CN111936670B - 表面处理铜箔及铜箔基板 - Google Patents
表面处理铜箔及铜箔基板 Download PDFInfo
- Publication number
- CN111936670B CN111936670B CN202080002048.XA CN202080002048A CN111936670B CN 111936670 B CN111936670 B CN 111936670B CN 202080002048 A CN202080002048 A CN 202080002048A CN 111936670 B CN111936670 B CN 111936670B
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- Prior art keywords
- copper foil
- treated
- layer
- void volume
- treated copper
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 239000011889 copper foil Substances 0.000 title claims abstract description 186
- 239000000758 substrate Substances 0.000 title claims description 32
- 239000011800 void material Substances 0.000 claims abstract description 60
- 239000010410 layer Substances 0.000 claims description 93
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000002335 surface treatment layer Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000002161 passivation Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000003490 calendering Methods 0.000 claims 1
- 230000008054 signal transmission Effects 0.000 description 31
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- -1 3-methacryloxypropyl triethoxysilane (methoxypropyl trimethoxysilane) Chemical compound 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000002500 effect on skin Effects 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000003449 preventive effect Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920001074 Tenite Polymers 0.000 description 2
- 241001422033 Thestylus Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000000788 chromium alloy Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000004643 cyanate ester Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 210000004767 rumen Anatomy 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- WVEVJDPBAZTUEE-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane;trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1.CCO[Si](OCC)(OCC)CCCOCC1CO1 WVEVJDPBAZTUEE-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/16—Electroplating with layers of varying thickness
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0469—Electroforming a self-supporting electrode; Electroforming of powdered electrode material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0237—High frequency adaptations
- H05K1/0242—Structural details of individual signal conductors, e.g. related to the skin effect
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/18—Printed circuits structurally associated with non-printed electric components
-
- 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
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Abstract
一种表面处理铜箔,包括处理面,其中处理面的空隙体积(Vv)为0.4至2.2μm3/μm2,且处理面的峰度(Sku)为1.6至4.0。
Description
技术领域
本发明涉及一种铜箔的技术领域,特别是关于一种表面处理铜箔及其铜箔基板。
背景技术
随着电子产品逐渐朝向轻薄以及传递高频信号的趋势发展,对于铜箔和铜箔基板的需求也日益提升。一般而言,铜箔基板的铜导电线路会被绝缘载板承载,且通过导电线路的布局设计,其可将电信号沿着预定的路径传递至预定区域。此外,对于用于传递高频电信号(例如高于10GHz)的铜箔基板而言,其铜箔基板的导电线路也必须进一步优化,以降低因集肤效应(skin effect)而产生的信号传递损失(signal transmission loss)。所谓的集肤效应,是指随着电信号的频率增加,电流的传递路径会更集中于导线的表面,尤其是更集中于紧邻于载板的导线表面。为了降低集肤效应而产生的信号传递损失,现有作法是尽可能将铜箔基板中紧邻于载板的导线表面予以平坦化。此外,为了同时维持导线表面和载板之间的附着性,也可采用反转处理铜箔(reverse treated foil,RTF)以制作导线。其中,反转处理铜箔指铜箔的辊筒面(drum side)会被施行粗化处理制程的一种铜箔。
然而,即便上述作法确实可有效降低铜箔基板所产生的信号传递损失,其仍存有待克服的技术缺陷。举例而言,由于面向载板的导线表面会较平坦,因此导线和载板之间的附着性通常会较低。在这样的情况下,即便采用了反转处理铜箔以制作导线,铜箔基板中的导线仍很容易从载板的表面剥离,导致电信号无法沿着预定路径传递至预定区域。
因此,仍有必要提供一种表面处理铜箔及铜箔基板,以解决现有技术中所存在的缺陷。
发明内容
有鉴于此,本发明提供有一种改良的表面处理铜箔及铜箔基板,解决了现有技术中所存在的缺陷。
根据本发明的一实施例,提供一种表面处理铜箔,表面处理铜箔包括处理面,其中处理面的空隙体积(void volume,Vv)为0.4至2.2μm3/μm2(μm3/μm2是指单位面积为1μm2的表面所具有的体积),且处理面的峰度(Sku)为1.6至4.0。
根据本发明的另一实施例,提供一种铜箔基板。铜箔基板包括载板以及设置于载板的至少一表面的表面处理铜箔,其中表面处理铜箔包括面向载板的处理面,且处理面的空隙体积(Vv)为0.4至2.2μm3/μm2,处理面的峰度(Sku)为1.6至4.0。
可选择地,根据本发明的又一实施例,提供一种表面处理铜箔。表面处理铜箔包括主体铜箔,以及设置于主体铜箔至少一表面的表面处理层。其中,表面处理层的外侧为表面处理铜箔的处理面,且表面处理层包括粗化层。处理面的空隙体积(Vv)为0.4至2.2μm3/μm2,处理面的峰度(Sku)为1.6至4.0。
可选择地,根据本发明的又一实施例,提供一种表面处理铜箔,表面处理铜箔包括电解铜箔以及设置于电解铜箔的辊筒面的表面处理层。其中,表面处理层的外侧为表面处理铜箔的处理面,且表面处理层包括粗化层。处理面的空隙体积(Vv)为0.4至2.2μm3/μm2,处理面的峰度(Sku)为1.6至4.0。
根据上述实施例,通过将表面处理铜箔的处理面的空隙体积(Vv)控制为0.4至2.2μm3/μm2,且处理面的峰度(Sku)控制为1.6至4.0,当后续将表面处理铜箔压合至载板时,处理面和载板之间的附着性会更佳,且也能保持较低的信号传递损失程度。通过提升表面处理铜箔处理面和载板之间的附着性,后续经由蚀刻程序而形成的导电线路便不易从载板的表面剥离,进而提升了铜箔基板的良率及耐用性。
附图说明
图1是根据本发明一实施例所绘示的表面处理铜箔的剖面示意图。
图2是本发明一实施例的表面处理铜箔的表面高度和负载率之间的关系图。
图3是根据本发明一实施例所绘示的带状线(strip-line)的示意图。
附图标记说明如下:
100:表面处理铜箔;100A:处理面;110:主体铜箔;110A:第一面;110B:第二面;112:表面处理层;114:粗化层;116:钝化层;118:防锈层;120:耦合层;202:空隙体积;202A:波谷部空隙体积;202B:核心部空隙体积;300:带状线;302:导线;304:树脂载板;306-1:接地电极;306-2:接地电极;h:厚度;t:厚度;w:宽度
具体实施方式
在下文中,加以陈述的表面处理铜箔、铜箔基板及印刷电路板的具体实施方式,使本技术领域中具有通常技术者可据以实现本发明。这些具体实施方式可参考相对应的图式,使这些图式构成实施方式的一部分。虽然本发明的实施例公开如下,然而其并非用以限定本发明,任何熟习此技艺者,在不脱离本发明的精神和范畴内,当可作些许的改动与修饰。其中,各实施例以及实验例所使用的方法,如无特别说明,则为常规方法。
针对本发明中所提及的空间相关的叙述词汇,“在…上”及“在…上方”等用语在本发明中的含义应该以最宽泛方式来解释,使得“在…上”及“在…上方”等用语不仅指直接处于某物上,而且还可以包括在有中间特征或中间层位于二者之间的情况下而处于某物上,并且“在…上”或“在…上方”不仅指处于某物之上或上方,而且还可以包括在二者之间没有中间特征或中间层的情况下而处于在某物之上或上方(即直接处于某物上)的态样。
此外,在下文中除非有相反的指示,本发明及权利要求的范围所阐述的数值参数是约略数,其可视需要而变化,或至少应根据所公开的有意义的位数数字并且使用通常的进位方式,以解读各个数值参数。本发明中,范围可表示为从一端点至另一端点,或是在两个端点之间。除非特别声明,否则本发明中的所有范围都包含端点。
须知悉的是,在不脱离本发明的精神下,下文所描述的不同实施方式中的技术特征彼此之间可以被置换、重组、混合,以构成其他的实施例。
图1是根据本发明一实施例所绘示的表面处理铜箔的剖面示意图。如图1所示,表面处理铜箔100至少包括主体铜箔110。主体铜箔110可以是压延铜箔或是电解铜箔,其厚度通常大于或等于6μm,例如介于7-250μm之间,或介于9μm~210μm之间。对于主体铜箔110为电解铜箔的情形,此电解铜箔可通过电沉积(或称电解、电解沉积、电镀)制程而被形成。主体铜箔110具有两相对设置的第一面110A和第二面110B。根据本发明的一实施例,当主体铜箔110为压延铜箔时,第一面110A和第二面110B至少一者的算术平均高度(Ra)为0.1μ~0.4μm,但不限定于此。根据本发明的一实施例,当主体铜箔110为电解铜箔时,电解铜箔的辊筒面(drum side)可以对应至主体铜箔110的第一面110A,而电解铜箔的沉积面(depositedside)可以对应至主体铜箔110的第二面110B,但不限定于此。
根据本发明的一实施例,主体铜箔110的第一面110A和第二面110B上可分别设置有其他的层,例如可在第一面110A设置表面处理层112,及/或在第二面110B设置另一表面处理层112。根据本发明的其他实施例,主体铜箔110的第一面110A和第二面110B可以进一步设置有其他的单层或多层结构、或是第一面110A和第二面110B的表面处理层112可以被其他的单层或多层结构取代、或是第一面110A和第二面110B未设置有任何层,但不限定于此。因此,在这些实施例中,表面处理铜箔100的处理面100A便不会对应至表面处理层112的外侧面,而可能会对应至其他单层或多层结构的外侧面,或可能会对应至主体铜箔110的第一面110A和第二面110B,但不限定于此。
前述表面处理层112可以是单层,或是包括多个子层的堆叠层。对于表面处理层112是堆叠层的情形,各子层可选自由粗化层114、钝化层116、防锈层118以及耦合层120所构成的群组。对于设置有表面处理层112的表面处理铜箔100而言,表面处理层112的外侧面可以被视为是表面处理铜箔100的处理面100A,经由后续将表面处理铜箔100压合至载板的制程,此处理面100A会接触载板。值得一提的是,当表面处理层112有多个时,表面处理层112彼此之间的子层结构可以相同或不同。根据本发明的一实施例,主体铜箔110为压延铜箔,且表面处理层112至少包含粗化层114。根据本发明的一实施例,主体铜箔110为电解铜箔,表面处理层112设置于电解铜箔的辊筒面,且包含粗化层114。根据本发明的一实施例,主体铜箔110为电解铜箔,表面处理层112设置于电解铜箔的辊筒面,且包含粗化层114及钝化层116。
前述粗化层包括粗化粒子(nodule)。粗化粒子可用于增进主体铜箔的表面粗糙度,其可为铜粗化粒子或铜合金粗化粒子。其中,为了防止粗化粒子从主体铜箔剥离,可进一步在粗化层上设置覆盖层,以覆盖住粗化粒子。
钝化层可以是相同或不同组成,例如是金属层或金属合金层。其中,前述金属层可以选自但不限于镍、锌、铬、钴、钼、铁、锡,及钒,例如是:镍层、镍锌合金层、锌层、锌锡合金层或铬层。此外,金属层及金属合金层可以是单层或多层结构,例如彼此堆叠的含锌及含镍的单层。当为多层结构时,各层间的堆叠顺序可以依据需要而调整,并无一定限制,例如含锌层叠于含镍层上,或含镍层叠于含锌层上。
防锈层是施加至金属的被覆层,其可用于避免金属受到腐蚀等而劣化。防锈层包含金属或有机化合物。当防锈层包含金属时,前述金属可以是铬或铬合金,而铬合金可进一步包含选自镍、锌、钴、钼、钒及其组合中的一者。当防锈层包含有机化合物时,前述有机化合物可以选自由***、噻唑、咪唑及其衍生物所组成的群组中的至少一者。
耦合层可以是由硅烷制成,其可选自但不限于3-胺基丙基三乙氧基硅烷(3-aminopropyltriethoxysilane,APTES)、N-2-(胺基乙基)-3-胺基丙基三甲氧基硅烷(N-(2-aminoethyl)-3-aminopropyltrimethoxysilane)、缩水甘油氧基丙基三乙氧基硅烷((3-glycidyloxypropyl)triethoxysilane)、8-缩水甘油氧基辛基三甲氧基硅烷((8-glycidyloxyoctyl)trimethoxysilane)、3-甲基丙烯酰氧基丙基三乙氧基硅烷(methacryloylpropyltriethoxysilane)、8-甲基丙烯酰氧基辛基三甲氧基硅烷(methacryloyloctyltrimethoxysilane)、3-丙烯酰氧基丙基三甲氧基硅烷(methacryloylpropyltrimethoxysilane)、3-巯基丙基三甲氧基硅烷((3-mercaptopropyl)trimethoxysilane)、3-缩水甘油丙基三甲氧基硅烷((3-glycidyloxypropyl)trimethoxysilane),其用于增进表面处理铜箔与其他材料(例如载板)之间的附着性。
根据本发明的实施例,由于表面处理层中的钝化层和耦合层的总和厚度远小于粗化层的厚度,因此表面处理铜箔的处理面的表面粗糙度,例如:空隙体积(Vv)、核心部空隙体积(Vvc)、波谷部空隙体积(Vvv)、峰度(Sku)、及算术平均波度(Wa)等,主要受粗化层的影响。
上述空隙体积(Vv)、核心部空隙体积(Vvc)、及波谷部空隙体积(Vvv)是根据ISO25178-2(2012)的定义,其等的量测可例示如图2所示。图2是本发明一实施例的表面处理铜箔的表面高度和负载率(material ratio,mr)之间的关系图。其中,空隙体积(Vv)202的计算是将曲线上方及水平切割线下方所围住的空隙的体积予以积分,其中水平切割线是该曲线在负载率为P1时所对应的高度。也即,空隙体积(Vv)202为负载率(mr)为P1(10%)的高度水平线下方,至负载率(mr)为100%的区间内的曲线上方所围绕的范围。此外,空隙体积(Vv)202是由波谷部空隙体积(Vvv)202A和核心部空隙体积(Vvc)202B加总而得。进一步而言,波谷部空隙体积(Vvv)202A的计算是将曲线上方及另一水平切割线下方所围住的空隙的体积予以积分,其中该另一水平切割线的位置是该曲线在负载率(mr)为P2时所对应的高度;而核心部空隙体积(Vvc)202B的计算是将曲线及两水平切割线所围住的空隙的体积予以积分,其中两水平切割线的位置是该曲线分别在负载率(mr)为P1和P2时所对应的高度。需注意的是,如未特别声明,本发明所指的空隙体积(Vv)是到负载率(mr)为10%所计算的值,波谷部空隙体积(Vvv)是负载率(mr)为80%所计算的值,核心部空隙体积(Vvc)是负载率(mr)为10%至80%之间所计算的值。
在本发明中,处理面的空隙体积(Vv)为0.4~2.2μm3/μm2,较佳为0.4~1.9μm3/μm2。此外,空隙体积(Vv)是由波谷部空隙体积(Vvv)和核心部空隙体积(Vvc)加总而得,在本发明中,核心部空隙体积(Vvc)较佳为0.3~2.1μm3/μm2,且波谷部空隙体积(Vvv)较佳为0.01~0.10μm3/μm2。
上述峰度(Sku)是指衡量一表面的高度分布的尖锐度(sharpness)的指标。当Sku的数值越低,代表此表面的高度分布越趋平整状;反之,当Sku的数值越高,则代表此表面的峰或谷的尖锐度较高,也即陡峭的峰或谷较多。在本发明中,处理面的峰度(Sku)为1.6~4.0,较佳为2.0~4.0。
上述算术平均波度(Wa)是指由比粗糙度大的间隔所引起的表面的周期性起伏。其中,处理面的算术平均波度(Wa)较佳为0.10~0.40μm、更佳为0.10~0.30μm。
根据本发明的实施例,当处理面的空隙体积(Vv)及峰度(Sku)分别位于0.4~2.2μm3/μm2和1.6~4.0的范围时,对于相应的铜箔基板和印刷电路板而言,表面处理铜箔和相接触的载板除了可以具有较佳的剥离强度(例如高于或等于5.01lb/in),也可以同时降低高频电信号在导电图案中传递时所产生的信号传递损失(信号传递损失的绝对值小于或等于0.82dB/in)。
根据本发明的另一实施例,当处理面的空隙体积(Vv)及峰度(Sku)分别位于0.4~2.2μm3/μm2和2.0~4.0的范围时,对于相应的铜箔基板和印刷电路板而言,可以进一步降低高频电信号在导电图案中传递时所产生的信号传递损失(信号传递损失的绝对值小于或等于0.77dB/in)。
根据本发明的又一实施例,当处理面的空隙体积(Vv)及峰度(Sku)分别位于0.4~2.2μm3/μm2和1.6~4.0的范围时,且算术平均波度(Wa)小于或等于0.40μm时,对于相应的铜箔基板和印刷电路板而言,可以进一步降低高频电信号在导电图案中传递时所产生的信号传递损失(信号传递损失的绝对值小于或等于0.77dB/in)。且当算术平均波度(Wa)再进一步小于0.30μm时,信号传递损失的绝对值会再进一步抑制为低于0.75dB/in。因此,根据本发明的各实施例,通过控制表面处理铜箔的处理面的表面粗糙度参数,则对于相应的铜箔基板和印刷电路板而言,除了可以提升表面处理铜箔和载板之间的附着性,也可以同时降低高频电信号在导电图案中传递时所产生的信号传递损失。
前述表面处理铜箔可再进一步加工制成铜箔基板。铜箔基板至少包括载板和表面处理铜箔。该表面处里铜箔设置于该载板的至少一表面,且包括一处理面。其中,表面处理铜箔的处理面面向且直接接触载板。
其中,上述载板可采用电木板、高分子板、或玻璃纤维板,但并不限于此。所述高分子板的高分子成分可例如:环氧树脂(epoxy resin)、酚醛树脂(phenolic resins)、聚酯树脂(polyester resins)、聚酰亚胺树脂(polyimide resins)、压克力(acrylics)、甲醛树脂(formaldehyde resins)、双马来酰亚胺三嗪树脂(bismaleimidetriazine resins,又称BT树脂)、氰酸酯树脂(cyanate ester resin)、含氟聚合物(fluoropolymers)、聚醚砜(polyether sulfone)、纤维素热塑性塑料(cellulosic thermoplastics)、聚碳酸酯(polycarbonate)、聚烯烃(polyolefins)、聚丙烯(polypropylene)、聚硫化物(polysulfide)、聚氨酯(polyurethane)、聚酰亚胺树脂(polyimide)、液晶高分子(LiquidCrystal Polymer,LCP)、聚氧二甲苯(polyphenylene oxide,PPO)。上述玻璃纤维板可以是玻璃纤维布织物料浸泡于前述高分子(如:环氧树脂)后所形成的预浸渍材料(prepreg)。
在下文中,进一步针对表面处理铜箔以及铜箔基板的制作方法予以例示性地描述。制作方法中的各步骤分述如下:
(1)步骤A
实施步骤A,以提供主体铜箔。其中,主体铜箔可以是压延铜箔或是电解铜箔。对于主体铜箔是压延铜箔的情况,此压延铜箔表面的算术平均高度(Ra)可介于特定区间,例如0.1μ~0.4μm,或0.15~0.25μm;而对于主体铜箔是电解铜箔的情况,可以利用电解沉积(electrodeposition)的方式,以形成此电解铜箔。在电解沉积过程中,金属阴极辊筒会持续转动,且电解铜箔会被连续形成于金属阴极辊筒的表面,并自金属阴极辊筒的某一侧被剥离。其中,电解铜箔面向金属阴极辊筒的表面可称作是辊筒面,而电解铜箔远离金属阴极辊筒的表面可称作是沉积面。此外,在电解沉积的过程中,由于金属阴极辊筒的表面会被些许氧化,而产生不平坦的表面,进而降低了电解铜箔的辊筒面的平坦度。因此,可以进一步在金属阴极辊筒的相邻处设置抛光辊筒(polishbuff),使金属阴极辊筒和抛光辊筒之间具有接触面。通过让金属阴极辊筒和抛光辊筒以相反的方向转动,便可以使得金属阴极辊筒表面的氧化层被抛光辊筒去除,进而维持了金属阴极辊筒的表面平坦度。
对于压延铜箔而言,其特征例示如下:
〈1.1压延铜箔〉
算术平均高度(Ra):0.1μ~0.4μm
对于电解铜箔而言,其制造参数范围例示如下:
〈1.2硫酸铜电解液的组成及电解条件〉
硫酸铜(CuSO4·5H2O):320g/L
硫酸:100g/L
氯离子(从盐酸而来,RCI Labscan Ltd.):20mg/L
明胶(SV,Nippi,Inc.):0.35mg/L
液温:50℃
电流密度:70A/dm2
〈1.3金属阴极辊筒〉
材质:钛
转速:3m/min
〈1.4抛光辊筒〉
型号(Nippon Tokushu Kento Co.,Ltd):#500、#1000、#1500、#2000
转速:250~550rpm
(2)步骤B
本步骤B是对上述主体铜箔施行表面清洁的制程,以确保主体铜箔的表面不具有污染物(例如油污、氧化物),其制造参数范围例示如下:
〈2.1清洗液的组成及清洁条件〉
硫酸铜:130g/L
硫酸:50g/L
液温:27℃
浸渍时间:30秒
(3)步骤C
本步骤C是在上述主体铜箔的表面形成粗化层。可通过电解沉积,以将粗化层形成于主体铜箔的某一面,例如辊筒面。其中,粗化层可以包括粗化粒子,或称为瘤状结构(nodule),和覆盖住粗化粒子的覆盖层。其中,在形成粗化粒子时,可以选择性地在电解液中添加适当的盐类,例如钨酸钠或硫酸亚铁,以控制粗化粒子的分布情形。制造参数范围例示如下:
〈3.1制作粗化粒子的参数〉
硫酸铜(CuSO4·5H2O):70g/L
硫酸:100g/L
钨酸钠(Na2WO4):50~450mg/L(ppm)
硫酸亚铁(FeSO4):1000~3000mg/L(ppm)
邻苯甲酰磺酰亚胺(糖精,Sigma-Aldrich Company):5~20mg/L(ppm)
液温:25℃
电流密度:10A/dm2
时间:10秒
(4)步骤D
本步骤D是在上述粗化层上形成覆盖层,其制造参数范围例示如下:
〈4.1制作覆盖层的参数〉
硫酸铜(CuSO4·5H2O):320g/L
硫酸:100g/L
液温:40℃
电流密度:15A/dm2
时间:10秒
(5)步骤E
本步骤E是在上述铜箔的至少一表面形成钝化层。可以通过电解沉积制程以形成钝化层,对于钝化层是例示由镍、锌所构成的两层堆叠结构,其制造参数范围例示如下:
〈5.1含镍层的电解液组成及电解条件〉
硫酸镍(NiSO4):188g/L
硼酸(H3BO3):32g/L
次磷酸(H3PO2):4g/L
液温:20℃
溶液pH:3.5
电流密度:0.7A/dm2
时间:3秒
〈5.2含锌层的电解液组成及电解条件〉
硫酸锌(ZnSO4):11g/L
偏钒酸铵(NH4VO3):0.25g/L
液温:15℃
溶液pH:13
电流密度:0.5A/dm2
时间:2秒
(6)步骤F
本步骤F是在上述铜箔上形成防锈层,其制造参数范围例示如下:
〈6.1含铬层的电解液组成及电解条件〉
铬酸:5g/L
液温:35℃
溶液pH:12.5
电流密度:10A/dm2
时间:5秒
(7)步骤G
本步骤G是在上述铜箔设置粗化层的一侧上形成耦合层。举例而言,完成上述电解制程后,用水洗涤铜箔,但不干燥铜箔表面。之后将含有硅烷耦合剂的水溶液喷涂至铜箔设有粗化层侧的防锈层上,使得硅烷耦合剂吸附于钝化层的表面。制造参数范围例示如下:
〈7.1硅烷耦合剂的参数〉
硅烷耦合剂:(3-胺基丙基)三乙氧基硅烷(3-aminopropyltriethoxysilane)
水溶液的硅烷耦合剂浓度:0.25wt.%
喷涂时间:10秒
(8)步骤H
本步骤H是将经由上述步骤而形成的表面处理铜箔压合至载板,以形成铜箔基板。根据本发明的一实施例,可通过将图1所示的表面处理铜箔100热压至载板,而形成铜箔基板。
为了使本领域的通常知识者得据以实现本发明,下文将进一步详细描述本发明的各具体实施例,以具体说明本发明的表面处理铜箔及铜箔基板。需注意的是,以下实施例仅为例示性,不应以其限制性地解释本发明。也即,在不超出本发明范畴的情况下,可适当地改变各实施例中所采用的材料、材料的用量及比率以及处理流程等。
实施例1
实施例1为表面处理铜箔,其制造程序对应于上述制作方法中的步骤A至步骤G。实施例1与上述制作方法之间相异的制造参数,记载于表1中。其中,主体铜箔为电解铜箔,且粗化层设置在电解铜箔的辊筒面上。
实施例2-19
实施例2-19的制造程序大致相同于实施例1的制造程序,其彼此之间不同的制造参数记载于表1中。其中,实施例2-1、13-18中的主体铜箔为电解铜箔,且粗化层设置在电解铜箔的辊筒面上。
实施例12及实施例19在制作方法所采用的主体铜箔为压延铜箔(Ra=0.2μm),而非电解铜箔。
表1
以下进一步描述上述各实施例1-19的各项检测结果,例如:〈算术平均波度(Wa)〉、〈峰度(Sku)〉、〈核心部空隙体积(Vvc)〉、〈波谷部空隙体积(Vvv)〉、〈空隙体积(Vv)〉、〈剥离强度〉、及〈信号传递损失〉。
〈算术平均波度(Wa)〉
根据标准JIS B0601-20134.2.1,以表面粗糙度测量仪(SE 600Series,KosakaLaboratory Ltd.)检测各实施例的表面处理铜箔的处理面的算术平均波度(Wa)。具体量测条件如下:测针尖端的直径为2μm、测针尖端的锥角为90°、测量长度为7.5mm、轮廓曲线过滤器的截止值为λc=0.8mm、λf=2.5mm。检测结果记载于表2中。
〈峰度(Sku)〉
根据标准ISO 25178-2:2012,以激光显微镜(LEXT OLS5000-SAF,Olympus)的表面纹理分析,测量表面处理铜箔的处理面的峰度(Sku)。具体测量条件如下:
光源波长:405nm
物镜倍率:100倍物镜(MPLAPON-100x LEXT,Olympus)
光学变焦:1.0倍
观察面积:129μm×129μm
分辨率:1024像素×1024像素
条件:启用激光显微镜的自动倾斜消除功能(Auto tilt removal)
滤镜:无滤镜(unfiltered)
空气温度:24±3℃
相对湿度:63±3%
〈核心部空隙体积(Vvc)〉、〈波谷部空隙体积(Vvv)〉、〈空隙体积(Vv)〉
根据标准ISO 25178-2:2012,以激光显微镜(LEXT OLS5000-SAF,Olympus)的表面纹理分析,测量表面处理铜箔的处理面的核心部空隙体积(Vvc)、波谷部空隙体积(Vvv)、及空隙体积(Vv)。其中,核心部空隙体积(Vvc)是由设定负载率(mr)的P1值及P2值分别为10%及80%而予以获得,波谷部空隙体积(Vvv)是负载率(mr)P2值设定为80%而予以获得,空隙体积(Vv)为前述核心部空隙体积(Vvc)及波谷部空隙体积(Vvv)之和。检测结果记载于表2中。具体测量条件如下:
光源波长:405nm
物镜倍率:100倍物镜(MPLAPON-100x LEXT,Olympus)
光学变焦:1.0倍
观察面积:129μm×129μm
分辨率:1024像素×1024像素
条件:启用激光显微镜的自动倾斜消除功能(Auto tilt removal)
滤镜:无滤镜(unfiltered)
空气温度:24±3℃
相对湿度:63±3%
〈剥离强度〉
将6片厚度各自为0.076mm的市售树脂片(S7439G,SyTech Corporation.)堆叠在一起,以形成树脂片堆叠层,并将上述任一实施例的表面处理铜箔设置于树脂片堆叠层上。接着,将表面处理铜箔压合至树脂片堆叠层,以形成积层板。压合条件如下:温度200℃、压力400psi、及压合时间120分钟。
之后,根据标准JIS C 6471,使用万能试验机,以将表面处理铜箔以90°的角度从积层板剥离。检测结果记载于表2中。
〈信号传递损失〉
将上述任一实施例的表面处理铜箔制作成带状线(stripline),并测量其相应的信号传递损失。其中,带状线的结构可例示如图3所示。带状线300是在152.4μm的树脂(取自SyTech Corporation之S7439G)上先贴合上述任一实施例的表面处理铜箔,而后将表面处理铜箔制作成导线302,再使用另外两片树脂(S7439G,取自SyTech Corporation之S7439G)分别覆盖两侧表面,使导线302被设置于树脂载板(S7439G,SyTech Corporation.)304之中。带状线300还可包括两接地电极306-1和接地电极306-2,分别设置于树脂载板304的相对两侧。接地电极306-1和接地电极306-2彼此之间可以通过导电通孔而彼此电连接,而使得接地电极306-1和接地电极306-2具有等电位。
带状线300中各部件的规格如下:导线302的长度为100mm、宽度w为120μm、厚度t为35μm;树脂载板304的Dk为3.74、Df为0.006(依据IPC-TM 650No.2.5.5.5,以10GHz信号测量);特征阻抗为50Ω。
根据标准Cisco S3方法,利用信号分析仪(PNA N5230C network analyzer,Agilent)在接地电极306-1、306-2均为接地电位的情况下,将电信号由导线302的某一端输入,并测量导线302的另一端的输出值,以判别带状线300所产生的信号传递损失。具体量测条件如下:电信号频率为200MHz至15GHz、扫描数为6401点、校正方式为TRL。
最后,以电信号频率为8GHz的情况,判别相应带状线的信号传递损失的程度,检测结果记载于表2中。其中,当信号传递损失的绝对值越小,代表信号在传递时的损失程度越少。具体而言,当信号传递损失的绝对值大于0.82dB/in时,代表信号传递表现差;当信号传递损失的绝对值小于或等于0.82dB/in时,代表信号传递表现良好;而当信号传递损失的绝对值小于0.75dB/in时,代表信号传递表现最佳。
表2
根据上述实施例1-14,当处理面的空隙体积(Vv)及峰度(Sku)分别位于0.4~2.2μm3/μm2和1.6~4.0的范围时,对于相应的铜箔基板和印刷电路板而言,表面处理铜箔和相接触的载板除了可以具有较佳的剥离强度(例如高于或等于5.01lb/in),也可以同时降低高频电信号在导电图案中传递时所产生的信号传递损失(信号传递损失的绝对值小于或等于0.82dB/in)。
根据本发明的实施例1-12,当处理面的空隙体积(Vv)及峰度(Sku)分别位于0.4~2.2μm3/μm2和1.6~4.0的范围时,且算术平均波度(Wa)小于或等于0.40μm时,对于相应的铜箔基板和印刷电路板而言,可以进一步降低高频电信号在导电图案中传递时所产生的信号传递损失(信号传递损失的绝对值小于或等于0.77dB/in)。
根据本发明的实施例1-12,当处理面的空隙体积(Vv)及峰度(Sku)分别位于0.4~2.2μm3/μm2和2.0~4.0的范围时,对于相应的铜箔基板和印刷电路板而言,可以进一步降低高频电信号在导电图案中传递时所产生的信号传递损失(信号传递损失的绝对值小于或等于0.77dB/in)。
根据本发明的上述各实施例,通过将表面处理铜箔的处理面的上述表面粗糙度参数控制在特定范围,则对于相应的铜箔基板和印刷电路板而言,除了可以提升表面处理铜箔和载板之间的附着性(剥离强度大于5lb/in),也可以同时降低高频电信号在导电图案中传递时所产生的信号传递损失(信号传递损失的绝对值小于0.75dB/in)。
以上所述仅为本发明的较佳实施例,凡依本发明权利要求范围所做的均等变化与修饰,都应属本发明的涵盖范围。
Claims (15)
1.一种表面处理铜箔,其特征在于,包括一处理面,其中所述处理面的空隙体积(Vv)为0.4至2.2μm3/μm2,且所述处理面的峰度(Sku)为1.6至4.0,所述空隙体积(Vv)是根据标准ISO 25178-2:2012的定义,在负载率(mr)10%至100%区间所计算的值。
2.如权利要求1所述的表面处理铜箔,其特征在于,所述处理面的算术平均波度(Wa)小于或等于0.40μm。
3.如权利要求1所述的表面处理铜箔,其特征在于,所述处理面的峰度(Sku)为2.0至4.0。
4.如权利要求3所述的表面处理铜箔,其特征在于,所述处理面的算术平均波度(Wa)为0.10至0.40μm。
5.如权利要求4所述的表面处理铜箔,其特征在于,所述处理面的空隙体积(Vv)为0.4至1.9μm3/μm2,且所述处理面的算术平均波度(Wa)为0.10至0.30μm。
6.如权利要求1所述的表面处理铜箔,其特征在于,所述处理面的核心部空隙体积(Vvc)为0.3至2.1μm3/μm2。
7.如权利要求1所述的表面处理铜箔,其特征在于,所述处理面的波谷部空隙体积(Vvv)为0.01至0.10μm3/μm2。
8.如权利要求1至7中任一项所述的表面处理铜箔,其特征在于,所述表面处理铜箔进一步包括:
一主体铜箔;以及
一表面处理层,设置于所述主体铜箔的至少一表面,其中,所述表面处理层的外侧为所述处理面。
9.如权利要求8所述的表面处理铜箔,其特征在于,所述主体铜箔为压延铜箔。
10.如权利要求8所述的表面处理铜箔,其特征在于,所述主体铜箔为电解铜箔,且包括一辊筒面以及一沉积面,所述表面处理层设置在所述辊筒面。
11.如权利要求10所述的表面处理铜箔,其特征在于,所述表面处理层包括一子层,所述子层为粗化层。
12.如权利要求11所述的表面处理铜箔,其特征在于,所述表面处理层还进一步包括至少一个其他的子层,所述至少一个其他的子层选自由钝化层及耦合层所构成的群组。
13.如权利要求12所述的表面处理铜箔,其特征在于,所述钝化层包含至少一金属,所述金属选自由镍、锌、铬、钴、钼、铁、锡及钒所构成的群组。
14.一种铜箔基板,其特征在于,包括:
一载板;以及
一表面处理铜箔,设置于所述载板的至少一表面,其中所述表面处理铜箔包括面向所述载板的一处理面,且所述处理面的空隙体积(Vv)为0.4至2.2μm3/μm2,所述处理面的峰度(Sku)为1.6至4.0,所述空隙体积(Vv)是根据标准ISO 25178-2:2012的定义,在负载率(mr)10%至100%区间所计算的值。
15.如权利要求14所述的铜箔基板,其特征在于,所述表面处理铜箔的所述处理面直接接触所述载板。
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