可攜式裝置的外殼等之導電圖案的形成方法以便同時符合這些要求。
因為對於將導電圖案形成於該聚合物樹脂基材表面上的技術的興趣提昇，所以有人提議關此的數種技術。例如，有人提議一種將導電圖案形成於聚合物樹脂基材上的方法，其係藉由將含有過渡金屬如銅和鉻等特定無機添加物(例如，具有尖晶石結構的CuCr2O4等)摻混且在聚合物樹脂晶片中成形而形成聚合物樹脂基材，將電磁波如雷射等直接輻射於預定區域上，且鍍敷該雷射輻射區以形成金屬層。在此方法中，使該雷射輻射區中的無機添加物衍生組分曝光且產生一種鍍敷晶種的功能以致於可以形成該金屬層和導電圖案。
然而，因為該導電圖案的形成方法中得使用實質量的高價特定無機添加物，所以會有總製造成本提高的缺點。除此之外，因為該無機添加物必須混入該聚合物樹脂晶片本身中，所以該無機添加物可能損及該聚合物樹脂基材或其所形成的樹脂產物之物性如機械性質等。另外，該特定無機添加物如具有尖晶石結構的CuCr2O4等本身具有相當深的顏色，使該特定無機添加物可能在提供客戶期望的顏
色之含有該特定無機添加物的聚合物樹脂基材或樹脂產物時損及多重因子。例如，為了提供具有期望顏色的含有該無機添加物之聚合物樹脂基材，得使用大量的顏料，且不容易提供白色。
由於該缺點，所以需要一種能藉由簡單製程將精細導電圖案形成於不同種類的聚合物樹脂產物或樹脂層上的技術，即使是該聚合物樹脂本身中沒有特定無機添加物。
本發明提供一種藉由電磁波的直接輻射而形成導電圖案的方法，該電磁波能藉由簡單製程將精細導電圖案形成於不同種類的聚合物樹脂產物或樹脂層上。
除此之外，本發明提供一種樹脂結構，其具有藉由該導電圖案的形成方法製得的導電圖案。
本發明之一代表性具體實例提供一種藉由電磁波的直接輻射而形成導電圖案的方法，該方法包括藉由將該電磁波選擇性地輻射於聚合物樹脂基材上而形成具有預定表面粗糙度的第一區；將導電晶種形成於該聚合物樹脂基材上；藉由鍍敷其上形成具有導電晶種的該聚合物樹脂基材而形成金屬層；及從該聚合物樹脂基材的第二區移除該導電晶種和該金屬層，其中該第二區具有比該第一區小的表
面粗糙度。
除此之外，該第一和第二區的表面粗糙度可藉由其他方法界定。例如，當藉由使用黏著力為4.0至6.0N/10mm寬的膠帶進行根據ISO 2409標準方法之間距為2mm或更小的橫割試驗時，該聚合物樹脂基材的第一區之表面粗糙度可藉由試驗中的標的金屬層脫層面積相當於該金屬層面積的5%或更小時之黏著力界定，且當在剩下的第二區上進行相同試驗時，該聚合物樹脂基材剩下的第二區之表面粗糙度可藉由試驗中的標的金屬層脫層面積相當於該金屬層面積的65%或更大時之黏著力界定。
本發明之另一代表性具體實例提供一種具有導電圖案之樹脂結構，其包括：包括被形成為具有預定表面粗糙度的第一區和表面粗糙度比該第一區小的第二區之聚合物樹脂基材；及選擇地形成於該聚合物樹脂基材的第一區上之導電晶種和金屬層。
根據本發明，即使聚合物樹脂基材本身不含高價的特定無機添加物如具有尖晶石結構的CuCr2O4等，藉由輻射電磁波如雷射等形成導電圖案的區域之表面粗糙度及對金屬層的黏著力也可予以調整，以致於該導電圖案可藉由簡單製程形成於該聚合物樹脂基材上。
因此，形成該導電圖案的製程之製造成本可以被減降，且該聚合物樹脂基材或該特定無機添加物引致的產物
之物性如機械性質和介電常數等或高功率電磁波輻射等可以最小化。除此之外，因為期望的精細導電圖案可被形成於該聚合物樹脂基材上而不使用該特定無機添加物，所以該樹脂本身的顏色可以清楚顯示出來，且易於提供預期顏色的該聚合物樹脂基材或產物顏色。
因此，藉由使用該導電圖案的形成方法，天線、RFID標籤、不同種類的感測器和MEMS結構等的導電圖案均可相當有效地形成於不同種類的樹脂產物如智慧式手機外殼等上。
第1圖係顯示根據本發明的代表性具體實例依照製程順序直接輻射電磁波而形成導電圖案的方法之一實例的示意圖。
第2a圖顯示在實施例1的導電圖案形成方法中，預定區域藉由將雷射輻射於該聚合物樹脂基材而具有表面粗糙度的情況之照片(第一張照片)、顯示在輻射雷射之後藉由無電鍍敷形成銅金屬層的情況之照片(第二張照片)及顯示從沒被雷射輻射的剩下區域移除鍍敷層的情況之照片(第三張照片)。
第2b圖係根據實施例1具有表面粗糙度的雷射輻射區域之光學顯微鏡照片。
第2c圖係顯示在實施例1中形成該金屬層(導電圖案)的掃描式電子顯微鏡(SEM)照片，其中有導電晶種
長成，且該金屬層藉由鍍敷而形成於該導電晶種上。
第3圖係顯示在實施例9的導電圖案形成方法中從沒被雷射輻射的區域選擇性地移除該金屬層等而將該導電圖案形成於該聚合物樹脂基材上的情況之照片。
第4a圖係顯示在實施例6的雷射輻射區中使用光學剖面儀之依高度而定的顏色變化之照片(左側)，及顯示三維結構中的顏色變化之照片(右側)。
第4b圖係顯示在實施例8的雷射輻射區中使用光學剖面儀之依高度而定的顏色變化之照片(左側)，及顯示三維結構中的顏色變化之照片(右側)。
後文中，要來描述根據本發明的特定代表性具體實例藉由電磁波的直接輻射而形成導電圖案的方法及具有其所形成的導電圖案樹脂結構。
根據本發明的代表性具體實例，藉由電磁波的直接輻射而形成導電圖案的方法包括：藉由將該電磁波選擇性地輻射於聚合物樹脂基材上而形成具有預定表面粗糙度的第一區；將導電晶種形成於該聚合物樹脂基材上；藉由鍍敷其上形成具有導電晶種的該聚合物樹脂基材而形成金屬層；及從該聚合物樹脂基材的第二區移除該導電晶種和該金屬層，其中該第二區具有比該第一區小的表面粗糙度。
根據本發明的該代表性具體實例，首先，形成具有某個外形如凹凸、預定圖案或不定形外形的表面結構以便藉
由將電磁波如雷射等輻射於形成導電圖案的第一區上而使該第一區的聚合物樹脂基材具有預定表面粗糙度。在該第一區中，該聚合物樹脂基材表面與藉由鍍敷於該一區所形成的金屬層之間的黏著力由於該預定表面粗糙度而可獲得改善。
另一方面，在沒被電磁波如雷射等輻射的第二區中，可能由於該聚合物樹脂基材本身的原始表面性質而顯示該聚合物樹脂基材表面與該第二區中的金屬層之間的黏著力不足。
相應地，當該第一區的聚合物樹脂基材上形成用於促成鍍敷製程的導電晶種時，與該聚合物樹脂基材具有優良黏著力的金屬層可有利地形成於該第一區上；另一方面，由於黏著力不足而易於移除的金屬層可形成於該第二區上。因此，當弱物理力應用於該聚合物樹脂基材以選擇性地移除該第二區的金屬層及導電晶種時，期望的導電圖案便可輕易地形成於該聚合物樹脂基材上。
如上所述，根據本發明的代表性具體實例，例如，即使聚合物樹脂基材本身不含高價的特定無機添加物如具有尖晶石結構的CuCr2O4等，藉由輻射電磁波如雷射等形成導電圖案的區域之表面粗糙度及黏著力等也可予以調整，以致於該導電圖案可藉由簡單製程形成於該聚合物樹脂基材上。
因此，形成該導電圖案的製程之製造成本可以被減降，且該聚合物樹脂基材或該特定無機添加物引致的產物
之物性如機械性質等可以最小化。除此之外，因為期望的精細導電圖案可被形成於該聚合物樹脂基材上而不使用該特定無機添加物，所以該樹脂本身的顏色可以清楚顯示出來，且易於提供預期顏色的該聚合物樹脂基材或產物顏色。
另一方面，在後文中，針對各製程步驟參照圖式更明確地描述根據本發明的代表性具體實例藉由直接輻射電磁波而形成該導電圖案之方法。第1圖係顯示根據本發明的代表性具體實例依照製程順序直接輻射電磁波而形成導電圖案的方法之一實例的示意圖。
如第1圖的①和②所示，在根據代表性具體實例形成該導電圖案之方法中，先藉由將電磁波選擇性地輻射於該聚合物樹脂基材上而形成具有預定表面粗糙度的第一區。
該聚合物樹脂基材可藉由使用任何熱固性樹脂或任何熱塑性樹脂形成。能形成該聚合物樹脂基材如熱固性樹脂或熱塑性樹脂的聚合物樹脂指定實例可包括ABS樹脂、聚對苯二甲酸烷二酯樹脂(如聚對苯二甲酸丁二酯樹脂或對苯二甲酸乙二酯樹脂等)、聚碳酸酯樹脂、聚丙烯樹脂及聚鄰苯二甲醯胺樹脂等，且除此之外，該聚合物樹脂基材可藉由使用不同聚合物樹脂形成。
除此之外，該聚合物樹脂基材可由可由上述聚合物樹脂形成；但是，需要時，可另含有一般用以形成該聚合物樹脂產物的添加物，例如，UV安定劑、熱安定劑或耐衝擊性補強劑(impact reinforcing agent)。該添加物可依
以該聚合物樹脂基材的總重量為基準，約2重量%或約0.01至2重量的適當量內含。另一方面，該聚合物樹脂基材並不一定包括此技藝中已知且藉由輻射該電磁波而用以形成該導電圖案的具有尖晶石結構的特定無機添加物如CuCr2O4。
另一方面，該第一區藉由將電磁波如雷射等輻射於上述聚合物樹脂基材上而具有預定表面粗糙度，其中在具有該表面粗糙度的第一區中，可形成相對標準化的圖案如孔或網眼花紋等或凹凸形，或可形成其中複合成形的多數不規則孔、圖案或凹凸形的不定形表面結構，且該第一區的聚合物樹脂基材由於不同表面形狀或結構而具有預定表面粗糙度。
至於實例，為了確保形成於該第一區中的金屬層(導電圖案)與該聚合物樹脂基材表面之間的優良黏著力，該聚合物樹脂基材的第一區以中線算術平均粗糙度絕對值(Ra)所界定的表面粗糙度可為500nm或更大，或約1μm或更大，或約1至3μm，且沒被該電磁波輻射到的該第二區以中線算術平均粗糙度絕對值(Ra)所界定的表面粗糙度可能比該第一區小，例如，約400nm或更小，或約100nm或更小，或約0至90nm。
除此之外，上述表面粗糙度也可藉由其他方法來界定。例如，該第一區和第二區的表面粗糙度可依照根據ISO 2409標準方法的橫割試驗藉由對該金屬層的黏著程度。例如，當根據ISO 2409標準方法之間距為2mm或更
小的橫割試驗係藉由使用黏著力為4.0至6.0N/10mm寬的膠帶進行時，該聚合物樹脂基材的第一區可能具有藉由黏著力界定的表面粗糙度(例如ISO 0級或1級)，其中試驗中的該標的金屬層脫層面積相當於該金屬層面積的約5%或更小，且當根據ISO 2409標準方法之間距為2mm或更小的橫割試驗係藉由使用黏著力為4.0至6.0N/10mm寬的膠帶進行時，該聚合物樹脂基材的第二區可具有藉由黏著力界定的表面粗糙度(例如ISO 5級或更高級)，其中試驗中的該標的金屬層脫層面積相當於該金屬層面積的65%或更大。
因為該第一區的聚合物樹脂基材藉由輻射該電磁波如雷射等而具有上述表面粗糙度，所以當依照下述鍍敷製程將該金屬層形成於該第一區上時，該金屬層便可利用優良的黏著力形成且保持於該聚合物樹脂基材上，以形成優良的導電圖案。比起該第一區，因為沒藉由電磁波如雷射等輻射的第二區之聚合物樹脂基材由於其表面性質而具有上述表面粗糙度，所以當該金屬層係依照下述鍍敷製程形成時，該第二區可能具有相當低的黏著力而易於移除。結果，該第二區的金屬層可以輕易且選擇性地移除而將該導電圖案形成於該第一區的聚合物樹脂基材上。
另一方面，電磁波如雷射等可在下述的預定條件下輻射使該第一區的聚合物樹脂基材具有上述表面粗糙度。
首先，在該電磁波的輻射中，可以輻射雷射電磁波，例如，可以輻射波長為248nm、約308nm、約355nm、約
532nm、約585nm、約755nm、約1064nm、約1070nm、約1550nm、約2940nm或約10600nm的雷射電磁波。在另一實例中，可以輻射波長在紅外線(IR)區的雷射電磁波。
除此之外，輻射該雷射電磁波時的特定條件可依據該聚合物樹脂基材的樹脂種類、物性、厚度、該待形成的金屬層的種類或厚度或考慮上述因子的適當黏著力水準做控制或變更。另一方面，該雷射電磁波可以在平均功率為約0.1至50W，或約1至30W，或約5至25W，之輻射條件下輻射，使該第一區的聚合物樹脂基材具有上述預定表面粗糙度。
除此之外，該雷射電磁波的輻射可藉由較高功率輻射一次，但是該雷射電磁波可藉由較低功率輻射二或更多次。當該雷射電磁波的輻射次數增加時，該表面粗糙度提高，形成於該表面上的結構如凹凸形等可能從孔形圖案變成網眼圖案化或不定形表面結構。因此，藉由控制該雷射電磁波的輻射條件及次數，可在該第一區的聚合物樹脂基材上形成適當表面結構，且可提供與該金屬層具有適當程度和優良的黏著力之表面粗糙度。
除此之外，在輻射該雷射電磁波時，電磁波輻射痕跡可能依據輻射該雷射電磁波時的輻射間距而形成於該聚合物樹脂基材的孔形中。然而，為了使該第一區的聚合物樹脂基材具有上述適當表面粗糙度，較佳為可以輻射該雷射電磁波使電磁波輻射痕跡之中間部分的間距或該電磁波的
輻射間距為約20μm或更大或約20至70μm，但是並不特別限於此。結果，該第一區的聚合物樹脂基材可具有適當表面粗糙度及該聚合物樹脂基材與該金屬層之間的適當黏著力。
另一方面，如上所述，等到將該電磁波如雷射等輻射於該第一區之後，可按照第1圖的③所示將導電晶種形成於該該聚合物樹脂基材上。該導電晶種係於鍍敷時長在該聚合物樹脂基材上，且藉由該鍍敷促進該金屬層的形成。因此，更優良的金屬層和該導電圖案可適當地形成於該第一區的聚合物樹脂基材上。
該導電晶種可能含有金屬奈米粒子、金屬離子或金屬錯合物離子。除此之外，該金屬離子或該金屬錯合物離子可以當離子本身、或當該金屬離子所結合的含金屬化合物或當含金屬錯合物的金屬錯合物離子、或甚至當該含金屬化合物或該金屬錯合物的粒子使用。
該導電晶種中包括的金屬原子種類沒有特別限制，只要該金屬原子具有導電性。例如，該導電晶種可包括選自由以下所組成的群組中的至少一種金屬：銅(Cu)、鉑(Pt)、鈀(Pd)、銀(Ag)、金(Au)、鎳(Ni)、鎢(W)、鈦(Ti)、鉻(Cr)、鋁(Al)、鋅(Zn)、錫(Sn)、鉛(Pb)、鎂(Mg)、錳(Mn)和鐵(Fe)、其離子或錯合物離子。
除此之外，為了將該導電晶種形成於該聚合物樹脂基材上，含有上述導電晶種如金屬奈米粒子、該金屬離子或
該金屬錯合物離子的導電晶種、分散液或溶液可應用於該聚合物樹脂基材上，緊接著多種方法如沉澱法、乾燥法及/或還原法，以形成呈粒子形式的導電晶種。更明確地說，當該分散液等含有該金屬奈米粒子時，該金屬奈米粒子係藉由溶解度的差異而沉澱並乾燥而形成呈粒子形式的導電晶種，且當該分散液等含有該金屬離子或該金屬錯合物離子(或含有這些離子的金屬化合物或錯合物；例如，該金屬化合物或該錯合物如AgNO3、Ag2SO4、KAg(CN)2)時，該金屬離子或該金屬錯合物離子係還原且乾燥以適當地形成呈粒子形式的導電晶種。
在此，該金屬離子或該金屬錯合物離子的還原可藉由使用一般還原劑進行，例如，至少一種選自由以下所組成的群組之還原劑：以醇為底質的還原劑、以醛為底質的還原劑、以次磷酸為底質的還原劑如次磷酸鈉或其水合物等、以肼為底質的還原劑如胼或其水合物等、硼氫化鈉及氫化鋰鋁。
除此之外，該分散液或該溶液可適當地包括能改善該聚合物樹脂基材與該導電晶種之間的緊密黏著力之以水為底質的溶液(例如，含有以聚乙烯基吡咯烷酮為底質的聚合物之溶液等)或能將該金屬離子或該金屬錯合物離子安定化之以水為底質的錯合劑(例如，NH3、EDTA或羅謝爾鹽(Rochelle salt)等)當成液相介質。
另外，該導電晶種的分散液或溶液可藉由將液相組合物應用於該該聚合物樹脂基材的一般製程應用，例如，如
浸漬、旋塗及噴佈的多種方法。
按上述形成的導電晶種可形成於包括形成於該第一區上的表面凹凸形、圖案或表面結構之間的空間在內之整個聚合物樹脂基材表面上，且可負責依照該鍍敷製程促進該金屬層的有利形成且控制該金屬層的鍍敷速率或物性。
另一方面，就在上述電磁波輻射之後，立即進行形成該導電晶種的製程；然而，等到以表面張力比該分散液或溶液低的表面活化劑選擇性地表面處理該聚合物樹脂基材之後，可進行形成該導電晶種的製程。除此之外，該聚合物樹脂基材可依照將該表面活化劑加於該分散液或該溶液本身以便形成該導電晶種的情況做表面處理。在此，在添加該表面活化劑之前該表面活化劑可具有比該分散液或溶液低的表面張力。
該表面活化劑可使該導電晶種能更均勻地形成且保持於該聚合物樹脂基材表面上，特別是，介於該凹凸形、圖案或表面結構之間。理由是因為該表面活化劑移除該表面結構之間的空氣以幫助該導電晶種輕易地滲入該表面結構之間。因此，當增加以該表面活化劑做處理時，該導電晶種係有利地完全吸到該第一區上，且該金屬層可藉由該鍍敷製程更均勻地或有利地形成。除此之外，由於利用該表面活化劑做處理及該導電晶種形成，使該金屬層與該第一區上的聚合物樹脂基材之間的黏著力可獲得更進一步改善以有利地形成具有優良導電性的導電圖案。
該表面活化劑的種類可能依據上述導電晶種的分散液
或該溶液種類而有所不同，且可包括表面張力比該分散液或溶液低的任何液相介質。例如，具有較低表面張力的有機溶劑如乙醇等均可用作該表面活化劑。
除此之外，該表面活化劑可藉由將該聚合物樹脂基材沉浸數秒至數分鐘的方法等做處理。
另一方面，參照第1圖的④，等到該導電晶種形成於該聚合物樹脂基材上之後，該金屬層可藉由鍍敷其上形成具有該導電晶種的該聚合物樹脂基材而形成。形成該金屬層的製程可藉由將該導電金屬無電鍍敷於該聚合物樹脂基材上而進行，且進行該無電鍍敷製程的方法及條件可藉由一般方法及條件進行。
例如，該鍍敷製程係藉由使用含有構成該金屬層的導電金屬(例如，金屬源如銅等)、錯合劑、pH調節劑及還原劑等之鍍敷溶液進行以將該金屬層形成於包括該一區和該第二區的聚合物樹脂基材上。在此，該金屬層可形成於上述長出的導電晶種上。
該金屬層可藉由優良的黏著力有利地形成於該第一區上；另一方面，該金屬層由於對該聚合物樹脂基材的黏著力不足而可輕易地從該第二區移除(例如，如第2a圖的第二圖所示，該金屬層可以從該聚合物樹脂基材分層)。
等到形成該金屬層之後，該導電晶種和該金屬層可從該聚合物樹脂基材的第二區選擇性地移除以將該導電圖案形成於剩下的第一區上，如第1圖的⑤和⑥所示。
如上所述，因為該金屬層係依照相當易於移除該金屬
層的狀態形成於該第二區上，所以該金屬層及該導電晶種可藉由簡單方法如將弱物理力施於該聚合物樹脂基材等而從該第二區選擇性地移除。在此，由於介於該金屬層與該第一區上的聚合物樹脂基材之間的優良黏著力，使該金屬層可留下而形成該導電圖案。
如上所述，從該第二區移除該導電晶種和該金屬層的製程，可藉由將弱物理力施於該聚合物樹脂基材的任何方法進行，如超音波輻射(音波處理)、液相清洗、液相沖洗、空氣噴吹、繞絕緣帶(taping)、塗刷(brushing)及利用人力的方法如用手直接除塵或擦拭，或藉由從其中選出的二或更多種方法之組合進行。
例如，清洗或沖洗係於水中在超音波輻射預定時間下進行，且空氣噴吹等係依照使該第二區的導電晶種和金屬層可選擇性地移除之方式進行。
藉由上述方法形成的具有該導電圖案的樹脂結構可包括被分成該第一區及該第二區的該聚合物樹脂基材，該第一區以中線算術平均粗糙度絕對值(Ra)所界定的表面粗糙度為500nm或更大，且該第二區的表面粗糙度比該第一區小；及選擇性地形成於該聚合物樹脂基材的第一區上的該導電晶種和該金屬層。
在此，因為根據代表性具體實例的方法中已經充分描述該第一和第二區的表面粗糙度，所以能省略其附加的描述。除此之外，如上所述，該第一區可表示該電磁波如雷射等輻射的區域。
上述樹脂結構可能是具有供天線用的導電圖案之不同樹脂產物或樹脂層如智慧式手機外殼等，或可能是具有導電圖案如其他RFID標籤、不同種類的感測器或MEMS結構等之不同樹脂產物或樹脂層。
如上所述，根據本發明，即使是該聚合物樹脂本身中沒有高價的特定無機添加物如具有尖晶石結構的CuCr2O4等，也能調整藉由輻射電磁波如雷射等而形成導電圖案的區域之表面粗糙度及對金屬層的黏著力，以致於該導電圖案可藉由簡單方法形成於該聚合物樹脂基材上。
因此，形成該導電圖案的製程之製造成本及原料成本可以減降，且該聚合物樹脂基材或該特定無機添加物引致的產物之物性如機械性質等的衰退可以最小化。除此之外，因為期望的精細導電圖案可被形成於該聚合物樹脂基材上而不使用該特定無機添加物，所以該樹脂本身的顏色可以清楚顯示出來，且易於提供預期顏色的該聚合物樹脂基材或產物顏色。因此，根據本發明的代表性具體實例，精細導電圖案可於較低製造成本且藉由簡單方法形成於不同樹脂產物或樹脂層上，以致於可提供具有不同顏色和外形的樹脂產物，包括以前沒被提過的新樹脂產物。
後文中，本發明的作用及效果係藉由本發明的特定實施例詳細地描述。另一方面，這些實例係藉由實施例提供，且因此，不得視為限制本發明的範疇。
製備含有UV安定劑、熱安定劑及總量小於2重量%的耐衝擊性補強劑而沒有其他不同無機添加物之聚碳酸樹脂基材。波長為1064nm的雷射係於具有21.4W的平均功率之輻射條件下輻射於聚碳酸樹脂基材的預定區上一次。在此，該聚碳酸樹脂的雷射輻射痕跡之中間部分的間距係藉由控制該雷射的輻射間距而控制為約35μm。
相應地，被該雷射輻射的聚碳酸樹脂基材之預定區上具有預定表面粗糙度。第2a圖的第一張照片中顯示如以上製好的聚碳酸樹脂基材之照片，且第2b圖中顯示被雷射輻射形成以便具有該表面粗糙度的區域之光學顯微照片。
接著，將該聚碳酸樹脂基材浸於包括Pd離子的水溶液中約5分鐘，以將包括Pd的導電晶種形成於該基材上。接下來，以去離子水清洗該基材，且藉由使用銅當導電金屬進行無電鍍敷。在無電鍍敷時，使用含有銅源(硫酸銅)、錯合劑(羅謝爾鹽)、pH調節劑(氫氧化鈉水溶液)和還原劑(甲醛)的鍍敷溶液。該無電鍍敷係於室溫進行約1小時以形成該金屬層。
第2a圖的第二張照片中顯示的是顯示上述形成的金屬層之照片。參照第2a圖，可以確定的是該金屬層係有利地形成於該雷射輻射的區域；然而，剩下區域中的金屬層由於黏著力不足變得相當容易移除而以脫層狀態形成。
接著，將該基材浸於該去離子水中，緊接著超音波輻射(音波處理)經過20分鐘，及空氣噴吹，以選擇性地
移除沒被雷射輻射的區域之金屬層。第2a圖的第三張照片係顯示從沒被輻射的區域選擇性地移除該金屬層等以將導電圖案形成於該基材上的情況之照片，且第2c圖係顯示形成該導電圖案的部位之掃描式電子顯微鏡(SEM)照片。參照第2c圖，可確認該導電晶種係長於對應部位，且該金屬層係藉由鍍敷形成於導電薄層(導電金屬粒子)上。
除了實施例1中之該雷射的平均功率輻射條件及該雷射輻射痕跡之中間部分的間距係於一次輻射中更換成約15.7W和約25μm(實施例2)、約15.7W和約35μm(實施例3)、約18.6W和約45μm(實施例4)、約21.4W和約45μm(實施例5)、約21.4W和約55μm(實施例6)、約24.2W和約55μm(實施例7)、約28.5W和約55μm(實施例8)以外，各自具有導電圖案的實施例2至8的樹脂結構係藉由與實施例1的相同方法製造。
除了乙醇和含有Ag錯合物離子而非Pd的水性錯合物離子溶液(含有AgNO3和錯合劑NH3的溶液)係用作形成該導電晶種的溶液以外，具有導電圖案的實施例9的樹脂結構係藉由與實施例1的相同方法製造。第3圖係顯示從沒被雷射輻射的區域選擇性地移除該金屬層等而將該
導電圖案形成於該基材上的情況之照片。
表面粗糙度係於該聚碳酸樹脂基材的預定區域上藉由根據實施例1至9的雷射輻射。面積0.2mm X 0.3mm的中線算術平均粗糙度絕對值(Ra)係藉由使用光學剖面儀(Nano view E1000,Nanosystem,Korea)測量。在第4a圖中，在實施例6的雷射輻射區中使用光學剖面儀顯示依高度而定的顏色變化之照片(左側)，且顯示提供三維結構的顏色變化之照片(右側)。除此之外，第4a圖也顯示測得的表面粗糙度。第4b圖係顯示實施例8的照片且分別顯示依雷射條件變化而定的表面狀態變化及表面粗糙度的變化值。藉由於被實施例1至9的雷射輻射的區域之不同6個點處使用上述方法測量表面粗糙度且平均測量值所獲得之Ra值係彙總且顯示於以下表1中。為了對照，第4a和4b圖顯示於6個點當中的任一點處測到的表面粗糙度，且表1顯示於6個點處測到的值之平均值。
藉由使用根據ISO 2409標準方法之黏著力為4.0至6.0N/10mm寬的膠帶(3M思高膠帶(scotch tape)#371)在其上形成根據實施例1至9的該金屬層及該導電圖案之區域中橫割試驗。在此，介於該基材與該金屬層之間的黏著力或緊密黏著力(close adhesion)係藉由將該金
屬層切割成10X10圖形(約2mm或更小的間距)，且測量由於貼上和撕下該膠帶而脫層的金屬層面積而測試。
該導電圖案的脫層面積之黏著力評估係依據以下ISO等級標準的規定進行。
1. 0級：當該導電圖案的脫層面積相當於評估中的標的導電圖案面積的0%的時候。
2. 1級：當該導電圖案的脫層面積相當於評估中的標的導電圖案面積的0%至5%或更小的時候。
3. 2級：當該導電圖案的脫層面積相當於評估中的標的導電圖案面積的5%至15%或更小的時候。
4. 3級：當該導電圖案的脫層面積相當於評估中的標的導電圖案面積的15%至35%或更小的時候。
5. 4級：當該導電圖案的脫層面積相當於評估中的標的導電圖案面積的35%至65%或更小的時候。
6. 5級：當該導電圖案的脫層面積相當於評估中的標的導電圖案面積的65%以上的時候。
除此之外，依照實施例1至9形成該導電圖案之後的金屬層(導電圖案)的均勻度係依據以下標準的規定評估。
1. O：用肉眼，具有由雷射輻射形成的表面粗糙度之所有區域中形成上色均勻的金屬層(鍍敷薄膜)，且當藉由光學顯微鏡觀察該金屬層表面時，沒顯示細孔。
2. △：用肉眼，具有由雷射輻射形成的表面粗糙度之所有區域中形成上色均勻的金屬層(鍍敷薄膜)；然
而，當藉由光學顯微鏡觀察該金屬層表面時，部分顯示細孔。
3. X：用肉眼，並非具有由雷射輻射形成的表面粗糙度之所有區域中均形成上色均勻的金屬層(鍍敷薄膜)；且當藉由光學顯微鏡觀察該金屬層表面時，至少部分顯示細孔。
將評估結果顯示於以下表1。
參照表1，可確認在實施例1至9中，透過包括在被雷射輻射的區域中形成約500nm或更大的表面粗糙度(Ra)以改善該聚合物樹脂基材與該金屬層之間的黏著力之製程及形成該導電晶種等之製程的方法，可在被雷射輻射的區域選擇性地形成相當優良的金屬層(導電圖案)。特別是，可確認該導電圖案具有優良均勻性及對該聚合物
樹脂基材的優良黏著力，而能有利地形成。
總之，根據以上實施例，即使是該聚合物樹脂基材本身不含高價特定無機添加物如CuCr2O4等，也可調整藉由雷射電磁波如雷射等而形成導電圖案的區域之表面粗糙度及對金屬層的黏著力，以致於該導電圖案可藉由簡單方法形成於該聚合物樹脂基材上。
Claims (19)
- 一種藉由電磁波的直接輻射而形成導電圖案之方法，該方法包含：藉由將該電磁波選擇性地輻射於含有熱固性樹脂或熱塑性樹脂之聚合物樹脂基材上而形成具有預定表面粗糙度的第一區；將導電晶種形成於該聚合物樹脂基材上；藉由鍍敷其上形成具有導電晶種的該聚合物樹脂基材而形成金屬層；及從該聚合物樹脂基材的第二區移除該導電晶種和該金屬層，其中該第二區具有比該第一區小的表面粗糙度，其中該聚合物樹脂基材的第一區以中線算術平均粗糙度絕對值(Ra)所界定的表面粗糙度為500nm至3μm，且該第二區的中線算術平均粗糙度絕對值(Ra)比該第一區小。
- 如申請專利範圍第1項之方法，其中當藉由使用黏著力為4.0至6.0N/10mm寬的膠帶進行根據ISO 2409標準方法之間距為2mm或更小的橫割試驗時，該聚合物樹脂基材的第一區之表面粗糙度係藉由試驗中的標的金屬層脫層面積相當於該金屬層面積的5%或更小時之黏著力界定。
- 如申請專利範圍第1項之方法，其中當藉由使用黏著力為4.0至6.0N/10mm寬的膠帶進行根據ISO 2409標準方法之間距為2mm或更小的橫割試驗時，該聚合物樹脂基材的第二區之表面粗糙度係藉由試驗中的標的金屬 層脫層面積相當於該金屬層面積的65%或更大時之黏著力界定。
- 如申請專利範圍第1項之方法，其中該聚合物樹脂基材含有選自由ABS樹脂、聚對苯二甲酸烷二酯樹脂、聚碳酸酯樹脂、聚丙烯樹脂及聚鄰苯二甲醯胺樹脂所組成的群組中之至少一種。
- 如申請專利範圍第1項之方法，其中該電磁波的輻射係藉由輻射出波長為248nm、308nm、355nm、532nm、585nm、755nm、1064nm、1070nm、1550nm、2940nm或10600nm的雷射電磁波而進行。
- 如申請專利範圍第1項之方法，其中該電磁波的輻射係藉由在具有0.1至50W的平均功率之輻射條件下輻射出雷射電磁波而進行。
- 如申請專利範圍第1項之方法，其中該電磁波的輻射係藉由輻射出雷射電磁波使該聚合物樹脂基材上所示的電磁波輻射痕跡之中間部分的間距為20至70μm而進行。
- 如申請專利範圍第1項之方法，其中該電磁波的輻射係藉由輻射出雷射電磁波一次或藉由輻射出該雷射電磁波兩次或更多次而進行。
- 如申請專利範圍第1項之方法，其中該導電晶種含有金屬奈米粒子、金屬離子或金屬錯合物離子。
- 如申請專利範圍第9項之方法，其中該導電晶種含有選自由以下所組成的群組中的至少一種金屬：銅 (Cu)、鉑(Pt)、鈀(Pd)、銀(Ag)、金(Au)、鎳(Ni)、鎢(W)、鈦(Ti)、鉻(Cr)、鋁(Al)、鋅(Zn)、錫(Sn)、鉛(Pb)、鎂(Mg)、錳(Mn)和鐵(Fe)、其離子或錯合物離子。
- 如申請專利範圍第9項之方法，其中該導電晶種的形成包括：將含有該金屬奈米粒子、金屬離子或金屬合錯合物離子的分散液或溶液施塗於該聚合物樹脂基材上；及使該金屬奈米粒子沉澱並乾燥或將該金屬離子或金屬錯合物離子還原並乾燥而形成呈粒子形式的導電晶種。
- 如申請專利範圍第11項之方法，其中該金屬離子或金屬錯合物離子的還原係在至少一種選自由以下所組成的群組之還原劑存在下進行：以醇為底質的還原劑、以醛為底質的還原劑、以次磷酸鹽為底質的還原劑、以肼為底質的還原劑、硼氫化鈉及氫化鋰鋁。
- 如申請專利範圍第11項之方法，其另外包含：在形成該導電晶種時添加表面張力比該分散液或溶液低的表面活化劑，或在該電磁波輻射和該導電晶種形成之間以表面張力比該分散液或溶液低的表面活化劑進行該聚合物樹脂基材的表面處理。
- 如申請專利範圍第1項之方法，其中該金屬層的形成包括將導電金屬電鍍於該聚合物樹脂基材上。
- 如申請專利範圍第1項之方法，其中從該第二區 移除該導電晶種和該金屬層包括藉由組合選自由以下所組成的群組中之一或二或更多種方法將物理力(physical power)應用於該聚合物樹脂基材上：超音波輻射(音波處理)、液相清洗、液相沖洗、空氣噴吹、繞絕緣帶(taping)、塗刷(brushing)及利用人力的方法。
- 一種具有導電圖案之樹脂結構，其包含：包括被形成為具有預定表面粗糙度的第一區和表面粗糙度比該第一區小的第二區之聚合物樹脂基材；及選擇地形成於該聚合物樹脂基材的第一區上之導電晶種和金屬層，其中該聚合物樹脂基材的第一區以中線算術平均粗糙度絕對值(Ra)所界定的表面粗糙度為500nm至3μm，且該第二區的中線算術平均粗糙度絕對值(Ra)比該第一區小，及其中該聚合物樹脂基材含有熱固性樹脂或熱塑性樹脂。
- 如申請專利範圍第16項之樹脂結構，其中該第一區相當於該電磁波所輻射的區域。
- 如申請專利範圍第16項之樹脂結構，其中當藉由使用黏著力為4.0至6.0N/10mm寬的膠帶進行根據ISO 2409標準方法之間距為2mm或更小的橫割試驗時，該聚合物樹脂基材的第一區之表面粗糙度係藉由試驗中的標的金屬層脫層面積相當於該金屬層面積的5%或更小時之黏著力界定。
- 如申請專利範圍第16項之樹脂結構，其中當藉 由使用黏著力為4.0至6.0N/10mm寬的膠帶進行根據ISO 2409標準方法之間距為2mm或更小的橫割試驗時，該聚合物樹脂基材的第二區之表面粗糙度係藉由試驗中的標的金屬層脫層面積相當於該金屬層面積的65%或更大時之黏著力界定。
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| TW103127269A TWI563889B (en) | 2013-08-09 | 2014-08-08 | Method for forming conductive pattern by direct radiation of electromagnetic wave, and resin structure having conductive pattern there |
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| US10103056B2 (en) * | 2017-03-08 | 2018-10-16 | Lam Research Corporation | Methods for wet metal seed deposition for bottom up gapfill of features |
| US10892671B2 (en) * | 2017-07-25 | 2021-01-12 | GM Global Technology Operations LLC | Electrically conductive copper components and joining processes therefor |
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