CN117321254A - Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board - Google Patents
Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board Download PDFInfo
- Publication number
- CN117321254A CN117321254A CN202280035832.XA CN202280035832A CN117321254A CN 117321254 A CN117321254 A CN 117321254A CN 202280035832 A CN202280035832 A CN 202280035832A CN 117321254 A CN117321254 A CN 117321254A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- roughened
- peaks
- valleys
- peak
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 239000011889 copper foil Substances 0.000 title claims abstract description 203
- 238000004458 analytical method Methods 0.000 claims abstract description 41
- 238000010191 image analysis Methods 0.000 claims abstract description 26
- 238000011282 treatment Methods 0.000 claims description 52
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 21
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- 230000005540 biological transmission Effects 0.000 abstract description 33
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 92
- 239000011347 resin Substances 0.000 description 37
- 229920005989 resin Polymers 0.000 description 37
- 229910052802 copper Inorganic materials 0.000 description 34
- 239000010949 copper Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 32
- 238000007747 plating Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- 238000007788 roughening Methods 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 16
- 239000011888 foil Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229910000365 copper sulfate Inorganic materials 0.000 description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 7
- -1 and the like Chemical compound 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- 230000000007 visual effect Effects 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000009499 grossing Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-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
- ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 1H-imidazole silane Chemical compound [SiH4].N1C=NC=C1 ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 0.000 description 1
- UYWWLYCGNNCLKE-UHFFFAOYSA-N 2-pyridin-4-yl-1h-benzimidazole Chemical compound N=1C2=CC=CC=C2NC=1C1=CC=NC=C1 UYWWLYCGNNCLKE-UHFFFAOYSA-N 0.000 description 1
- NNRAOBUKHNZQFX-UHFFFAOYSA-N 2H-benzotriazole-4-thiol Chemical compound SC1=CC=CC2=C1NN=N2 NNRAOBUKHNZQFX-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- DUYKOAQJUCADEC-UHFFFAOYSA-N [SiH4].N1=NN=CC=C1 Chemical compound [SiH4].N1=NN=CC=C1 DUYKOAQJUCADEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001336 alkenes Chemical class 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical group [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PPTYNCJKYCGKEA-UHFFFAOYSA-N dimethoxy-phenyl-prop-2-enoxysilane Chemical compound C=CCO[Si](OC)(OC)C1=CC=CC=C1 PPTYNCJKYCGKEA-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005357 flat glass 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
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 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
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-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
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- VMYXFDVIMUEKNP-UHFFFAOYSA-N trimethoxy-[5-(oxiran-2-yl)pentyl]silane Chemical compound CO[Si](OC)(OC)CCCCCC1CO1 VMYXFDVIMUEKNP-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
-
- 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
-
- 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
- H05K3/46—Manufacturing multilayer circuits
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Abstract
Provided is a roughened copper foil which can achieve both excellent transmission characteristics and high shear strength in the processing of a copper-clad laminate to the production of a printed wiring board. The roughened copper foil has a roughened surface on at least one side. The roughened surface has a plurality of peaks that are raised with respect to the reference surface and a plurality of valleys that are recessed with respect to the reference surface. When three-dimensional image analysis is performed on an image obtained by using a FIB-SEM for a roughened surface and a peak is divided into a plurality of voxels, the ratio of the total volume of voxels constituting the surface of the peak to the total volume of all voxels constituting the peak, that is, the surface voxel ratio, is 0.25 to 0.60 inclusive, and the average height of the peak and the valley calculated as the sum of the average height of the peak and the average height of the valley in the 2000nm×2000nm analysis region is 40nm to 90nm inclusive.
Description
Technical Field
The present invention relates to a roughened copper foil, a copper foil with a carrier, a copper-clad laminate, and a printed circuit board.
Background
In recent years, MSAP (modified semi-additive process) method has been widely used as a method for manufacturing printed circuit boards suitable for circuit miniaturization. The MSAP method is a method suitable for forming an extremely fine circuit, and is performed using a copper foil with a carrier in order to use the characteristics thereof. For example, as shown in fig. 1 and 2, an extra thin copper foil (roughened copper foil 10) is pressed against an insulating resin substrate 11 with a prepreg 12 and a primer layer 13 interposed therebetween to be in close contact with each other, the insulating resin substrate 11 is provided with a lower layer circuit 11b on a base substrate 11a (step (a)), a carrier (not shown) is peeled off, and then a via hole 14 is formed by laser perforation as needed (step (b)). Next, after electroless copper plating 15 is performed (step (c)), exposure and development using a dry film 16 are performed to mask the film in a predetermined pattern (step (d)), and copper plating 17 is performed (step (e)). After the dry film 16 is removed to form the wiring portion 17a (step (f)), unnecessary extra thin copper foil or the like between the wiring portions 17a and 17a adjacent to each other is removed by etching over the entire thickness thereof (step (g)), and the wiring 18 formed in a predetermined pattern is obtained. Here, in order to improve the physical adhesion between the circuit and the substrate, the surface of the extra thin copper foil is generally roughened.
In practice, several carrier-attached copper foils excellent in fine circuit formability based on the MSAP method or the like have been proposed. For example, patent document 1 (international publication No. 2016/117587) discloses a carrier-equipped copper foil comprising an extra thin copper foil having an average surface peak-to-peak distance of 20 μm or less on the release layer side surface and a maximum level difference of 1.0 μm or less on the opposite side surface of the release layer, and it is considered that this system can achieve both fine circuit formation and laser processability. Patent document 2 (japanese patent application laid-open No. 2018-26590) discloses a copper foil with a carrier, in which the ratio Sp/Spk of the maximum peak height Sp to the protruding peak height Spk of the surface of the ultra-thin copper layer according to ISO25178 is 3.271 to 10.739.
On the other hand, as the miniaturization of circuits progresses, physical stress (i.e., shear stress) from the lateral direction is applied to the circuits in the mounting process of printed circuit boards, which causes the circuits to be easily peeled off, and the yield is remarkably lowered. In this regard, as one of the physical adhesion indexes of the circuit and the substrate, there is shear strength (shear strength), and in order to effectively avoid the peeling of the circuit, a roughened copper foil suitable for improving the shear strength has been proposed. For example, patent document 3 (international publication No. 2020/031721) discloses a roughened copper foil in which the maximum height Sz, the interface expansion area ratio Sdr, and the peak top density Spd defined in ISO25178 are controlled to be within predetermined ranges. According to the roughened copper foil, excellent etching properties and high shear strength can be achieved at the same time in the processing of the copper-clad laminate to the production of a printed wiring board.
On the other hand, with recent high-functionality of portable electronic devices and the like, in order to process a large amount of information at high speed, a high frequency signal has been developed, and a printed circuit board particularly suitable for high frequency applications such as a fifth generation mobile communication system (5G) and a sixth generation mobile communication system (6G) has been demanded. In order to transmit a high-frequency signal without deteriorating the quality of the high-frequency signal, a reduction in transmission loss is desired for such a high-frequency printed circuit board. The printed circuit board includes a copper foil processed into a wiring pattern and an insulating resin base material, and the transmission loss is mainly composed of a conductor loss due to the copper foil and a dielectric loss due to the insulating resin base material.
Conductor loss may increase due to the skin effect of the copper foil which becomes more pronounced with higher frequencies. Therefore, in order to suppress transmission loss in high frequency applications, smoothing of the copper foil and miniaturization of the roughened particles are required to reduce the skin effect of the copper foil. In this regard, roughened copper foil is known for the purpose of reducing transmission loss. For example, patent document 4 (japanese patent No. 6462961) relates to a surface-treated copper foil in which a roughened layer, an anti-rust treatment layer, and a silane coupling layer are laminated in this order on at least one surface of the copper foil, and discloses that the interface expansion area ratio Sdr measured from the surface of the silane coupling layer is 8% or more and 140% or less, the root mean square slope Sdq is 25 ° or more and 70 ° or less, and the aspect ratio Str of the surface properties is 0.25 or more and 0.79 or less. According to the surface-treated copper foil, a printed wiring board having less transmission loss of high-frequency electric signals and excellent adhesion at the time of reflow soldering can be produced.
Prior art literature
Patent literature
Patent document 1: international publication No. 2016/117587
Patent document 2: japanese patent laid-open publication No. 2018-26590
Patent document 3: international publication No. 2020/031721
Patent document 4: japanese patent No. 6462961
Disclosure of Invention
As described above, from the viewpoint of high frequency transmission, a copper foil with low transmission loss (i.e., a copper foil excellent in high frequency characteristics) is required as a material for forming a circuit wiring for a flow signal. Although transmission loss can be suppressed by smoothing of the copper foil and miniaturization of the roughened particles, the physical bonding force (in particular, shear strength) of the copper foil and the substrate resin or the like is lowered. Therefore, it is not easy to achieve both excellent transfer characteristics and high circuit adhesion.
The inventors have found the following findings at this time: in the roughened copper foil, a surface profile in which the total volume of voxels constituting the surface of the peak relative to the total volume of all voxels constituting the peak, that is, the surface voxel ratio, and the average height of the peak and the average height of the valley calculated as the sum of the average height of the peak and the average height of the valley are controlled within a predetermined range are provided, whereby excellent transmission characteristics and high shear strength can be simultaneously achieved in the processing of the copper-clad laminate to the manufacture of the printed wiring board.
Accordingly, an object of the present invention is to provide a roughened copper foil which can achieve both excellent transfer characteristics and high shear strength in the processing of a copper-clad laminate to the production of a printed wiring board.
According to the present invention, the following manner is provided.
Mode 1
A roughened copper foil having a roughened surface on at least one side, the roughened surface having a plurality of peaks protruding from a reference surface and a plurality of valleys recessed from the reference surface,
when three-dimensional image analysis is performed on an image obtained by using a FIB-SEM for the roughened surface and the peak is divided into a plurality of voxels, the ratio of the total volume of voxels constituting the surface of the peak to the total volume of all voxels constituting the peak, that is, the surface voxel ratio, in an analysis region of 2000nm×2000nm is 0.25 to 0.60 inclusive,
when performing three-dimensional image analysis on an image obtained by using a FIB-SEM for the roughened surface, the average height of the peaks and the average height of the valleys calculated as the sum of the average heights of the peaks and the average heights of the valleys in an analysis region of 2000nm×2000nm is 40nm to 90 nm.
Mode 2
The roughened copper foil according to embodiment 1, wherein the surface voxel ratio is 0.25 or more and 0.35 or less.
Mode 3
The roughened copper foil according to embodiment 1 or 2, wherein the average height of the peaks and valleys is 40nm or more and 80nm or less.
Mode 4
The roughened copper foil according to any one of modes 1 to 3, wherein, in the case of performing three-dimensional image analysis on an image obtained by using FIB-SEM for the roughened surface, the three-dimensional image analysis is performed every 1nm 2 The total volume of the peaks per unit area is 7.0nm 3 Above and 50.0nm 3 The following is given.
Mode 5
The roughened copper foil according to mode 4, wherein, every 1nm 2 The total volume of the peaks per unit area is 30.0nm 3 Above and 50.0nm 3 The following is given.
Mode 6
The roughened copper foil according to any one of embodiments 1 to 5, wherein, in the case of performing three-dimensional image analysis on an image obtained by using a FIB-SEM for the roughened surface, the sum of the heights of the peaks and the valleys calculated as the sum of the volumes of the peaks and the volumes of the valleys in an analysis region of 2000nm×2000nm is 1.4X10 8 nm 3 Above and 3.5X10 8 nm 3 。
Mode 7
The roughened copper foil according to mode 6, wherein the sum of the heights of the peaks and valleys is 2.0X10 8 nm 3 Above and 3.5X10 8 nm 3 The following is given.
Mode 8
The roughened copper foil according to any one of aspects 1 to 7, further comprising a rust-preventive treatment layer and/or a silane coupling agent layer on the roughened surface.
Mode 9
A copper foil with a carrier, comprising: the roughened copper foil according to any one of aspects 1 to 8, wherein the roughened copper foil is provided on the release layer so that the roughened surface is on the outside.
Mode 10
A copper-clad laminate comprising the roughened copper foil according to any one of modes 1 to 8.
Mode 11
A printed wiring board comprising the roughened copper foil according to any one of modes 1 to 8.
Drawings
Fig. 1 is a process flow chart for explaining the MSAP method, and is a diagram showing the first half steps (a) to (d)).
Fig. 2 is a process flow chart for explaining the MSAP method, and is a diagram showing the second half of the process (steps (e) to (g)).
Fig. 3 is a schematic cross-sectional view for explaining the sum of the heights of the peaks and valleys and the reference plane of the roughened surface in the roughened copper foil.
Fig. 4 is a schematic cross-sectional view for explaining the reference plane of the roughened surface and the average heights of peaks and valleys in the roughened copper foil.
Fig. 5 is a diagram showing a virtual division of peaks existing on a roughened surface in a roughened copper foil by voxels.
Fig. 6 is a view showing a region where laser light is not incident when the roughened surface is measured by a laser microscope.
Fig. 7 is a graph showing the relationship between the x-axis, y-axis and z-axis, and the sliced surface S and the roughened copper foil in 3D-SEM observation.
Fig. 8 is a graph showing the relationship between each axis after rotation of the x-axis, y-axis and z-axis and the roughened copper foil in 3D-SEM image analysis.
Detailed Description
Definition of the definition
The following illustrates definitions of terms and/or parameters used to define the invention.
In the present specification, "an image obtained by using FIB-SEM for the roughened surface" means: the roughened surface of the roughened copper foil is an aggregate of cross-sectional images obtained by cross-sectional processing by FIB (focused ion beam) and cross-sectional observation by SEM (scanning electron microscope), and the aggregate as a whole constitutes three-dimensional shape data. Specifically, as shown in fig. 7, the x-axis and the z-axis are defined as the in-plane direction of the roughened copper foil 10, and the y-axis is defined as the thickness direction of the roughened copper foil 10, and then a cross-sectional image of the roughened surface including the roughened copper foil 10 on a slice surface S parallel to the x-y plane is acquired, and the slice surface is moved in parallel at predetermined intervals (for example, 10 nm) in the z-axis direction, and then an aggregate of (for example, 1000 pieces in total) cross-sectional images acquired in a predetermined analysis area (for example, 2000nm×2000 nm) is acquired.
In the present specification, as schematically shown in fig. 3 and 4, the "peak" of the roughened surface means: in the roughened surface of the roughened copper foil 10, the roughened surface has a convex portion with respect to the reference surface R. In this specification, as schematically shown in fig. 3 and 4, the "valleys" of the roughened surface means: in the roughened surface of the roughened copper foil 10, the roughened surface has a concave-convex structure, which is recessed with respect to the reference surface R. The "reference plane" of the roughened surface can be determined by performing three-dimensional image analysis on an image obtained by using FIB-SEM for the roughened surface. Specifically, first, in an analysis region (size in plan view) of 2000nm×2000nm, a median value (reference point) of the height (y direction) of the roughened surface in a predetermined matrix size (for example, 99) in the x-z plane centered on a pixel of interest (hereinafter referred to as pixel of interest) in the x-z plane of an image constituting the concave-convex structure is obtained. For example, when the matrix size is 99, the median value is obtained from the height of the roughened surface in each of 99 pixels×99 pixels centering on the pixel of interest. This operation is performed for all pixels (each of which is a pixel of interest) in the x-z plane of the image constituting the concave-convex structure, and the median value (reference point) of the height of the roughened surface in each pixel of interest is obtained. Next, the surface of all the reference points in each pixel of interest thus obtained is plotted, whereby it can be used as a reference surface. The three-dimensional image analysis can be automatically performed using commercially available software, and the standard plane can be uniquely determined by applying a median filter having a matrix size (for example, 99) to the roughened copper foil (i.e., in commercially available software, there is no item for setting conditions other than the matrix size with respect to the setting of the standard plane). For example, for an image of the roughened surface (a slice image of three-dimensional shape data of the roughened copper foil), three-dimensional position alignment software "ExFact Slice Aligner (version 2.0)" (Nihon Visual Science, manufactured by inc.) and three-dimensional image Analysis software "extract VR (version 2.2)", and "foil Analysis (version 1.0)" (both Nihon Visual Science, manufactured by inc.) may be used to perform image Analysis according to the conditions described in the examples of the present specification. The method for acquiring a cross-sectional image obtained by using the FIB-SEM is as shown in examples described later.
In the present specification, the "sum of the heights of the peaks and the valleys" is a parameter indicating the sum of the volumes of the peaks and the volumes of the valleys in an analysis region (size in plan view) of 2000nm×2000 nm. That is, as schematically shown in fig. 3, the sum of the volumes Ap of the peaks with respect to the reference plane R (the total volume of all the peaks in the analysis region) and the sum of the volumes Av of the valleys with respect to the reference plane R (the total volume of all the valleys in the analysis region) corresponds to the sum of the heights of the peaks and the valleys. Although the term "sum of peak and valley heights" may be referred to as "sum of peak and valley volumes", the term "sum of peak and valley heights" is specifically used in the specification of commercially available image analysis software because it is calculated by accumulating values mentioned by the names of "peak heights" and "valley heights", in order to facilitate measurement by those skilled in the art.
In the present specification, the "average height of peaks and valleys" is a parameter indicating the sum of the average height of peaks and the average height of valleys in an analysis region (size in plan view) of 2000nm×2000 nm. That is, as schematically shown in fig. 4, the sum of the average value of the heights Hp of the peaks with respect to the reference plane R (the average height of all the peaks in the analysis region) and the average value of the heights Hv of the valleys with respect to the reference plane R (the average height of all the valleys in the analysis region) corresponds to the average height H of the peaks and the valleys.
In the present specification, "every 1nm 2 The total volume of peaks per unit area "is a parameter calculated by dividing the total volume of all peaks in an analysis region (size in plan view) of 2000nm×2000nm by the area of the analysis region.
The sum of the heights of the peaks and valleys, the average height of the peaks and valleys, and the average height of the peaks and valleys per 1nm 2 The total volume of peaks per unit area can be determined by three-dimensional image analysis of an image obtained by using FIB-SEM for the roughened surface. Such three-dimensional image analysis can be performed using commercially available software. For example, for a cross-sectional image of the roughened surface (a slice image of three-dimensional shape data of the roughened copper foil), three-dimensional position alignment software "ExFact Slice Aligner (version 2.0)" (NihonVisual Science, manufactured by inc.) and three-dimensional image Analysis software "extract VR (version 2.2)", and "foil Analysis (version 1.0)" (both manufactured by NihonVisual Science, manufactured by inc.) may be used to perform image Analysis according to the conditions described in the examples of the present specification. The method for acquiring a cross-sectional image obtained by using the FIB-SEM is as shown in examples described later.
In the present specification, "voxel" refers to an element of a volume in three-dimensional image data, and is a concept corresponding to a pixel of two-dimensional image data. Voxels can be represented by cubes, cuboids, or the like, and for example, each 1 voxel has a size of (length, width, height) = (1 nm ), and thus can be converted into SI units.
In the present specification, "surface voxel ratio" means: when the peak of the roughened surface is divided into a plurality of voxels, the ratio of the total volume of voxels (surface voxels) constituting the surface of the peak to the total volume of all voxels constituting the peak in an analysis region (size in plan view) of 2000nm×2000nm is determined. The surface voxel ratio can be determined by performing three-dimensional image analysis on an image obtained by using FIB-SEM for the roughened surface. Specifically, as schematically shown in FIG. 5, the z-axis is perpendicular to the roughened surface and the x-y surface is parallel to the roughened surface as shown in FIG. 8The x-axis, y-axis, and z-axis are allocated in a row manner, and three-dimensional image analysis is performed on an image obtained by using FIB-SEM for the roughened surface, so that the peak (P 1 、P 2 、P 3 ) Imaginary division (labeling) is performed. At this time, the voxel constituting the surface of the peak (the surface in contact with the atmosphere) among the voxels B constituting the peak is defined as "surface voxel Bs", whereby the surface voxel ratio can be calculated. Such three-dimensional image analysis can be performed using commercially available software. For example, for an image of the roughened surface (a slice image of three-dimensional shape data of the roughened copper foil), three-dimensional position alignment software "ExFact Slice Aligner (version 2.0)" (Nihon Visual Science, manufactured by inc.) and three-dimensional image Analysis software "extract VR (version 2.2)", and "foil Analysis (version 1.0)" (both Nihon Visual Science, manufactured by inc.) may be used to perform image Analysis according to the conditions described in the examples of the present specification. The method for acquiring a cross-sectional image obtained by using the FIB-SEM is as shown in examples described later.
In the present specification, the "electrode surface" of the support means a surface on a side that contacts the cathode when the support is fabricated.
In the present specification, the "deposition surface" of the support means a surface on the electrolytic copper deposition side, that is, a surface on the side not in contact with the cathode when the support is produced.
Roughened copper foil
The copper foil according to the present invention is a roughened copper foil. The roughened copper foil has a roughened surface on at least one side. The roughened surface has a plurality of peaks that are raised with respect to the reference surface and a plurality of valleys that are recessed with respect to the reference surface. When a three-dimensional image analysis is performed on an image obtained by using a FIB-SEM for a roughened surface and a peak is divided into a plurality of voxels, the surface voxel ratio, which is the ratio of the total volume of voxels constituting the surface of the peak to the total volume of all voxels constituting the peak in an analysis region of 2000nm×2000nm, is 0.25 to 0.60. In addition, when a three-dimensional image analysis is performed on an image obtained by using a FIB-SEM for a roughened surface, the average height of peaks and valleys calculated as the sum of the average heights of peaks and the average heights of valleys in an analysis region of 2000nm×2000nm is 40nm to 90 nm. In this way, in the roughened copper foil, by providing the surface profile in which the surface voxel ratio and the average height of the peaks and valleys are controlled to be within predetermined ranges, excellent transmission characteristics (particularly excellent high-frequency characteristics) and high shear strength (further, high circuit adhesion in terms of shear strength) can be simultaneously achieved in the processing of the copper-clad laminate to the production of the printed wiring board.
It is inherently difficult to achieve both excellent transmission characteristics and high shear strength. This is because, as described above, in order to obtain excellent transmission characteristics, smoothing of the copper foil and miniaturization of the roughened particles are generally required, while in order to improve the shear strength of the circuit, it is generally required to increase the roughened particles. In contrast, the present inventors have found that the roughened copper foil can be three-dimensionally evaluated to control the roughened shape, and the roughened copper foil can have a fine uneven structure that contributes to reduction of transmission loss, while maintaining adhesion between the copper foil and the base material as desired. Such a concave-convex structure can be realized by controlling the surface voxel ratio and the average peak-to-valley height within predetermined ranges.
Although the mechanism is not clear, the following is considered. That is, as described above with reference to fig. 4, the average height of the peaks and valleys represents the sum of the average value of the peak heights and the average value of the valley heights with respect to the reference plane R. That is, the smaller the average height of the peaks and valleys, the smaller the surface irregularities. If the surface irregularities are small, even when the skin depth is reduced by increasing the frequency, the current path becomes less affected by the surface irregularities, and the transmission loss is reduced. As described above, fig. 5 schematically shows the peak (P) of the roughened surface of the roughened copper foil 10 by voxel B 1 、P 2 、P 3 ) An example of the virtual division is performed. Peak P shown in FIG. 5 1 Peak P 2 Peak sum P 3 Since the total volume is the same, the number of voxels B for dividing the peaks is also the same (20). Another partyAt the peak P 1 Peak P 2 Peak sum P 3 Since the number of surface voxels Bs (voxels located at the outermost surface portion in contact with the resin) constituting the surface of the peak is 20, 14, and 10, the surface voxel ratio (ratio of total volume of surface voxels to total volume of all voxels) is 1.0 (=20/20), 0.7 (=14/20), and 0.5 (=10/20), respectively. And according to peak P 3 Peak P 2 Peak P 1 The proportion of the volume occupied in the transverse direction (direction indicated by arrow in fig. 5) (the proportion of the volume other than the surface voxel) is large, so that in this order a greater force from the transverse direction (i.e. in terms of peak P) can be tolerated 3 Peak P 2 Peak P 1 Is high). That is, it can be said that the smaller the surface voxel ratio, the greater the shear strength, with the same total volume of peaks. Since the portion composed of only surface voxels is brittle and easily broken, it is considered that the influence on the shear strength is small. In the case where only the width of the peak of the roughened surface is expressed, the portion composed of only surface voxels, which has little influence on the shear strength, is also included, and thus is insufficient to correspond to the shear strength. Therefore, shear strength is preferably expressed by a surface voxel ratio. Therefore, by controlling both the surface voxel ratio and the average height of the peaks and valleys within the predetermined ranges, excellent transmission characteristics and high shear strength can be realized with good balance when used in a copper-clad laminate or a printed circuit board.
On the other hand, in the prior art, the roughened shape is evaluated using a laser microscope, but there is a limit to accurately evaluating the characteristics of a minute roughened shape by this method. Fig. 6 schematically shows an example of measurement of the roughened surface by a laser microscope. As shown in fig. 6, in the measurement by the laser microscope, laser light is irradiated from above the roughened surface. At this time, there is a region N where laser light cannot be incident due to shielding by the roughened particles 10 a. Because of this region N, it may be difficult to accurately evaluate the characteristics such as the surface area and volume of peaks and valleys in the measurement of the roughened surface using a laser microscope. This problem is remarkable when a minute roughened shape is required that combines excellent transfer characteristics and high circuit adhesion. In addition, in the prior art, a method of three-dimensional evaluation of a sample has been studied, but it is not sufficient as an evaluation method that can achieve both excellent transmission characteristics and high shear strength. In contrast, in the present invention, focusing on the surface voxel ratio and the average height of the peaks and valleys, by controlling these to be in appropriate ranges, when used in a copper-clad laminate or a printed wiring board, excellent transmission characteristics and high shear strength can be simultaneously achieved.
The surface voxel ratio in the roughened surface of the roughened copper foil is 0.25 or more and 0.60 or less from the viewpoint of achieving high shear strength, preferably 0.25 or more and 0.35 or less from the viewpoint of further improving the shear strength, or preferably 0.40 or more and 0.60 or less from the viewpoint of further improving the transmission characteristics.
The average height of peaks and valleys in the roughened surface of the roughened copper foil is 40nm to 90nm, preferably 40nm to 80nm, from the viewpoint of achieving excellent transfer characteristics, more preferably 40nm to 50nm, or from the viewpoint of further improving the transfer characteristics, more preferably 70nm to 80 nm.
Every 1nm in the roughened surface of the roughened copper foil 2 The total volume of the peaks per unit area is preferably 7.0nm 3 Above and 50.0nm 3 Hereinafter, more preferably 30.0nm 3 Above and 50.0nm 3 The following is given. In this way, a high shear strength can be achieved even further in the case of use in copper-clad laminates or printed circuit boards.
From the viewpoint of achieving high shear strength, the sum of the heights of peaks and valleys in the roughened surface of the roughened copper foil is preferably 1.4X10 8 nm 3 Above and 3.5X10 8 nm 3 Hereinafter, from the viewpoint of further improving the shear strength, it is more preferably 2.0X10 8 nm 3 Above and 3.5X10 8 nm 3 Hereinafter, or from the viewpoint of further improving the transmission characteristicsMore preferably 1.4X10 8 nm 3 Above and 1.8X10 8 nm 3 The following is given.
Although the mechanism by which the shear strength can be improved by controlling the sum of the heights of the peaks and valleys is not clear, the following is considered. That is, as described above with reference to fig. 3, the sum of the heights of the peaks and the valleys represents the total volume of the peaks and the valleys with respect to the reference plane R, which corresponds approximately to the volume of the portion in contact with the substrate (the portion entering the substrate). Thus, the greater the sum of the heights of the peaks and valleys, the greater the volume of the portion in contact with the substrate, thereby resulting in an increase in shear strength. In order to achieve both excellent transmission characteristics, it is desirable to control the sum of the heights of the peaks and the valleys to be within the above range when the average heights of the peaks and the valleys are simultaneously achieved.
The thickness of the roughened copper foil is not particularly limited, but is preferably 0.1 μm or more and 35 μm or less, more preferably 0.5 μm or more and 5.0 μm or less, and still more preferably 1.0 μm or more and 3.0 μm or less. The roughened copper foil is not limited to the copper foil roughened on the surface of a conventional copper foil, and may be a copper foil roughened on the surface of a copper foil with a carrier. The roughened copper foil has a thickness (thickness of the copper foil itself constituting the roughened copper foil) of a height not including the roughened particles formed on the surface of the roughened surface. A copper foil having a thickness in the above range is sometimes referred to as an extra thin copper foil.
The roughened copper foil has a roughened surface on at least one side. That is, the roughened copper foil may have roughened surfaces on both sides, or may have roughened surfaces on only one side. Typically, the roughened surface is provided with a plurality of roughened particles (protrusions), and the plurality of roughened particles are preferably each formed of copper particles. The copper particles may be formed of metallic copper or a copper alloy.
The roughening treatment for forming the roughened surface may be more preferably performed by forming roughened particles from copper or a copper alloy on top of the copper foil. The roughening treatment is preferably carried out in accordance with a process that has undergone 3 stagesThe plating method of the plating process is performed. In this case, it is preferable to use a copper sulfate solution having a copper concentration of 5g/L or more and 15g/L or less and a sulfuric acid concentration of 200g/L or more and 250g/L or less in the plating step of the 1 st stage, and to use a copper sulfate solution having a liquid temperature of 25 ℃ or more and 45 ℃ or less and a current density of 2A/dm 2 Above and 4A/dm 2 Electrodeposition was performed under the following plating conditions. In particular, it is preferable that the plating step in the 1 st stage is performed twice in total using two tanks. Preferably, in the plating step of the 2 nd stage, a copper sulfate solution having a copper concentration of 60g/L to 80g/L and a sulfuric acid concentration of 200g/L to 260g/L is used, and the solution temperature is 45 ℃ to 55 ℃ inclusive and the current density is 10A/dm 2 Above and 15A/dm 2 Electrodeposition was performed under the following plating conditions. Preferably, in the plating step of the 3 rd stage, a copper sulfate solution having a copper concentration of 5g/L to 20g/L, a sulfuric acid concentration of 60g/L to 90g/L, a chlorine concentration of 20mg/L to 40mg/L, and a 9-phenylacridine (9 PA) concentration of 100mg/L to 200mg/L is used, and the solution has a current density of 30A/dm at a liquid temperature of 25 ℃ to 35 ℃ inclusive 2 Above and 60A/dm 2 Electrodeposition was performed under the following plating conditions. The plating steps in the 2 nd and 3 rd stages may be performed twice in total using two tanks, but the total is preferably completed 1 time. By undergoing such a plating process, it becomes easy to form protrusions on the treated surface that are suitable for satisfying the surface parameters described above.
The roughened copper foil may be subjected to an anti-rust treatment to form an anti-rust treated layer, as desired. The rust inhibitive treatment preferably includes a plating treatment using zinc. The plating treatment using zinc may be any of a zinc plating treatment and a zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably a zinc-nickel alloy treatment. The zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, cr, co, mo. The Ni/Zn attachment ratio in the zinc-nickel alloy plating is preferably 1.2 to 10, more preferably 2 to 7, still more preferably 2.7 to 4 in terms of mass ratio. In addition, the rust inhibitive treatment further preferably includes a chromate treatment, which is more preferably performed on the surface of the zinc-containing plating layer after the plating treatment with zinc. This can further improve rust resistance. Particularly preferred rust inhibitive treatments are a combination of zinc-nickel alloy plating treatments followed by chromate treatments.
If desired, a silane coupling agent treatment may be performed on the surface of the roughened copper foil to form a silane coupling agent layer. This can improve moisture resistance, chemical resistance, adhesion to adhesives, and the like. The silane coupling agent layer may be formed by appropriately diluting and coating the silane coupling agent and drying it. Examples of the silane coupling agent include: epoxy functional silane coupling agents such as 4-glycidyl butyl trimethoxysilane and 3-glycidoxypropyl trimethoxysilane; or amino-functional silane coupling agents such as 3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyl trimethoxysilane, and N-phenyl-3-aminopropyl trimethoxysilane; or 3-mercaptopropyl trimethoxy silane and other mercapto functional silane coupling agents; or an olefin functional silane coupling agent such as vinyltrimethoxysilane or vinylphenyltrimethoxysilane; or an acrylic functional silane coupling agent such as 3-methacryloxypropyl trimethoxysilane; or imidazole functional silane coupling agents such as imidazole silane; or a triazine functional silane coupling agent such as a triazine silane.
For the above reasons, the roughened copper foil is preferably further provided with a rust-preventive treatment layer and/or a silane coupling agent layer on the roughened surface, and more preferably with both the rust-preventive treatment layer and the silane coupling agent layer. The rust inhibitive treatment layer and the silane coupling agent layer may be formed not only on the roughened surface side of the roughened copper foil but also on the side on which the roughened surface is not formed.
Copper foil with carrier
As described above, the roughened copper foil of the present invention may be provided in the form of a copper foil with a carrier. By adopting the copper foil with carrier, excellent laser processability and fine line circuit formability can be achieved. That is, according to a preferred embodiment of the present invention, there is provided a copper foil with a carrier, comprising: the copper foil is provided with a support, a release layer provided on the support, and the roughened copper foil provided on the release layer so that the roughened surface is outside. Of course, the copper foil with carrier may have a known layer structure in addition to the roughened copper foil of the present invention.
The carrier is a support for supporting the roughened copper foil so as to improve its handling properties, and typically the carrier comprises a metal layer. Examples of such a carrier include aluminum foil, copper foil, stainless steel (SUS) foil, resin film having a surface coated with metal such as copper, glass, and the like, and copper foil is preferable. The copper foil may be either a rolled copper foil or an electrolytic copper foil, and is preferably an electrolytic copper foil. The thickness of the support is typically 250 μm or less, preferably 7 μm or more and 200 μm or less.
The release layer side surface of the support is preferably smooth. That is, in the process for producing a copper foil with a carrier, an extra thin copper foil is formed on the release layer side surface of the carrier (before the roughening treatment). When the roughened copper foil of the present invention is used as a copper foil with a carrier, the roughened copper foil can be obtained by roughening such an extra thin copper foil. Therefore, by smoothing the surface of the carrier on the release layer side in advance, the surface of the outer side of the extra thin copper foil can be smoothed, and by roughening the smooth surface of the extra thin copper foil, it becomes easy to realize a roughened surface having the sum of the heights of the peaks and the valleys and the average height of the peaks and the valleys within the above-described predetermined range. In order to smooth the surface of the carrier on the release layer side, the surface roughness of the cathode used for electrolytic foil forming of the carrier may be adjusted by polishing the surface of the cathode with a polishing wheel of a predetermined model, for example. That is, the surface profile of the cathode thus adjusted is transferred to the electrode surface of the support, and the extra thin copper foil is formed on the electrode surface of the support via the peeling layer, whereby a smooth surface state that can easily achieve the above-described roughened surface can be imparted to the surface on the outer side of the extra thin copper foil. The polishing wheel is preferably a polishing wheel having a model number of #2000 or more and #3000 or less, more preferably #2000 or more and #2500 or less. The electrode surface of the support obtained by using the cathode polished by the polishing wheel of #2000 or more and #2500 or less has slight waviness compared with the smooth foil deposition surface, and thus can ensure adhesion and smoothness, and can realize high adhesion and excellent transfer characteristics with a more balanced property. In addition, from the viewpoint of making the extra thin copper foil smoother and the various surface parameters of the resulting roughened copper foil easier to control in the above-described ranges, the deposition surface side of the carrier obtained by electrolytic foil production using the electrolyte containing the additive may be used as the release layer side surface of the carrier.
The release layer is a layer having the following functions: the peeling strength of the carrier is reduced, the stability of the strength is ensured, and further, the inter-diffusion possibly occurring between the carrier and the copper foil is suppressed at the time of press molding at high temperature. The release layer is typically formed on one side of the carrier, but may be formed on both sides. The release layer may be any one of an organic release layer and an inorganic release layer. Examples of the organic component used in the organic release layer include nitrogen-containing organic compounds, sulfur-containing organic compounds, carboxylic acids, and the like. Examples of the nitrogen-containing organic compound include triazole compounds and imidazole compounds, and among them, triazole compounds are preferable from the viewpoint of easy and stable peeling property. Examples of the triazole compound include 1,2, 3-benzotriazole, carboxybenzotriazole, N' -bis (benzotriazolomethyl) urea, 1H-1,2, 4-triazole, and 3-amino-1H-1, 2, 4-triazole. Examples of the sulfur-containing organic compound include mercaptobenzotriazole, thiocyanuric acid, and 2-benzimidazole mercaptan. Examples of carboxylic acids include monocarboxylic acids and dicarboxylic acids. Examples of the inorganic component used for the inorganic release layer include Ni, mo, co, cr, fe, ti, W, P, zn and a chromate treatment film. The formation of the release layer may be performed by bringing a solution containing the release layer component into contact with at least one surface of the support, fixing the release layer component to the surface of the support, or the like. In the case of bringing the support into contact with the release layer-containing component solution, the contact may be performed by immersing in the release layer-containing component solution, spraying the release layer-containing component solution, flowing down the release layer-containing component solution, or the like. Further, a method of forming a film of a release layer component by a vapor phase method such as vapor deposition or sputtering may be used. The fixation of the release layer component to the surface of the support may be performed by adsorption and drying of a solution containing the release layer component, electrodeposition of the release layer component in the solution containing the release layer component, or the like. The thickness of the release layer is typically 1nm to 1 μm, preferably 5nm to 500 nm.
Other functional layers may be provided between the release layer and the carrier and/or roughened copper foil, as desired. As examples of such other functional layers, an auxiliary metal layer may be cited. The auxiliary metal layer is preferably formed of nickel and/or cobalt. By forming such an auxiliary metal layer on the surface side of the carrier and/or the surface side of the roughened copper foil, it is possible to suppress interdiffusion which may occur between the carrier and the roughened copper foil during hot press molding at high temperature or for a long time, and to ensure the stability of the peel strength of the carrier. The thickness of the auxiliary metal layer is preferably set to 0.001 μm or more and 3 μm or less.
Copper-clad laminate
The roughened copper foil of the present invention is preferably used for producing a copper-clad laminate for a printed wiring board. That is, according to a preferred embodiment of the present invention, there is provided a copper-clad laminate comprising the roughened copper foil. The use of the roughened copper foil of the present invention can achieve both excellent transmission characteristics and high shear strength in the processing of copper-clad laminates. The copper-clad laminate is provided with the roughened copper foil of the present invention, and a resin layer provided in close contact with the roughened surface of the roughened copper foil. The roughened copper foil may be provided on one side or both sides of the resin layer. The resin layer is made of a resin, preferably an insulating resin. The resin layer is preferably a prepreg and/or a resin sheet. The prepreg is a generic term for a composite material obtained by impregnating a synthetic resin into a base material such as a synthetic resin sheet, a glass woven fabric, a glass nonwoven fabric, or paper. Preferable examples of the insulating resin include epoxy resin, cyanate resin, bismaleimide triazine resin (BT resin), polyphenylene ether resin, and phenol resin. Examples of the insulating resin constituting the resin sheet include insulating resins such as epoxy resin, polyimide resin, and polyester resin. In addition, filler particles formed of various inorganic particles such as silica and alumina may be contained in the resin layer from the viewpoint of improving insulation properties and the like. The thickness of the resin layer is not particularly limited, but is preferably 1 μm or more and 1000 μm or less, more preferably 2 μm or more and 400 μm or less, and still more preferably 3 μm or more and 200 μm or less. The resin layer may be composed of a plurality of layers. The resin layer such as prepreg and/or resin sheet may be provided on the roughened copper foil with a primer resin layer previously applied to the surface of the copper foil.
Printed circuit board with improved heat dissipation
The roughened copper foil of the present invention is preferably used for the production of printed circuit boards. That is, according to a preferred embodiment of the present invention, there is provided a printed circuit board comprising the roughened copper foil. The roughened copper foil of the present invention can provide both excellent transmission characteristics and high shear strength in the manufacture of printed wiring boards. The printed circuit board of the present embodiment includes a layer structure in which a resin layer and a copper layer are laminated. The copper layer is a layer derived from the roughened copper foil of the present invention. In addition, the resin layer is as described above for the copper-clad laminate. In any case, the printed circuit board may employ a known layer structure in addition to the roughened copper foil of the present invention. Specific examples of the printed wiring board include a single-sided or double-sided printed wiring board obtained by bonding the roughened copper foil of the present invention to one or both sides of a prepreg, curing the bonded copper foil to form a laminate, and then forming a circuit, and a multilayer printed wiring board obtained by layering the laminate and the double-sided printed wiring board. Further, as other specific examples, there are flexible printed circuit boards, COFs, TAB tapes, and the like in which the roughened copper foil of the present invention is formed on a resin film to form a circuit. As other specific examples, there may be mentioned: forming a resin-coated copper foil (RCC) having the resin layer applied to the roughened copper foil of the present invention, laminating the resin layer as an insulating adhesive material layer on the printed circuit board, and forming a build-up wiring board of a circuit by a modified semi-addition (MSAP) method, an subtractive method or the like using the roughened copper foil as all or a part of the wiring layer; removing the roughened copper foil and forming a laminated circuit board of a circuit by a semi-additive method; a direct lamination wafer (direct build up on wafer) and the like are alternately laminated with resin-coated copper foil and circuit formed on a semiconductor integrated circuit. As a specific example of further extension, there may be mentioned: an antenna element formed by laminating the resin-coated copper foil on a substrate to form a circuit; an electronic material for a panel/display and an electronic material for a window glass, which are laminated on glass or a resin film via an adhesive layer and formed with a pattern; an electromagnetic wave shielding film or the like obtained by applying a conductive adhesive to the roughened copper foil of the present invention. In particular, a printed circuit board provided with the roughened copper foil of the present invention is suitable for use as a high-frequency substrate for use in applications such as an automobile antenna, a mobile phone base station antenna, a high-performance server, and an anti-collision radar, which are used in a high frequency band of 10GHz or more in signal frequency. In particular, the roughened copper foil of the present invention is suitable for the MSAP method. For example, when the circuit formation is performed by the MSAP method, the configuration shown in fig. 1 and 2 may be adopted.
Examples
The present invention will be described more specifically by the following examples.
Examples 1, 2 and 4
The copper foil with carrier having the roughened copper foil was produced as follows.
(1) Preparation of the Carrier
A copper electrolyte, a cathode and DSA (dimensionally stable anode) as an anode were used in the compositions shown below, and the current density was 70A/dm at a solution temperature of 50 DEG C 2 Next, electrolysis was performed to prepare an electrolytic copper foil having a thickness of 18. Mu.m, as a carrier. At this time, as the cathode, an electrode whose surface roughness was adjusted by polishing the surface with a polishing wheel #2000 was used.
Composition of copper electrolyte
Copper concentration: 80g/L
Sulfuric acid concentration: 300g/L
Chlorine concentration: 30mg/L
-gum concentration: 5mg/L
(2) Formation of a release layer
In a CBTA aqueous solution containing Carboxybenzotriazole (CBTA) at a concentration of 1g/L, sulfuric acid at a concentration of 150g/L and copper at a concentration of 10g/L, the electrode surface of the support subjected to acid washing was immersed at a liquid temperature of 30℃for 30 seconds, whereby the CBTA component was adsorbed on the electrode surface of the support. Thus, a CBTA layer was formed as an organic peeling layer on the electrode surface of the support.
(3) Formation of auxiliary metal layer
Immersing the carrier with the organic stripping layer in a solution containing nickel with concentration of 20g/L prepared from nickel sulfate, and heating at 45deg.C, pH3 and current density of 5A/dm 2 Under the conditions of (2) the organic release layer was adhered with nickel in an adhering amount corresponding to a thickness of 0.001. Mu.m. Thereby, a nickel layer is formed as an auxiliary metal layer on the organic peeling layer.
(4) Formation of extra thin copper foil
Immersing the support on which the auxiliary metal layer was formed in a copper solution having the composition shown below at a solution temperature of 50℃and a current density of 5A/dm 2 Above and 30A/dm 2 An extra thin copper foil having a thickness of 1.5 μm was formed on the auxiliary metal layer by electrolysis.
< composition of solution >
Copper concentration: 60g/L
Sulfuric acid concentration: 200g/L
(5) Roughening treatment
The surface of the thus formed extra thin copper foil is roughened to form a roughened copper foil, thereby obtaining a carrier-attached copper foil. Regarding this roughening treatment, the following 3-stage roughening treatments were performed for examples 1 and 2.
The roughening treatment in stage 1 is carried out in two steps. Specifically, an acidic copper sulfate solution having copper concentration and sulfuric acid concentration shown in table 1 was used, and roughening treatment was performed 2 times at the current density and the liquid temperature shown in table 1.
The roughening treatment in stage 2 was performed using an acidic copper sulfate solution having copper concentration and sulfuric acid concentration shown in table 1, at a current density and a liquid temperature shown in table 1.
Stage 3 roughening treatment the roughening treatment was carried out at the current density and liquid temperature shown in table 1 using an acidic copper sulfate solution of copper concentration, sulfuric acid concentration, chlorine concentration and 9-phenylacridine (9 PA) concentration shown in table 1.
On the other hand, the two-stage roughening treatment was performed for example 4. The two-stage roughening treatment includes the following steps: a firing step of depositing and adhering fine copper particles on the extra thin copper foil; and a coating step for preventing the fine copper particles from falling off. In the baking step, carboxybenzotriazole (CBTA) was added to an acidic copper sulfate solution having a copper concentration of 10g/L and a sulfuric acid concentration of 200g/L to give the concentrations shown in Table 1, and roughening treatment was performed at the current densities and liquid temperatures shown in Table 1. In the subsequent coating step, electrodeposition was carried out under a smooth plating condition of a liquid temperature of 52℃and a current density as shown in Table 1 using an acidic copper sulfate solution having a copper concentration of 70g/L and a sulfuric acid concentration of 240 g/L.
(6) Rust-proof treatment
The roughened surface of the obtained copper foil with carrier was subjected to rust-proofing treatment comprising zinc-nickel alloy plating treatment and chromate treatment. First, a solution containing 1g/L of zinc, 2g/L of nickel and 80g/L of potassium pyrophosphate was used, and the current density was 0.5A/dm at a liquid temperature of 40 DEG C 2 The surface of the roughened layer and the carrier is subjected to zinc-nickel alloy plating treatment. Next, an aqueous solution containing 1g/L of chromic acid was used at a pH of 12 and a current density of 1A/dm 2 The surface subjected to the zinc-nickel alloy plating treatment is subjected to chromate treatment.
(7) Silane coupling agent treatment
The silane coupling agent treatment was performed by adsorbing an aqueous solution containing a commercially available silane coupling agent to the surface of the copper foil with carrier on the roughened copper foil side and evaporating water by an electric heater. At this time, the carrier side was not treated with the silane coupling agent.
Example 3
A roughened copper foil was produced in the same manner as in example 1, except for the following a) and b).
a) The following electrolytic copper foil was roughened on the deposition surface to replace the copper foil with carrier.
b) The roughening treatment conditions shown in table 1 were changed.
(preparation of electrolytic copper foil)
An acidic copper sulfate solution of sulfuric acid having the composition shown below was used as a copper electrolyte, an electrode made of titanium having a surface roughness Ra of 0.20 μm was used as a cathode, DSA (dimensionally stable anode) was used as an anode, and the solution temperature was 45℃and the current density was 55A/dm 2 The electrolytic copper foil having a thickness of 12 μm was obtained by electrolysis.
< composition of sulfuric acid copper sulfate solution >
Copper concentration: 80g/L
Sulfuric acid concentration: 260g/L
-bis (3-sulfopropyl) disulfide concentration: 30mg/L
Diallyl dimethyl ammonium chloride polymer concentration: 50mg/L
Chlorine concentration: 40mg/L
Example 5(comparison)
A roughened copper foil was produced in the same manner as in example 3, except that the roughening treatment in the 1 st stage and the 2 nd stage was not performed in the roughening treatment step, and the roughening treatment conditions in the 3 rd stage were changed as shown in table 1.
TABLE 1
Evaluation
The roughened copper foil or the copper foil with carrier produced in examples 1 to 5 were subjected to various evaluations shown below.
(a) Three-dimensional image analysis parameters of roughened surface
By roughening copper foil or copper with carrierThree-dimensional image analysis of roughened surface of foil, and calculation of average peak-to-valley height, sum of peak-to-valley heights, surface voxel ratio, and peak-to-valley height ratio per 1nm 2 Total volume of peaks per unit area. The specific steps are as follows.
(a-1) 3D-SEM observation
Three-dimensional shape data were obtained using a FIB-SEM apparatus (Cross beam540, SEM control: smartSEM Version 6.06with Service Pack 8, FIB control: smartFIB v1.11.0, manufactured by CarlZeiss Co.) under the following measurement conditions in a 10240nm×7680nm region of the roughened surface. The three-dimensional shape data is acquired by: as shown in fig. 7, the cross-sectional image of the roughened copper foil 10 on the dicing surface S parallel to the x-y surface was obtained by setting the x-axis and the z-axis as the in-plane directions of the roughened copper foil 10 and setting the y-axis as the thickness direction of the roughened copper foil 10, and the total of 1000 cross-sectional images in the analysis region were obtained while the dicing surface was moved in parallel at 10nm each time in the z-axis direction. Although the observation is performed under the following conditions, the observation conditions may be appropriately selected and/or changed according to the state (model, etc.) of the apparatus.
< SEM Condition >
Acceleration voltage: 1.0kV
-Working distance：5mm
-tin: 54 ° (Tilt correction with SEM image)
-a detector: inlens detector
-Column Mode：High Resolution
-number of pixels: 2048 (x-direction)
< FIB Condition >)
Acceleration voltage: 30kV
Slice thickness: 10nm (spacing of slice surfaces S)
-setting of voxel size:
the voxel size to be set is determined as (x, y, z) = (5 nm,10 nm). The pixel sizes of x and y can be set according to FIB-SEM conditions, and the magnification is adjusted so that the number of pixels of FIB-SEM multiplied by the number of pixel sizes of x and y is the scale size of FIB-SEM. When the pixel sizes of 2048, x, and y are 5nm and 5nm, the magnification is adjusted so that 2048×5 nm=10240 nm is the scale size of the x-axis of the FIB-SEM. As long as the scale size of the x-axis is determined, the scale size of the y-axis is also determined. Since the voxel size of z is determined by the value of the slice thickness (interval of the slice surface S), when z is to be set to 10nm, the slice thickness is set to 10nm. Note that the voxel size can be determined by appropriately changing the observation magnification by a device (model, software, or the like).
(a-2) 3D-SEM image analysis
Based on the slice image of the three-dimensional shape data of the roughened copper foil obtained by the 3D-SEM, correction of drift was performed by three-dimensional alignment software "ExFact Slice Aligner (version 2.0)" (Nihon Visual Science, manufactured by inc.) so that the observed length in the z-axis became 2 μm or more. For the drift corrected slice image, three-dimensional reconstruction was performed using three-dimensional image analysis software "extract VR (version 2.2)" (manufactured by Nihon Visual Science, inc.). In this case, the analysis region was set to 2000nm×1000nm×2000nm (2000 nm×2000nm in the case of the roughened copper foil 10 in plan view), and the size of each voxel was set to (x, y, z) = (5 nm,10 nm). Then, the shaft was rotated so that the roughened surface was an x-y surface as shown in fig. 8, and then image Analysis was performed by using "foil Analysis (version 1.0)" (manufactured by Nihon Visual Science, inc.) to obtain various data on the roughened surface as described below.
< pre-analysis: determination of peaks and troughs >
And (3) carrying out binarization treatment on the three-dimensional reconstruction data by using a binarization method of Ojin, and separating air and roughening copper foil. And (3) removing noise caused by gaps in the roughened copper foil, deposition cracks during 3D-SEM image acquisition and the like from the obtained binary data, and analyzing the concave-convex structure of the roughened copper foil. A median filter was applied to the roughened copper foil roughness structure, and a roughened surface roughness reference surface was produced. At this time, the matrix size of the median filter is set to 99. Then, respectively oppositeThe portion where the reference surface becomes convex is defined as a peak, and the portion where the reference surface becomes concave is defined as a valley. The peaks and valleys are labeled separately and the average peak to valley height, sum of peak to valley heights, surface voxel ratio, and per 1nm in the analysis region are calculated as follows 2 Total volume of peaks per unit area.
< average height of peaks and valleys in analysis area >
The sum of "plus mean" and "minus mean" calculated by the three-dimensional image Analysis software "foil Analysis (version 1.0)" is set as the average height (voxel value) of the peaks and valleys. Here, "plusMean" represents an average value (voxel value) of the heights of peaks, and "minusMean" represents an average value (voxel value) of the heights of valleys. The average height (nm) of the peaks and valleys in the analysis area was calculated by multiplying the average height (voxel value) of the peaks and valleys obtained by the height (i.e., 5 nm) of each voxel. The results are shown in Table 2.
< sum of heights of peaks and valleys >
The sum of "plusSum" and "minusSum" calculated by the three-dimensional image Analysis software "foil Analysis (version 1.0)" is set as the sum of the heights of the peaks and valleys (voxel value). Here, "plusu" represents the sum of the count pixels (voxels) in the peaks, and "minusu" represents the sum of the count pixels (voxels) in the valleys. The sum of the heights of the peaks and valleys (nm) in the analysis area is calculated by multiplying the sum of the heights of the peaks and valleys (voxel values) by the volume of each voxel (i.e., 5nm×5nm×10 nm) 3 ). The results are shown in Table 2.
< surface voxel ratio >)
As shown in fig. 5, voxels constituting the surface (surface in contact with the atmosphere) of each of the marked peaks are set as surface voxels Bs. Specifically, "volume_voxels_sum" calculated from "voidsSummary_kobu" Excel data generated by Analysis with three-dimensional image Analysis software "foil Analysis (version 1.0)" is set as the total volume (voxel value) of all voxels constituting a peak, and "surface_voxels_sum" is set as the total volume (voxel value) of the surface voxels Bs. The surface voxel ratio in the analysis region is calculated by dividing the total volume of the surface voxels Bs by the total volume of all voxels constituting the peak.
< every 1nm 2 Total volume of peaks per unit area >
The "volume_voxels_sum" calculated from "voidsSummary_kobu" Excel data generated by Analysis with three-dimensional image Analysis software "foil Analysis (version 1.0)", was set as the total volume of peaks (voxel values). The total volume of the peak (nm) was determined by multiplying the total volume of the peak (voxel value) by the volume of each voxel (i.e., 5 nm. Times.5 nm. Times.10 nm) 3 ) By dividing it by the area of the analysis region (2000 nm. Times.2000 nm), each 1nm was calculated 2 Total volume of peaks per unit area (nm 3 ). The results are shown in Table 2.
(b) Shear strength
Using the roughened copper foil or the copper foil with carrier, a laminate for evaluation was produced. Specifically, a copper foil with a carrier or a roughened copper foil was laminated on the surface of an inner layer substrate via a prepreg (GHPL-830 NSF, 30 μm thick, manufactured by Mitsubishi gas chemical Co., ltd.) so as to be in contact with the roughened surface, and was hot-pressed for 90 minutes at a temperature of 220℃under a pressure of 4.0 MPa. Then, in the case of the copper foil with carrier, the carrier was peeled off to obtain a laminate for evaluation.
A dry film was laminated on the above laminate for evaluation, and the laminate was exposed to light and developed. Copper was chromatographed by pattern plating on the laminate masked with the developed dry film, and then the dry film was peeled off. The exposed copper portion was etched using a sulfuric acid-hydrogen peroxide etching solution to prepare a sample for measuring shear strength having a height of 15 μm, a width of 14 μm and a length of 150 μm. The shear strength of the sample for measuring shear strength was measured by using a bond strength tester (4000 Plus bond tester, manufactured by Nordson DAGE Co.). In this case, the test type was a fracture test, and the measurement was performed under conditions of a test height of 5 μm, a descent speed of 0.05mm/s, a test speed of 200 μm/s, a tool movement amount of 0.03mm, and a fracture recognition point of 10%. The obtained shear strength was evaluated in a step manner according to the following criteria, and the evaluation a and B were judged to be acceptable. The results are shown in Table 2.
< shear Strength evaluation criterion >)
-evaluation a: shear strength of 21.3gf/cm or more
-evaluation B: shear strength exceeding 19.9gf/cm and less than 21.3gf/cm
-evaluation C: shear strength of 19.9gf/cm or less
(c) Transmission characteristics
Two prepregs (megron 6, manufactured by Panasonic corporation, actual thickness 68 μm) were stacked, and the both sides thereof were brought into contact with a copper foil with a carrier or a roughened surface of the roughened copper foil, and heat-pressed at 190 ℃ for 90 minutes using a vacuum press. Then, the carrier was peeled off in the case of the copper foil with carrier, to obtain a copper-clad laminate. Copper plating was performed so that the copper thickness of the copper-clad laminate was 18 μm, and a substrate for measuring transmission characteristics on which a microstrip circuit was formed was obtained by a subtractive method.
The obtained substrate for measuring transmission characteristics was subjected to measurement of transmission loss S21 (dB/cm) up to 50GHz by using a network analyzer (PNA-X N5245A, manufactured by Agilent corporation) and selecting a pattern having a characteristic impedance of 50Ω. The average value of the transmission loss amounts in the 45 to 50GHz values was calculated, and the absolute values thereof were evaluated in a stepwise manner according to the following criteria. Then, the transmission characteristics were evaluated as a or B, and the result was judged as acceptable. The results are shown in FIG. 2.
< Transmission characteristic evaluation criterion >)
-evaluation a: the absolute value of the transmission loss is less than 0.455dB/cm
-evaluation B: the absolute value of the transmission loss exceeds 0.455dB/cm and is less than 0.465dB/cm
-evaluation C: the absolute value of the transmission loss is more than 0.465dB/cm
TABLE 2
/>
Claims (11)
1. A roughened copper foil having a roughened surface on at least one side, the roughened surface having a plurality of peaks that are raised with respect to a reference surface and a plurality of valleys that are recessed with respect to the reference surface,
when three-dimensional image analysis is performed on an image obtained by using a FIB-SEM for the roughened surface and the peak is divided into a plurality of voxels, the ratio of the total volume of voxels constituting the surface of the peak to the total volume of all voxels constituting the peak, that is, the surface voxel ratio, in an analysis region of 2000nm×2000nm is 0.25 to 0.60 inclusive,
when performing three-dimensional image analysis on an image obtained by using a FIB-SEM for the roughened surface, the average height of peaks and valleys calculated as the sum of the average heights of the peaks and the average heights of the valleys in an analysis region of 2000nm×2000nm is 40nm to 90 nm.
2. The roughened copper foil according to claim 1, wherein the surface voxel ratio is 0.25 or more and 0.35 or less.
3. The roughened copper foil according to claim 1 or 2, wherein the average height of the peaks and valleys is 40nm or more and 80nm or less.
4. The roughened copper foil according to claim 1 or 2, wherein in the case of performing three-dimensional image analysis on an image obtained using FIB-SEM for the roughened surface, every 1nm 2 The total volume of the peaks per unit area is 7.0nm 3 Above and 50.0nm 3 The following is given.
5. The roughened copper foil according to claim 4, wherein each 1nm 2 The total volume of the peaks per unit area is 30.0nm 3 Above and 50.0nm 3 The following is given.
6. The roughened copper foil according to claim 1 or 2, wherein in the case of performing three-dimensional image analysis on an image obtained by using FIB-SEM for the roughened surface, the three-dimensional image analysis is performed at 2000nm×2000nmThe sum of the heights of the peaks and valleys calculated as the sum of the volumes of the peaks and the volumes of the valleys in the analysis area of (a) is 1.4X10 8 nm 3 Above and 3.5X10 8 nm 3 。
7. The roughened copper foil according to claim 6, wherein the sum of the heights of the peaks and valleys is 2.0 x 10 8 nm 3 Above and 3.5X10 8 nm 3 The following is given.
8. The roughened copper foil according to claim 1 or 2, further comprising an anti-rust treatment layer and/or a silane coupling agent layer on the roughened surface.
9. A copper foil with a carrier, comprising: the roughened copper foil according to claim 1 or 2, wherein the roughened copper foil is provided on the release layer so that the roughened surface is on the outside.
10. A copper-clad laminate comprising the roughened copper foil according to claim 1 or 2.
11. A printed wiring board comprising the roughened copper foil according to claim 1 or 2.
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| JP2021-085490 | 2021-05-20 | ||
| JP2021085490 | 2021-05-20 | ||
| PCT/JP2022/020748 WO2022244827A1 (en) | 2021-05-20 | 2022-05-18 | Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board |
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| CN117321254A true CN117321254A (en) | 2023-12-29 |
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| TW200738913A (en) * | 2006-03-10 | 2007-10-16 | Mitsui Mining & Smelting Co | Surface treated elctrolytic copper foil and process for producing the same |
| JP6373166B2 (en) * | 2014-10-30 | 2018-08-15 | Ｊｘ金属株式会社 | Surface-treated copper foil and laminate |
| CN107002265B (en) | 2015-01-22 | 2019-04-26 | 三井金属矿业株式会社 | Ultrathin copper foil and its manufacturing method with carrier |
| JP6200042B2 (en) * | 2015-08-06 | 2017-09-20 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, printed wiring board manufacturing method and electronic device manufacturing method |
| JP6182584B2 (en) * | 2015-12-09 | 2017-08-16 | 古河電気工業株式会社 | Surface-treated copper foil for printed wiring board, copper-clad laminate for printed wiring board, and printed wiring board |
| JP6462961B2 (en) * | 2016-12-14 | 2019-01-30 | 古河電気工業株式会社 | Surface treated copper foil and copper clad laminate |
| JP6430092B1 (en) * | 2017-05-19 | 2018-11-28 | 三井金属鉱業株式会社 | Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board |
| EP3708696A4 (en) * | 2017-11-10 | 2021-07-21 | Namics Corporation | Composite copper foil |
| KR102480377B1 (en) | 2018-08-10 | 2022-12-23 | 미쓰이금속광업주식회사 | Roughened copper foil, copper foil with carrier, copper-clad laminate and printed wiring board |
| US10581081B1 (en) * | 2019-02-01 | 2020-03-03 | Chang Chun Petrochemical Co., Ltd. | Copper foil for negative electrode current collector of lithium ion secondary battery |
-
2022
- 2022-05-18 CN CN202280035832.XA patent/CN117321254A/en active Pending
- 2022-05-18 KR KR1020237038901A patent/KR20240009404A/en unknown
- 2022-05-18 JP JP2023522711A patent/JPWO2022244827A1/ja active Pending
- 2022-05-18 WO PCT/JP2022/020748 patent/WO2022244827A1/en active Application Filing
- 2022-05-20 TW TW111118884A patent/TWI805378B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2022244827A1 (en) | 2022-11-24 |
| TW202302915A (en) | 2023-01-16 |
| TWI805378B (en) | 2023-06-11 |
| WO2022244827A1 (en) | 2022-11-24 |
| KR20240009404A (en) | 2024-01-22 |
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