TWI434637B - Surface treatment of copper foil - Google Patents
Surface treatment of copper foil Download PDFInfo
- Publication number
- TWI434637B TWI434637B TW098121954A TW98121954A TWI434637B TW I434637 B TWI434637 B TW I434637B TW 098121954 A TW098121954 A TW 098121954A TW 98121954 A TW98121954 A TW 98121954A TW I434637 B TWI434637 B TW I434637B
- Authority
- TW
- Taiwan
- Prior art keywords
- copper foil
- treated
- layer
- component
- copper
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 174
- 239000011889 copper foil Substances 0.000 title claims description 153
- 238000004381 surface treatment Methods 0.000 title description 7
- 229910052751 metal Inorganic materials 0.000 claims description 51
- 239000002184 metal Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 44
- 238000011282 treatment Methods 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 31
- 230000008018 melting Effects 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 238000005240 physical vapour deposition Methods 0.000 claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 230000003746 surface roughness Effects 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 30
- 238000004544 sputter deposition Methods 0.000 description 23
- 239000002335 surface treatment layer Substances 0.000 description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 17
- 239000011651 chromium Substances 0.000 description 15
- 229910052804 chromium Inorganic materials 0.000 description 14
- 239000011888 foil Substances 0.000 description 12
- 238000005530 etching Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007788 roughening Methods 0.000 description 6
- 239000002318 adhesion promoter Substances 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- -1 argon ion Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 239000000383 hazardous chemical Substances 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 241001422033 Thestylus Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/75—Printability
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0179—Thin film deposited insulating layer, e.g. inorganic layer for printed capacitor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0302—Properties and characteristics in general
- H05K2201/0317—Thin film conductor layer; Thin film passive component
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/032—Materials
- H05K2201/0323—Carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12431—Foil or filament smaller than 6 mils
- Y10T428/12438—Composite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12625—Free carbon containing component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12681—Ga-, In-, Tl- or Group VA metal-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
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Description
本發明是關於表面處理層。特別是關於將乾式薄膜形成法用於表面處理銅箔的表面處理層的形成所得到之用於製造印刷電路板的表面處理銅箔。
從前以來,從鋪銅層板加工到印刷電路板的製程,一直多為採用使用溶液的蝕刻製程。因此,一直要求在鋪銅層板的階段之銅箔對於絕緣樹脂基板的密接性、加工成印刷電路板以後的電路與絕緣樹脂基板的密接性均要良好。
為了滿足這樣的要求,一直以來是對用於製造印刷電路板的銅箔的黏著面施以種種的表面處理,以提升其與絕緣樹脂基材的密接性。而作為習知用於印刷電路板的銅箔的防鏽元素、表面改質元素的鉻成分,一直以來是廣泛使用鍍鉻或鉻酸鹽處理等。特別是鉻酸鹽處理,近年來市場上的銅箔幾乎都是使用鉻酸鹽處理。
若以鉻酸鹽作為表面處理成分者為例,例如專利文獻1(日本專利早期公開號:特開2000-340911號公報)中,揭露了與基材的密接性(基材與銅箔的黏著強度)、耐溼性、耐藥品性、耐熱性優異的用於印刷電路板的銅箔,其具有以蒸鍍法在銅箔的單面或雙面形成的金屬鉻層,例如為藉由濺鍍法而蒸鍍形成的金屬鉻層;還揭露一種用於印刷電路板的銅箔,其中銅箔的單面是經由剝離層而載置於承載箔上,而具有以蒸鍍法在此銅箔的相反面形成的金屬鉻層,例如為藉由濺鍍法而蒸鍍形成的金屬鉻層。
另外,專利文獻2(日本專利早期公開號:特開2001-177204號公報)中,揭露了一種用於印刷電路板的表面處理銅箔,其作為發揮矽烷偶合劑性能的最大限度的銅箔,其中矽烷偶合劑的使用是以增加銅箔與用於製造印刷電路板的銅箔的基材的黏著密度為目的,此用於印刷電路板的表面處理銅箔是藉由以下步驟而完成:防鏽處理,在銅箔表面形成鋅或氧化鋅合金層;在此鋅或氧化鋅合金層的表面形成電解鉻酸鹽層;以及在此電解鉻酸鹽層未乾燥的情況下,在此電解鉻酸鹽之上形成矽烷偶合劑吸附層,再使其乾燥。
如上作為表面處理成分的鉻成分,在以鉻化合物的形式存在的情況,其氧化價數為三價或六價。而其中以六價鉻對於生物的毒性極高,另外六價鉻化合物在土壤中的移動性也較大,而為環境負荷高的物質。
關於含有如鉻一般會對人體造成影響的有害物質的廢棄物,其跨國境移動,是從1970年代開始在全世界發生。其結果,將來自先進國家的有害廢棄物放置於開發中國家而產生環境污染等的問題是一直發生。因此,在1980年代,規定了關於一定的廢棄物之跨國境移動等的管制之國際性的規範及手續的「巴塞爾公約-管制有害廢棄物跨國境移動及處理公約」(Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and Their Disposl)已完成制訂,日本也在1993年生效。
近年來,EU(歐盟)的ELV指令中,已通過關於在EU市場註冊的新車,禁止鉛、六價鉻、水銀、鎘之環境負荷物質在2003年07月01日以後使用,並提倡三價鉻的積極使用。另外,在電氣‧電子業界中,則受到歐洲的WEEE(Waste Electrical and Electronic Equipment)指令與RoHS(Restriction on Hazardous Substances)指令的最終合意,對於作為廢電氣電子機器中所使用的特定有害物質之六價鉻(Cr6+
)等的六種物質,其為即使回收仍殘留環境風險的物質而管制其使用。而印刷電路板,也是受到管制的對象物品。
還有,由於近年來對環境問題的意識高漲,即使使用三價鉻,若廢棄物處理發生錯誤就會轉化成六價鉻,若分析手法錯誤則會有判斷為六價鉻之虞。考慮到以上情形,開始研究不使用鉻成分本身的用於印刷電路板的銅箔的使用。
例如專利文獻3(日本專利早期公開號:特平7-170064號公報)中,揭露了含有不使用鉻的銅箔的概念來作為金屬箔,此金屬箔的特徵是:(1)在至少一面具有黏著性促進劑的金屬箔,上述黏著性促進劑是含有至少一個矽烷偶合劑、而不存在鉻;(2)不增加在上述黏著性促進劑的下方所形成的上述金屬箔的基底表面的表面粗糙度、或是並無鋅層或鉻層附著於上述基底表面。其揭露的金屬箔中,在上述金屬箔的上述一面與上述黏著性促進劑之間設置一金屬層,此金屬層的金屬是由選自銦、錫、鎳、鈷、黃銅、或二個以上的這些金屬的混合物所組成之族群所構成;或者是,在上述金屬箔的上述一面與上述黏著性促進劑之間設置一金屬層,此金屬層的金屬是由選自錫、鉻-鋅混合物、鎳、鉬、鋁、以及二個以上的這些金屬的混合物所組成之族群所構成。
一般而言,防鏽處理層是保護銅箔而避免在大氣氧化,而用於確保長期保存性。然而此防鏽處理層的有些種類與基材樹脂的密接性會發生變化,特別是對加工成印刷電路板以後的電路的剝離強度、此剝離強度的耐藥品性裂化率、耐吸濕劣化率等會造成很大影響。
綜上所述,業界所希望的表面處理銅箔是在電解銅箔的表面處理層不使用鉻,並滿足加工成印刷電路板以後的電路的剝離強度、此剝離強度的耐藥品性裂化率、耐吸濕劣化率等的基本要件。
因此,本案諸位發明人的精心研究的成果得到了以下結論:藉由使用以下所述之無鉻的表面處理銅箔,可以得到其與絕緣樹脂基材的良好的密接性。以下,針對本發明相關之表面處理銅箔來作說明。
本發明相關之表面處理銅箔,其是在與絕緣樹脂基材鋪設而製造鋪銅層積板之時所使用的銅箔的鋪設面,設置一表面處理層而成的表面處理銅箔,其特徵在於:上述表面處理銅箔具有上述表面處理層,上述表面處理層是以乾式薄膜形成法使熔點1400℃以上的高熔點金屬成分、還有碳成分附著於已施以潔淨化處理的上述銅箔的鋪設面而形成。
本發明相關之表面處理銅箔的構成設置到上述銅箔的鋪設面的上述表面處理層之熔點1400℃以上的高熔點金屬成分,較好為使用物理蒸鍍法附著1nm~10nm的換算厚度量。
本發明相關之表面處理銅箔的構成設置到該銅箔的鋪設面的上述表面處理層之碳成分,較好為使用物理蒸鍍法附著1nm~5nm的換算厚度量。
本發明相關之表面處理銅箔,是較好為使用為鈦成分來作為熔點1400℃以上的高熔點金屬成分。
本發明相關之表面處理銅箔所使用的銅箔,其鋪設面較好為使用未施以粗化處理且表面粗糙度(Rzjis)為2.0μm以下者。
對本發明相關之表面處理銅箔所施行的潔淨化處理,較好為除去銅箔表面的銅氧化物的處理。
對本發明相關之表面處理銅箔所施行的潔淨化處理,較好為使用乾式薄膜形成法在銅箔表面形成一銅層。
【發明效果】
本發明相關之表面處理銅箔,是在作為相對於絕緣樹脂基材的鋪設面之銅箔的鋪設面施以潔淨化處理,再依序附著熔點1400℃以上的高熔點金屬成分、碳成分之各成分所完成者。而在進行熔點1400℃以上的高熔點金屬成分、碳成分之各成分的附著之時,積極地使用乾式薄膜形成法(包含物理蒸鍍法)。若使用乾式薄膜形成法,與使用電化學性的手法的情況不同,可以形成在同一平面內的膜厚均一性優異、無組成變異的表面處理層。因此,關於表面處理層的形成,不使用從以前就一直使用的電化學性手法,而是積極地使用乾式薄膜形成法,則可以形成與習知電解銅箔的表面處理全然不同的表面處理層。藉由使用本發明相關之表面處理銅箔,即使未得到對銅箔的鋪設面施以粗化處理之對絕緣樹脂基材的固著效應(anchor effect),關於加工為鋪銅層基板時的銅箔的密接性、及加工為印刷電路板時的電路的密接性,仍可達成實用上無障礙的剝離強度。
還有,本發明相關之表面處理銅箔,是在作為相對於絕緣樹脂基材的鋪設面之銅箔的鋪設面施以潔淨化處理,然後依序附著熔點1400℃以上的高熔點金屬成分、碳成分之各成分。藉此,可飛躍性地提昇銅箔表面與熔點1400℃以上的高熔點金屬成分及碳成分的密接性。
【用以實施發明的最佳形態】
以下,針對本發明相關之表面處理銅箔的形態來作說明。
本發明相關之表面處理銅箔的形態:本發明相關之表面處理銅箔,其是在與絕緣樹脂基材鋪設而製造鋪銅層積板之時所使用的銅箔的鋪設面,設置一表面處理層而成的表面處理銅箔。因此有必要在至少銅箔的鋪設面具有表面處理層,但是為了確保身為表面處理銅箔的長期保存性,亦可再其相反面設置用於達成防鏽效果的表面處理層。關於此時設置於相反面的表面處理層,亦可設置與鋪設面相同的表面處理層。然而,若是對於此相反面的表面處理只需要防鏽效果,考慮的成本,可以使用含鋅的無機防鏽、使用苯并三唑(benzotriazole)或咪唑(imidazole)等的有機防鏽等。
而本發明相關之表面處理銅箔,是使用尚未具備表面處理層的未處理銅箔而完成者。在此處所稱的銅箔,是不論其製造方法,可使用任何的電解銅箔、軋延銅箔。另外,關於此時的銅箔厚度,並無特別的限定,可因應用途而使用任意厚度的銅箔。一般而言,是使用6μm~300μm的範圍的厚度的銅箔。而關於厚度不滿6μm的銅箔,可形成經由接合介面而暫時性地鋪設承載箔與極薄銅箔的狀態,而較好為使用受到承載箔支持的狀態之極薄銅箔(附有承載箔的銅箔)。
針對以上所述之設置於銅箔之與絕緣樹脂基材的鋪設面的表面處理層來作說明。本發明相關之表面處理銅箔的情況,在形成表面處理層之前,是對形成的銅箔的鋪設面施以潔淨化處理。進行此一潔淨化處理的目的,是使銅箔表面接近於形成盡可能無銅氧化物的狀態而曝露金屬銅的狀態。也就是,因為形成於銅箔表面的氧化層、污染等,而會降低銅箔與表面處理層的密接性,但是藉由此潔淨化處理的進行,而成為在銅箔表面無多餘的銅氧化物的狀態,而防止密接性的降低。而潔淨化處理,只要至少在銅箔與絕緣樹脂基材的鋪設面這一側、也就是在形成表面處理層的這一側進行即可,亦可以在作為基材的銅箔的雙面都施以潔淨化處理。
關於潔淨化處理,藉由使用除去銅氧化物的方法、使用乾式薄膜形成法而使新鮮的銅附著於銅箔表面的方法的任一個,可以得到盡可能接近金屬銅曝露表面之銅箔表面。
針對從身為基材的銅箔除去銅氧化物的潔淨化處理來作說明。關於此情況的潔淨化處理方法,例如為濺擊(sputtering)處理、電漿處理等。使用濺擊處理的情況,是在真空反應室中,以離子槍等加速氬離子、氮離子等,使其撞擊銅箔表面,而將位於銅箔表面的銅氧化物離子化而帶離銅箔表面,藉此主要除去銅氧化物而盡量使金屬銅曝露於銅箔表面,而進行銅箔表面的清淨化。此時並用濺擊處理及電子射叢(electron shower),可進行良好的潔淨化。另外,使用電漿處理的情況,是使用電容耦合電漿源而使銅箔表面的銅氧化物瞬間昇華,藉此除去銅箔表面的銅氧化物,進行銅箔表面的清淨化。
接下來,針對對銅箔表面使用乾式薄膜形成法來得到曝露金屬銅的狀態之潔淨化處理來作說明。在此情況之潔淨化處理方法所使用的乾式薄膜形成法,是在被稱為所謂的物理蒸鍍法之濺鍍法、真空蒸鍍法、電子束蒸鍍法等之外,還包含化學氣相沈積法等的氣相反應法。若舉出一例,在使用濺鍍法的情況,是使用銅靶材,在真空反應室內使銅原子落在銅箔表面,而成為曝露新鮮的金屬銅的狀態。此一來,在使用物理蒸鍍法而在身為基材的銅箔表面進行清淨化處理的情況中,形成於銅箔表面的銅膜的厚度,若欲減少變異,則銅膜的厚度較好為10nm以上。
若銅箔的鋪設面的潔淨化處理終了,之後則進行表面處理層的形成。首先,使熔點1400℃以上的高熔點金屬成分附著於銅箔的鋪設面。其原因在於若在銅箔表面不附著此高熔點金屬成分而僅附著後文所述的碳成分,就容易發生表面處理銅箔與絕緣樹脂基材的密接狀態的變異,特別是會隨著鋪銅層積板的同一平面內的測定位置的不同而會有很大的變異,故不建議。而此處所稱之熔點1400℃以上的高熔點金屬成分,較好為使用任何的鈦、鎳、鈷、鋯、鉭。然而,考慮到印刷電路板的製程,一併考慮以蝕刻除去等的種種條件,更好為使用鈦。此時的熔點1400℃以上的高熔點金屬成分,較好為使用乾式薄膜形成法來使其形成薄膜並附著。其中若考慮到薄膜形成效率,較好為使用濺鍍法、真空蒸鍍、電子束蒸鍍法等物理蒸鍍法。還有,考慮到薄膜形成效率、薄膜形成厚度穩定性、步驟上控制的容易度等種種的控制要因,若考慮到這些方法的控制容易度,最好是使用濺鍍法。
而熔點1400℃以上的高熔點金屬成分(以下簡稱為「高熔點金屬成分」),較好是附著1nm~10nm的換算厚度量。高熔點金屬成分附著量不滿1nm的情況中,則得不到使高熔點金屬成分附著的效果,而得不到表面處理銅箔與絕緣樹脂基材的良好的密接性。另一方面,高熔點金屬成分量超過10nm的情況中,由於高熔點金屬成分附著量變得過多,而使加工成印刷電路板時難以藉由蝕刻液等將其溶解除去,則會使蝕刻時間變長,而難以形成具有良好的蝕刻因子(etching factor)的微細間距電路。而此處所稱的換算厚度,是將表面處理銅箔溶解於化學藥品再以ICP裝置等進行所得到的值,再以此值作換算所得到的厚度。如上所述,使高熔點金屬成分附著於銅箔表面。
之後,使碳成分附著於此高熔點金屬成分的表面。如此一來,藉由與高熔點金屬成分一併附著碳成分,使表面處理銅箔與絕緣樹脂層的密接性變得良好,並使其穩定化。而此一碳成分的附著,較好為使用物理蒸鍍法來進行。關於此時的手法雖無特別限定,但是在使用濺鍍法的情況中,使氬離子等撞擊碳靶材,而使碳成分落在銅箔的表面。
此時的碳成分,較好是附著1nm~5nm的換算厚度量。在碳成分附著量不滿1nm的情況中,會得不到使碳附著的效果,而成為僅附著高熔點金屬成分的狀態,而得不到表面處理銅箔與絕緣樹脂基材的良好的密接性。另一方面,在碳成份量超過5nm的情況中,碳成分附著量變得過多,而在加工成印刷電路板的情況中,由於使銅箔電路的下表面的導體電阻上升的碳成分變多,故不建議。而碳成分的換算厚度的測定方法,是將本發明相關之表面處理銅箔的試片置於氣體分析裝置的高溫氧氣流中,使此氣流中的氧與碳成分反應,而轉換為一氧化碳及二氧化碳氣體,再測定此一氧化碳及二氧化碳氣體量,求出每單位面積的碳成份量,再換算為每單位面積的厚度。
以上所敘述的表面處理層,可適用於不進行粗化處理而鋪設於絕緣樹脂基板的用途的表面處理銅箔。一般的銅箔,是在進行粗化處理之前,在表面施以粗化處理。在銅箔的鋪設面若存在凹凸形狀的粗化處理,此粗化處理的凹凸藉由衝壓加工,則發揮嵌入絕緣樹脂基材內部的固著效應,而提升密接性。然而若存在這樣的粗化處理,即使進行蝕刻加工而完成表面處理銅箔的主要部分的溶解,但無法除去嵌入絕緣樹脂基材的內部的粗化處理部,因此必須有更多的蝕刻時間(過蝕刻時間)。此過蝕刻時間愈長,已完成蝕刻的銅箔電路也會進行溶解,因此銅箔電路的蝕刻因子會劣化。相對於此,在本發明相關之表面處理銅箔中,即使在表面處理銅箔的製造使用為處理的銅箔,仍可以得到其與絕緣樹脂層的良好密接性。而上述未處理的銅箔的表面粗糙度(Rzjis)若為2.0μm以下,可飛躍式地縮短蝕刻加工時的過蝕刻時間,而可以容易提升所形成的銅箔電路的蝕刻因子。在此處,所顯示的表面粗糙度是未處理的銅箔的鋪設面的值,但是即使形成了本發明所稱的表面處理層,只要是以觸針式的粗度計來作測定,表面處理前後的表面粗糙度的值並無多大變化。
接下來,說明本發明相關之表面處理銅箔的製造方法。上述的表面處理銅箔的製造,是包含以下的步驟A及步驟B。以下,敘述每個步驟。
步驟A:在此步驟中,是進行銅箔表面的潔淨化處理。在此處所稱的潔淨化處理,就是在形成表面處理層之身為基材的銅箔的表面使金屬銅暴露的處理。關於潔淨化處理,因為已經敘述過了,故省略其說明。
步驟B:以乾式薄膜形成法在已潔淨化的銅箔形成由熔點1400℃以上的高熔點金屬成分與碳層所構成的表面處理層,以其作為表面處理銅箔。
而在此熔點1400℃以上的高熔點金屬成分的被膜的形成,使用屬於乾式薄膜形成法的物理蒸鍍法的情況,也是較好為使用濺鍍法。此濺鍍的條件並無特別限定,可以採用以下條件等等:使用鈦靶材、鎳靶材等、目標真空度Pu為1×10-3
Pa以下、濺鍍壓PAr為0.1Pa~3.0Pa、濺鍍電力密度0.1W/cm2
~3W/cm2
之下進行5秒~20秒之間、以氬離子撞擊靶材。
還有,關於之後進行的碳的物理蒸鍍法,並無限定特定的製造方法,可使用所有一般習知的物理蒸鍍法。
以下,為了可以更容易地理解本發明,敘述實施例及比較例。
【實施例】
關於實施例,製作將鈦成分及碳成分的附著量調整為表1所示的換算厚度之實施例1~實施例5的表面處理銅箔。之後,成為塗佈聚醚磺(polyethersulfone)樹脂的附有樹脂的銅箔,在與FR-4基材鋪設之後,進行其與此FR-4基材的密接性評量。
潔淨化處理:關於潔淨化處理,是顯示使用濺鍍法來得到在銅箔表面暴露金屬銅的狀態之實施例。首先,準備鋪設面的表面粗糙度Rzjis=1.3μm之厚度18μm的電解銅箔捲。使用水冷式DC磁控濺鍍裝置作為濺鍍裝置。使用尺寸為150mm×300mm的銅靶材,採用的濺鍍條件是目標真空度Pu為不滿1×10-4
Pa、濺鍍壓PAr為0.1Pa、濺鍍電力1500W之下進行10秒的處理之條件,藉此進行厚度50nm的銅成分的附著。
鈦成分的附著:將鈦成分附著至銅箔的鋪設面,是在水冷式DC磁控濺鍍裝置,使用尺寸為150mm×300mm的鈦靶材,採用的濺鍍條件是目標真空度Pu為1×10-3
Pa以下、濺鍍壓PAr為0.1Pa~1Pa、濺鍍電力100W~1000W之下進行10秒的處理之條件,藉此進行鈦成分的附著。
碳成分的附著:接下來,在已完成鈦成分的附著之銅箔的鋪設面進行碳成分的附著。在與鈦成分的附著相同的水冷式DC磁控濺鍍裝置,使用尺寸為150mm×300mm的碳靶材,採用的濺鍍條件是目標真空度Pu為不滿1×10-4
Pa、濺鍍壓PAr為0.1Pa~1Pa、濺鍍電力500W~3000W之條件,而進行碳成分的附著。
鈦成分及碳成分的附著,其附著量是藉由調整電力密度來達成表1的實施例1~實施例5所示的換算厚度,來進行附著。
對於經由以上步驟所得到的實施例1~實施例5的表面處理銅箔,塗佈由70重量份的聚醚磺樹脂(住友化學股份有限公司製的Sumikaexcel PES-5003P)、30重量份的環氧樹脂(日本化藥股份有限公司製的EPPN-502)所構成樹脂,風乾後,在140℃的加熱氣氛進行乾燥處理,而成為已塗佈半硬化狀態的厚度2μm的樹脂之附有樹脂的銅箔。
密接性評量:對於使用實施例1~實施例5的表面處理銅箔的附有樹脂的銅箔,與FR-4等級的預浸布(prepreg)進行180℃×60分鐘的熱壓合加工,來製造鋪銅層積板。然後,以蝕刻法製作具有0.4mm的寬度之用於測定剝離強度的直線電路的印刷電路板試片,進行其剝離強度的評量。剝離強度是針對常態、軟銲後、鹽酸浸漬後及壓力鍋試驗(pressure cooker test,以下稱「PCT」)後分別進行測定。關於其評量結果,整合於後文的圖1中。
軟銲後的剝離強度,使印刷電路板試片在260℃的軟銲料浴中漂浮10分鐘後,冷卻至室溫所測定的剝離強度。
鹽酸浸漬後的剝離強度,是將印刷電路板試片浸漬於以鹽酸:水=1:2的比例混合之60℃的溶液中,浸漬90分鐘之後,經水洗、乾燥後,直接測定的剝離強度。藉由鹽酸浸漬後的剝離強度的測定,可以評量電路的耐鹽酸性。
PCT是印刷電路板的層間連接可靠度的試驗的一種。PCT後的剝離強度,是將印刷電路板試片維持在121℃×100%RH的高溫高壓氣氛中24小時後,所測定的剝離強度。也就是,藉由測定PCT之後的剝離強度,可以評量電路的耐溼性。
【比較例】
關於比較例,是顯示身為高熔點金屬成分的鈦成分的附著量為超出本發明的範圍之0.4nm的表面處理銅箔。若見到表1則瞭解到,實施例1~實施例5的表面處理銅箔的任一個的剝離強度值,均大於比較例1的表面處理銅箔的值。
本發明相關之表面處理銅箔,是在作為相對於絕緣樹脂基材的鋪設面之銅箔的鋪設面施以潔淨化處理,再主要使用物理蒸鍍法而依序附著熔點1400℃以上的高熔點金屬成分與碳成分之各成分所完成者。藉由採用此構成,與使用電化學性的手法來形成表面處理層的情況不同,可以形成在同一平面內的膜厚均一性優異、無組成變異的表面處理層。其結果,縮小了加工為鋪銅層積板時的銅箔與絕緣樹脂層之密接性的因測定處所的變異。再加上本發明相關之表面處理銅箔,可具有適用於將未粗化的銅箔鋪設於絕緣樹脂基材而維持良好的密接性之表面處理層。
雖然本發明已以較佳實施例揭露如上,然其並非用以限定本發明,任何本發明所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (6)
- 一種表面處理銅箔,其是在與絕緣樹脂基材鋪設而製造鋪銅層積板之時所使用的銅箔的鋪設面,設置一表面處理層而成的表面處理銅箔,其特徵在於:該表面處理銅箔具有該表面處理層,該表面處理層是在已施以潔淨化處理的該銅箔的鋪設面使用物理蒸鍍法將熔點1400℃以上的高熔點金屬成分以1nm~10nm的換算厚度量附著、還有將碳成分附著而形成。
- 如申請專利範圍第1項所述之表面處理銅箔,其中構成設置到該銅箔的鋪設面的該表面處理層之碳成分,是使用物理蒸鍍法附著1nm~5nm的換算厚度量。
- 如申請專利範圍第1項所述之表面處理銅箔,其中該熔點1400℃以上的高熔點金屬成分為鈦成分。
- 如申請專利範圍第1項所述之表面處理銅箔,其中該銅箔的該鋪設面,是使用未施以粗化處理且表面粗糙度(Rzjis)為2.0μm以下者。
- 如申請專利範圍第1項所述之表面處理銅箔,其中該潔淨化處理是除去銅箔表面的銅氧化物的處理。
- 如申請專利範圍第1項所述之表面處理銅箔,其中該潔淨化處理是使用乾式薄膜形成法在銅箔表面形成一銅層。
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JP2005344174A (ja) * | 2004-06-03 | 2005-12-15 | Mitsui Mining & Smelting Co Ltd | 表面処理銅箔及びその表面処理銅箔を用いて製造したフレキシブル銅張積層板並びにフィルムキャリアテープ |
KR100951211B1 (ko) * | 2004-09-10 | 2010-04-05 | 미쓰이 긴조꾸 고교 가부시키가이샤 | 프라이머 수지층을 구비한 캐리어박 부착 전해 동박 및 그제조 방법 |
CN101146933B (zh) * | 2005-03-31 | 2010-11-24 | 三井金属矿业株式会社 | 电解铜箔及电解铜箔的制造方法、采用该电解铜箔得到的表面处理电解铜箔、采用该表面处理电解铜箔的覆铜层压板及印刷电路板 |
TW200704833A (en) * | 2005-06-13 | 2007-02-01 | Mitsui Mining & Smelting Co | Surface treated copper foil, process for producing surface treated copper foil, and surface treated copper foil with very thin primer resin layer |
JP2007081274A (ja) * | 2005-09-16 | 2007-03-29 | Oike Ind Co Ltd | フレキシブル回路用基板 |
JP2007146289A (ja) * | 2005-10-31 | 2007-06-14 | Mitsui Mining & Smelting Co Ltd | 電解銅箔の製造方法、該製造方法で得られる電解銅箔、該電解銅箔を用いて得られる表面処理銅箔及び該電解銅箔又は該表面処理銅箔を用いて得られる銅張積層板 |
TW200738913A (en) * | 2006-03-10 | 2007-10-16 | Mitsui Mining & Smelting Co | Surface treated elctrolytic copper foil and process for producing the same |
WO2007125994A1 (ja) * | 2006-04-28 | 2007-11-08 | Mitsui Mining & Smelting Co., Ltd. | 電解銅箔、その電解銅箔を用いた表面処理銅箔及びその表面処理銅箔を用いた銅張積層板並びにその電解銅箔の製造方法 |
JP4754402B2 (ja) * | 2006-05-17 | 2011-08-24 | 三井金属鉱業株式会社 | キャリア箔付銅箔、キャリア箔付銅箔の製造方法、キャリア箔付表面処理銅箔及びそのキャリア箔付表面処理銅箔を用いた銅張積層板 |
TW200804626A (en) * | 2006-05-19 | 2008-01-16 | Mitsui Mining & Smelting Co | Copper foil provided with carrier sheet, method for fabricating copper foil provided with carrier sheet, surface-treated copper foil provided with carrier sheet, and copper-clad laminate using the surface-treated copper foil provided with carrier she |
JP5024930B2 (ja) * | 2006-10-31 | 2012-09-12 | 三井金属鉱業株式会社 | 表面処理銅箔、極薄プライマ樹脂層付表面処理銅箔及びその表面処理銅箔の製造方法並びに極薄プライマ樹脂層付表面処理銅箔の製造方法 |
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2008
- 2008-07-11 JP JP2008181266A patent/JP5255349B2/ja not_active Expired - Fee Related
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2009
- 2009-06-26 WO PCT/JP2009/061710 patent/WO2010004885A1/ja active Application Filing
- 2009-06-26 KR KR1020117000305A patent/KR101599511B1/ko not_active IP Right Cessation
- 2009-06-26 CN CN2009801265223A patent/CN102089454B/zh not_active Expired - Fee Related
- 2009-06-26 US US13/002,394 patent/US8394509B2/en not_active Expired - Fee Related
- 2009-06-30 TW TW098121954A patent/TWI434637B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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WO2010004885A1 (ja) | 2010-01-14 |
CN102089454B (zh) | 2013-01-30 |
CN102089454A (zh) | 2011-06-08 |
KR20110039237A (ko) | 2011-04-15 |
KR101599511B1 (ko) | 2016-03-03 |
JP5255349B2 (ja) | 2013-08-07 |
US20110189503A1 (en) | 2011-08-04 |
US8394509B2 (en) | 2013-03-12 |
TW201016090A (en) | 2010-04-16 |
JP2010018855A (ja) | 2010-01-28 |
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