WO2022202921A1 - 積層体の製造方法 - Google Patents
積層体の製造方法 Download PDFInfo
- Publication number
- WO2022202921A1 WO2022202921A1 PCT/JP2022/013645 JP2022013645W WO2022202921A1 WO 2022202921 A1 WO2022202921 A1 WO 2022202921A1 JP 2022013645 W JP2022013645 W JP 2022013645W WO 2022202921 A1 WO2022202921 A1 WO 2022202921A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper
- copper member
- base material
- layer
- manufacturing
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 234
- 239000010949 copper Substances 0.000 claims abstract description 175
- 229910052802 copper Inorganic materials 0.000 claims abstract description 169
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 238000007747 plating Methods 0.000 claims abstract description 46
- 238000010030 laminating Methods 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 127
- 239000011347 resin Substances 0.000 claims description 127
- 239000000463 material Substances 0.000 claims description 71
- 229910052751 metal Inorganic materials 0.000 claims description 41
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 36
- 239000005751 Copper oxide Substances 0.000 claims description 35
- 229910000431 copper oxide Inorganic materials 0.000 claims description 35
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 20
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000001228 spectrum Methods 0.000 claims description 10
- 238000010183 spectrum analysis Methods 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000007772 electroless plating Methods 0.000 claims description 5
- DCCWEYXHEXDZQW-BYPYZUCNSA-N (2s)-2-[bis(carboxymethyl)amino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O DCCWEYXHEXDZQW-BYPYZUCNSA-N 0.000 claims description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- ZTVCAEHRNBOTLI-UHFFFAOYSA-L Glycine, N-(carboxymethyl)-N-(2-hydroxyethyl)-, disodium salt Chemical compound [Na+].[Na+].OCCN(CC([O-])=O)CC([O-])=O ZTVCAEHRNBOTLI-UHFFFAOYSA-L 0.000 claims description 4
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 4
- MLDWGLQSBBCMMO-UHFFFAOYSA-N [Na].[Na].[Na].CNCC(=O)O Chemical compound [Na].[Na].[Na].CNCC(=O)O MLDWGLQSBBCMMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 238000005102 attenuated total reflection Methods 0.000 claims description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 239000000176 sodium gluconate Substances 0.000 claims description 4
- 235000012207 sodium gluconate Nutrition 0.000 claims description 4
- 229940005574 sodium gluconate Drugs 0.000 claims description 4
- DTXLBRAVKYTGFE-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)-3-hydroxybutanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)C(O)C(C([O-])=O)NC(C([O-])=O)CC([O-])=O DTXLBRAVKYTGFE-UHFFFAOYSA-J 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- VCVKIIDXVWEWSZ-YFKPBYRVSA-N (2s)-2-[bis(carboxymethyl)amino]pentanedioic acid Chemical compound OC(=O)CC[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O VCVKIIDXVWEWSZ-YFKPBYRVSA-N 0.000 claims description 3
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 139
- 239000002585 base Substances 0.000 description 89
- 239000011889 copper foil Substances 0.000 description 61
- 239000002131 composite material Substances 0.000 description 35
- 229960004643 cupric oxide Drugs 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 31
- 125000004429 atom Chemical group 0.000 description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 238000009713 electroplating Methods 0.000 description 21
- 238000007254 oxidation reaction Methods 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 17
- 239000010408 film Substances 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 238000005530 etching Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 9
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 235000011181 potassium carbonates Nutrition 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 150000004032 porphyrins Chemical class 0.000 description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 description 5
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 5
- 229940112669 cuprous oxide Drugs 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 5
- 229960002218 sodium chlorite Drugs 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 101001134276 Homo sapiens S-methyl-5'-thioadenosine phosphorylase Proteins 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 102100022050 Protein canopy homolog 2 Human genes 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000002788 crimping Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 229920001955 polyphenylene ether Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- -1 porphyrin macrocycles Chemical class 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- NVEYHJNJWCDNIJ-UHFFFAOYSA-N CO[Si](CCCNC(=O)N)(OC)OC.CO[Si](CCCNC(=O)N)(OC)OC Chemical compound CO[Si](CCCNC(=O)N)(OC)OC.CO[Si](CCCNC(=O)N)(OC)OC NVEYHJNJWCDNIJ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- KXJLGCBCRCSXQF-UHFFFAOYSA-N [diacetyloxy(ethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(OC(C)=O)OC(C)=O KXJLGCBCRCSXQF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002577 polybenzoxazole Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
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- 229920006259 thermoplastic polyimide Polymers 0.000 description 2
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- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-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
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- KEJFADGISRFLFO-UHFFFAOYSA-N 1H-indazol-6-amine Chemical compound NC1=CC=C2C=NNC2=C1 KEJFADGISRFLFO-UHFFFAOYSA-N 0.000 description 1
- JVVRJMXHNUAPHW-UHFFFAOYSA-N 1h-pyrazol-5-amine Chemical compound NC=1C=CNN=1 JVVRJMXHNUAPHW-UHFFFAOYSA-N 0.000 description 1
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 description 1
- NDELSWXIAJLWOU-UHFFFAOYSA-N 2,5-dimethyl-4h-pyrazol-3-one Chemical compound CN1N=C(C)CC1=O NDELSWXIAJLWOU-UHFFFAOYSA-N 0.000 description 1
- CGZDWVZMOMDGBN-UHFFFAOYSA-N 2-Ethylthiazole Chemical compound CCC1=NC=CS1 CGZDWVZMOMDGBN-UHFFFAOYSA-N 0.000 description 1
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 1
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- XRPDDDRNQJNHLQ-UHFFFAOYSA-N 2-ethyl-1h-pyrrole Chemical compound CCC1=CC=CN1 XRPDDDRNQJNHLQ-UHFFFAOYSA-N 0.000 description 1
- VZWOXDYRBDIHMA-UHFFFAOYSA-N 2-methyl-1,3-thiazole Chemical compound CC1=NC=CS1 VZWOXDYRBDIHMA-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
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- GUABFMPMKJGSBQ-UHFFFAOYSA-N 5-methyl-1,3-thiazol-2-amine Chemical compound CC1=CN=C(N)S1 GUABFMPMKJGSBQ-UHFFFAOYSA-N 0.000 description 1
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- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 1
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- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 1
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- 238000001069 Raman spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
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- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
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- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
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- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- MILMJAFFMWCPLL-UHFFFAOYSA-J sodium;chromium(3+);disulfate Chemical compound [Na+].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MILMJAFFMWCPLL-UHFFFAOYSA-J 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 239000013076 target substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DRKXDZADBRTYAT-DLCHEQPYSA-J tetrasodium (2S)-2-[bis(carboxymethyl)amino]pentanedioate Chemical compound C(=O)(O)CN([C@@H](CCC(=O)[O-])C(=O)[O-])CC(=O)O.[Na+].[Na+].[Na+].[Na+].C(=O)(O)CN([C@@H](CCC(=O)[O-])C(=O)[O-])CC(=O)O DRKXDZADBRTYAT-DLCHEQPYSA-J 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GZNAASVAJNXPPW-UHFFFAOYSA-M tin(4+) chloride dihydrate Chemical compound O.O.[Cl-].[Sn+4] GZNAASVAJNXPPW-UHFFFAOYSA-M 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Substances O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
-
- 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
- C25D5/02—Electroplating of selected surface areas
-
- 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
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
-
- 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
- C25D7/12—Semiconductors
- C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/108—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by semi-additive methods; masks therefor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
-
- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/072—Electroless plating, e.g. finish plating or initial plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
Definitions
- the present invention relates to a method for manufacturing a laminate.
- the SAP method it is common to form a seed layer made of copper on a resin substrate. Roughened by processing. At this time, the surface roughness (Ra) of the roughened surface of the insulating resin layer is 300 nm or more. Subsequently, a seed layer made of copper is formed on the insulating resin layer by electroless plating or the like. Next, a resist is formed on the portion of the seed layer where the wiring layer is not arranged. Further, a thick copper plating layer is formed by electroplating on the portions where the resist is not formed. Finally, after removing the resist, the exposed seed layer is etched. Thereby, a wiring pattern composed of the seed layer and the metal plating layer is formed on the resin substrate (see FIG. 1A).
- An object of the present invention is to provide a novel method for manufacturing a laminate.
- One embodiment of the present invention is a method for manufacturing an insulating substrate layer and a copper laminate, comprising the steps of bonding the insulating substrate layer and a copper member having protrusions on the surface thereof; forming a seed layer by transferring the projections to the surface of the insulating base layer by peeling off; forming a resist on a predetermined location on the surface of the seed layer; and forming a resist on the surface of the seed layer. a step of laminating the copper by copper plating a region where the resist is not laminated, a step of removing the resist, and a step of removing the seed layer exposed by removing the resist.
- a manufacturing method comprising: The protrusions on the surface of the copper member may be formed on the surface of the copper member by chemical treatment. Projections may not be formed on the surface of the insulating base layer by the desmear treatment.
- the copper plating treatment may be electrolytic copper plating treatment.
- a step of electroless plating the surface of the seed layer may be performed between the step of forming the seed layer and the step of forming the resist.
- the insulating base layer and the copper member may be bonded together by thermocompression bonding.
- the S/N ratio of the peak corresponding to the substance derived from the resin substrate to be detected may be 10 or less or 7 or less.
- FT-IR/ATR method attenuated total reflection absorption Fourier transform infrared spectroscopy
- a total of main peak intensities of the metal elements detected from the surface of the resin base material from which the copper member has been peeled off may be greater than the peak intensity of C1s.
- [Surface atomic composition percentage (Atom%) of metal elements]/[C1s surface atomic composition percentage (Atom%)] calculated from the XPS measurement may be 0.03 or more, or 0.04 or more.
- the total surface atomic composition percentage of Cu2p3 and Ni2p3 was 3.0 atom%. or more, or 1.5 atom % or more.
- the surface atomic composition percentage of Cu2p3 is 2.8 atom % or more, or 1. It may be 0 atom % or more.
- the copper member having protrusions on the surface is obtained by: 1) partially coating the surface of the copper member as a material with a silane coupling agent or an antiseptic; and 2) oxidizing the partially coated surface. may be formed by a step of forming a layer containing copper oxide.
- the copper member having protrusions on the surface is formed by: 1) forming a layer containing copper oxide by oxidizing the surface of the copper member as a material; a step of treating with a dissolving agent that dissolves the copper oxide.
- the dissolving agent is Ni chloride, zinc chloride, iron chloride, chromium chloride, ammonium citrate, ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, diethanolglycine, L-glutamic acid diacetate/tetrasodium, ethylenediamine.
- -N,N'-disuccinic acid sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate and It may be selected from the group consisting of sodium gluconate.
- FIG. 1A is a schematic diagram showing a method of manufacturing a laminate in one embodiment of the present invention in comparison with a conventional SAP method.
- FIG. 1B is a schematic diagram of a seed layer, in accordance with one embodiment of the present invention.
- the gray portion represents the insulating substrate layer
- the black portion represents the portion of the copper member transferred to the insulating substrate layer.
- FIG. 2 shows the results of visual observation after the composite copper foils of Examples 1 to 8 and Comparative Examples 2 to 4 were crimped to the resin substrate and then peeled off (when the surface of the copper foil was transferred to the resin side , and X when not transferred), and representative photographs of the surfaces on both sides.
- FIG. 3 shows the results of XPS analysis of the resin substrates of Examples 1-3 and Comparative Examples 1-4.
- FIG. 4 shows the results of measuring the surface of the composite copper foils of Examples 1 to 3 and Comparative Examples 2 to 4 by the FT-IR/ATR method after thermal compression bonding to a resin substrate (R5670KJ) and peeling.
- FIG. 5 shows the results of measuring the surfaces of the composite copper foils of Example 3 and Comparative Example 3 by the FT-IR/ATR method after being thermally pressed onto a resin substrate (R1551GG) and peeled off.
- FIG. 6 shows the results of measuring the surfaces of the composite copper foils of Examples 4 to 8 by the FT-IR/ATR method after the composite copper foils of Examples 4 to 8 were thermally bonded to a resin base material (R5680J) and peeled off.
- FIG. 7 shows the results of measurement of the surfaces of the composite copper foils of Example 3 and Comparative Example 3 by the FT-IR/ATR method after the composite copper foils of Example 3 and Comparative Example 3 were thermally bonded to a resin substrate (NX9255) and peeled off.
- FIG. 8 shows the results of measuring the surface of the composite copper foils of Example 3 and Comparative Example 3 by the FT-IR/ATR method after the composite copper foils of Example 3 and Comparative Example 3 were thermally bonded to a resin substrate (CT-Z) and then peeled off.
- FIG. 9 shows a laminated wiring circuit board manufactured in one example of the present invention.
- An embodiment of the disclosure of the present specification is a method for manufacturing an insulating substrate layer and a copper laminate, comprising a step of bonding an insulating substrate layer and a copper member having protrusions on the surface; A step of transferring the projections to the surface of the insulating base layer by peeling off to form a seed layer; a step of forming a resist at a predetermined location on the surface of the seed layer; A manufacturing method comprising the steps of depositing copper by copper plating the areas where the resist is not deposited, removing the resist, and removing the seed layer exposed by removing the resist. .
- the seed layer refers to the surface of the peeled copper member and the surface configured to include the bottom of the recesses formed in the insulating base layer by the protrusions of the copper member. Refers to the layer formed in between (FIG. 1B), so that the recess and the metal from the copper member transferred to the recess are contained within that layer.
- the bottom of the recess refers to the farthest bottom from the surface of the stripped copper member among the bottoms of the plurality of recesses, and the surface configured to include the bottom of the recess is the surface of the stripped copper member. parallel to the surface.
- Step of bonding an insulating base layer and a copper member ⁇ copper member> The surface of the copper member has fine protrusions.
- the arithmetic mean roughness (Ra) of the surface of the copper member is preferably 0.03 ⁇ m or more, more preferably 0.05 ⁇ m or more, and is preferably 0.3 ⁇ m or less, more preferably 0.2 ⁇ m or less. .
- the maximum height roughness (Rz) of the surface of the copper member is preferably 0.2 ⁇ m or more, more preferably 1.0 ⁇ m or more, and is preferably 2.0 ⁇ m or less, more preferably 1.7 ⁇ m or less. preferable.
- Ra and Rz are too small, the adhesion to the resin substrate will be insufficient, and if they are too large, fine wiring formability and high frequency characteristics will be inferior.
- Ra and Rz can be calculated by the method specified in JIS B 0601:2001 (in accordance with the international standard ISO4287-1997).
- the average length (RSm) of the surface roughness curve element of the copper member is not particularly limited, but is 1500 nm or less, 1400 nm or less, 1300 nm or less, 1200 nm or less, 1100 nm or less, 1000 nm or less, 900 nm or less, 800 nm or less, 750 nm or less, It is preferably 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 450 nm or less, or 350 nm or less, and preferably 100 nm or more, 200 nm or more, or 300 nm or more.
- RSm represents the average length of unevenness for one cycle included in the roughness curve at a certain reference length (lr) (that is, the length of the contour curve element: Xs1 to Xsm), It is calculated by the following formula.
- RSm can be measured and calculated according to "Method for measuring surface roughness of fine ceramic thin film by atomic force microscope (JIS R 1683:2007)".
- the copper member is preferably a composite copper member having a layer containing copper oxide formed on at least a part of its surface.
- the copper member specifically includes, but is not limited to, copper foils such as electrolytic copper foil, rolled copper foil, and copper foil with a carrier, copper wires, copper plates, and copper lead frames.
- the copper member contains Cu as a main component, which is part of the structure, but a material made of pure copper with a Cu purity of 99.9% by mass or more is preferable, and is made of tough pitch copper, deoxidized copper, or oxygen-free copper. More preferably, it is made of oxygen-free copper with an oxygen content of 0.001% by mass to 0.0005% by mass.
- the copper member is a copper foil
- its thickness is not particularly limited, but is preferably 0.1 ⁇ m or more and 100 ⁇ m or less, more preferably 0.5 ⁇ m or more and 50 ⁇ m or less.
- the layer containing copper oxide is formed on the surface of the copper member and contains copper oxide (CuO) and/or cuprous oxide (Cu 2 O).
- This layer containing copper oxide can be formed by oxidizing the surface of the copper member. This oxidation treatment roughens the surface of the copper member.
- a surface roughening treatment step such as soft etching or etching is not necessary, but may be performed.
- degreasing treatment acid cleaning for uniformizing the surface by removing a natural oxide film, or alkali treatment for preventing acid from being brought into the oxidation process may be performed after acid cleaning.
- the method of alkali treatment is not particularly limited, but preferably 0.1 to 10 g/L, more preferably 1 to 2 g/L alkaline aqueous solution, such as sodium hydroxide aqueous solution, at 30 to 50 ° C. for 0.5 to 2 minutes. It should be treated to some extent.
- the oxidizing agent is not particularly limited, and for example, an aqueous solution of sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, etc. can be used.
- Various additives eg, phosphates such as trisodium phosphate dodecahydrate
- surface active molecules may be added to the oxidizing agent.
- Surface active molecules include porphyrins, porphyrin macrocycles, extended porphyrins, ring contracted porphyrins, linear porphyrin polymers, porphyrin sandwich coordination complexes, porphyrin sequences, silanes, tetraorgano-silanes, aminoethyl-aminopropyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea) ((l-[3-(Trimethoxysilyl)propyl]urea)), (3-aminopropyl)triethoxysilane , ((3-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)
- the protrusions on the surface of the oxidized copper member may be adjusted using a dissolving agent.
- the dissolving agent used in this dissolving step is not particularly limited, but is preferably a chelating agent, particularly a biodegradable chelating agent, such as ethylenediaminetetraacetic acid, diethanolglycine, tetrasodium L-glutamic acid diacetate, ethylenediamine-N,N'.
- the pH of the solution for dissolution is not particularly limited, but it is preferably alkaline, more preferably pH 8 to 10.5, still more preferably pH 9.0 to 10.5, and pH 9.8 to 10.5. 2 is more preferred.
- the surface of the layer containing copper oxide may be subjected to reduction treatment with a reducing agent, in which case cuprous oxide may be formed on the surface of the layer containing copper oxide.
- a reducing agent in which case cuprous oxide may be formed on the surface of the layer containing copper oxide.
- the reducing agent used in this reduction step include dimethylamine borane (DMAB), diborane, sodium borohydride, hydrazine and the like.
- Pure copper has a specific resistance of 1.7 ⁇ 10 -8 ( ⁇ m), while copper oxide has a specific resistance of 1 to 10 ( ⁇ m).
- Cuprous oxide is 1 ⁇ 10 6 to 1 ⁇ 10 7 ( ⁇ m), so the layer containing copper oxide has low conductivity. At most, transmission loss due to the skin effect is less likely to occur when forming a circuit of a printed wiring board or a semiconductor package substrate using the copper member according to the present invention.
- the layer containing copper oxide may contain a metal other than copper.
- the contained metal is not particularly limited, but contains at least one metal selected from the group consisting of Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au and Pt. good too.
- metals having higher acid resistance and heat resistance than copper such as Ni, Pd, Au and Pt.
- a layer containing a metal other than copper may be formed on the layer containing copper oxide.
- This layer can be formed on the outermost surface of the copper member by plating.
- the plating method is not particularly limited. Plating can be performed by electrolytic plating, electroless plating, vacuum deposition, chemical conversion treatment, or the like, but electrolytic plating is preferred because it is preferable to form a uniform and thin plating layer.
- nickel plating and nickel alloy plating are preferable.
- Metals formed by nickel plating and nickel alloy plating include, for example, pure nickel, Ni—Cu alloy, Ni—Cr alloy, Ni—Co alloy, Ni—Zn alloy, Ni—Mn alloy, Ni—Pb alloy, Ni— P alloy etc. are mentioned.
- metal salts used for plating include nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, zinc oxide, zinc chloride, diamminedichloropalladium, iron sulfate, iron chloride, chromic anhydride, chromium chloride, sodium chromium sulfate, copper sulfate, copper pyrophosphate, cobalt sulfate, manganese sulfate, and the like;
- the bath composition is, for example, nickel sulfate (100 g/L or more and 350 g/L or less), nickel sulfamate (100 g/L or more and 600 g/L or less), nickel chloride (0 g/L or more and 300 g/L or less). and mixtures thereof are preferred, but sodium citrate (0 g/L or more and 100 g/L or less) or boric acid (0 g/L or more and 60 g/L or less) may be contained as additives.
- the copper oxide on the surface is first reduced, and an electric charge is used to turn it into cuprous oxide or pure copper. After that, the metal that forms the metal layer begins to deposit.
- the amount of charge varies depending on the type of plating solution and the amount of copper oxide. For example, when Ni plating is applied to a copper member, 10 C per area dm 2 of the copper member to be electrolytically plated is required to keep the thickness within a preferable range. It is preferable to apply an electric charge of 90C or more, and it is more preferable to apply an electric charge of 20C or more and 65C or less.
- the amount of metal deposited on the outermost surface of the copper member by plating is not particularly limited, it is preferably 0.8 to 6.0 mg/dm 2 .
- the amount of adhered metal can be calculated by, for example, dissolving in an acidic solution, measuring the amount of metal by ICP analysis, and dividing the amount by the plane visual field area of the structure.
- the surface of the copper member is partially coated with a coating agent such as a silane coupling agent or an antiseptic before the oxidation treatment; Steps such as treating the oxide-containing layer with a dissolving agent may be performed.
- a coating agent such as a silane coupling agent or a preservative
- the portion is prevented from being subjected to oxidation treatment, and voids are generated in the layer containing copper oxide, and the copper is removed from the copper member.
- Layers containing oxides tend to break.
- the dissolving agent is an agent that dissolves copper oxide, and by treating with the dissolving agent, the copper oxide near the interface between the copper member and the layer containing copper oxide is partially dissolved, The layer containing copper oxide is likely to break from the copper member.
- Silane coupling agents are not particularly limited, but silane, tetraorgano-silane, aminoethyl-aminopropyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea ) ((l-[3-(Trimethoxysilyl)propyl]urea)), (3-aminopropyl)triethoxysilane, ((3-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriacetoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane
- Rust inhibitors are not particularly limited, but 1H-tetrazole, 5-methyl-1H-tetrazole, 5-amino-1H-tetrazole, 5-phenyl-1H-tetrazole, 1,2,3-triazole, 1,2,4 -triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 5-amino-1H-benzotriazole, 2-mercaptobenzothiazole, 1,3-dimethyl-5-pyrazolone, pyrrole, 3- methylpyrrole, 2,4-dimethylpyrrole, 2-ethylpyrrole, pyrazole, 3-aminopyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole, thiazole, 2-aminothiazole, 2-methylthiazole, 2- amino-5-methylthiazole, 2-ethylthiazole, benzothiazole, imidazole, 2-methylimidazole, 2-ethylimid
- the treatment with a silane coupling agent or antiseptic may be performed at any time before the oxidation treatment, such as degreasing, acid cleaning for uniform treatment by removing the native oxide film, or acid to the oxidation process after acid cleaning.
- the dissolving agent for making it easier to break the layer containing copper oxide from the copper member is not limited to Ni chloride, as long as it contains a component that dissolves copper oxide, and chlorides (potassium chloride, zinc chloride , iron chloride, chromium chloride, etc.), ammonium salts (ammonium citrate, ammonium chloride, ammonium sulfate, nickel ammonium sulfate, etc.), chelating agents (ethylenediaminetetraacetic acid, diethanolglycine, L-glutamic acid diacetic acid/tetrasodium, ethylenediamine-N, N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, sodium gluconate etc.), tin(II) chloride, and citric acid.
- the copper member on which the layer containing copper oxide is formed is immersed in a Ni chloride solution (concentration of 45 g/L or more) at room temperature or at a temperature higher than room temperature for 5 seconds or more. is preferred.
- a Ni chloride solution concentration of 45 g/L or more
- treatment may be performed simultaneously with oxidation treatment, or treatment may be performed simultaneously with plating treatment after oxidation treatment.
- Ni chloride is contained in the plating solution, and a layer containing copper oxide is formed in the plating solution for 5 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, 1 minute, or 2 minutes before plating.
- the formed copper member may be immersed.
- the immersion time can be appropriately changed depending on the oxide film thickness.
- the base material of the insulating base material layer should be such that when the surface of the copper member on which the unevenness is formed is bonded to the insulating base material layer, the surface profile including the uneven shape of the copper member is transferred to the resin base material.
- a resin substrate is preferable.
- the resin base material is a material containing resin as a main component, but the type of resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin, polyphenylene ether (PPE), Epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), thermoplastic polyimide (TPI), fluororesin, polyetherimide, polyetheretherketone, polycyclo Olefins, bismaleimide resins, low dielectric constant polyimides, cyanate resins, or mixed resins thereof can be exemplified.
- the resin base material may further contain an inorganic filler or glass fiber.
- the dielectric constant of the insulating substrate layer used is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.8 or less.
- the surface of the copper member having the unevenness is attached to the insulating substrate layer, the surface profile including the uneven shape of the copper member is transferred to the resin substrate. Accordingly, recesses that complement the protrusions on the surface of the copper member and protrusions that complement the recesses are formed on the surface of the insulating base layer.
- the bonding method is not particularly limited, but thermal press fitting is preferred.
- the resin base material and the copper member may be adhered and laminated, and then heat treated under predetermined conditions.
- predetermined conditions eg, temperature, pressure, time, etc.
- Predetermined conditions include, for example, the following conditions.
- a copper member is heated to the resin base material by applying a pressure of 0 to 20 MPa at a temperature of 50 ° C. to 300 ° C. for 1 minute to 5 hours. Crimping is preferred.
- the resin substrate is GX13 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), it is heated while being pressurized at 1.0 MPa and held at 180° C. for 60 minutes for thermocompression bonding.
- the resin base material contains or consists of a PPE resin
- a copper member is attached to the resin base material by applying a pressure of 0 to 20 MPa at a temperature of 50° C. to 350° C. for 1 minute to 5 hours. Thermocompression bonding is preferred.
- thermocompression bonding for example, 2-1
- the resin base material is R5620 (manufactured by Panasonic)
- thermocompression bonding When the resin base material is R5670 (manufactured by Panasonic), After thermocompression bonding while heating to 110° C. under a pressure of 0.49 MPa, the temperature and pressure are increased, and thermocompression bonding is performed by holding at 2.94 MPa and 210° C. for 120 minutes.
- the temperature and pressure are increased to 3.0 to 4.0 MPa after thermocompression bonding while heating to 110 ° C. under a pressure of 0.5 MPa. , and 195° C. for 75 minutes for thermocompression bonding.
- the heat of the copper member is applied to the resin base material by applying a pressure of 0 to 20 MPa at a temperature of 50 ° C. to 400 ° C. for 1 minute to 5 hours. Crimping is preferred.
- a copper member is formed on the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50 ° C. to 400 ° C. for 1 minute to 5 hours.
- Heat crimping is preferred.
- the resin substrate is CT-Z (manufactured by Kuraray)
- it is heated under a pressure of 0 MPa, held at 260 ° C. for 15 minutes, further heated while being pressurized at 4 MPa, and held at 300 ° C. for 10 minutes. heat press.
- Step of peeling off the copper member After the copper member is attached to the insulating base layer, when the copper member is peeled off from the insulating base layer under predetermined conditions, the protrusions on the surface of the copper member are removed from the insulating base layer. to form a seed layer on the surface of the insulating base layer. Therefore, the surface of the insulating base layer becomes flat.
- the thickness of the seed layer may be 2.50 ⁇ m or less, more preferably 2.00 ⁇ m or less, and even more preferably 1.70 ⁇ m or less. Moreover, it is preferably 0.01 ⁇ m or more, more preferably 0.10 ⁇ m or more, and even more preferably 0.36 ⁇ m or more. If the thickness is less than 0.01 ⁇ m, the plating formability is poor and the adhesion to the insulating substrate is lowered. If it exceeds 2.50 ⁇ m, the wiring formability is deteriorated.
- the method for measuring the thickness of the seed layer is not particularly limited, and for example, the thickness of the seed layer may be measured in the SEM image.
- the seed layer thus produced is used as it is as part of the circuit.
- the adhesion between the copper and the insulating base layer is improved.
- the conditions for peeling off the copper member from the insulating base layer are not particularly limited, but a 90° peeling test (Japanese Industrial Standards (JIS) C5016 "Flexible printed wiring board test method"; corresponding international standards IEC249-1: 1982, IEC326- 2:1990).
- the method of peeling off the copper member from the insulating base material layer is not particularly limited, but a machine may be used, or a manual operation may be performed.
- the metal transferred to the surface of the insulating substrate layer after peeling off the copper member can be analyzed by various methods (e.g., X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), ICP emission spectroscopy). (Inductively Coupled Plasma Emission Spectroscopy, ICP-OES/ICP-AES)).
- XPS X-ray photoelectron spectroscopy
- EDS energy dispersive X-ray spectroscopy
- ICP emission spectroscopy ICP emission spectroscopy
- ICP-OES/ICP-AES Inductively Coupled Plasma Emission Spectroscopy
- XPS is a technique for performing energy analysis by irradiating an object with X-rays and capturing photoelectrons e ⁇ emitted as the object is ionized.
- XPS it is possible to examine the types, abundances, chemical bonding states, etc. of elements present on the surface of the sample or from the surface to a predetermined depth (for example, up to a depth of 6 nm).
- the diameter of the analysis spot (that is, the diameter of the cross section of the cylindrical portion that can be analyzed so that the cross section is circular) is suitably 1 ⁇ m or more and 1 mm or less.
- the metal atoms contained in the layer containing copper oxide may be detected from the surface of the insulating base material from which the copper member has been peeled off by XPS Survey spectrum analysis.
- the metal contained in the convex part of the copper member is insulated so as to fill 70% or more, 80% or more, 90% or more, 95% or more, 99% or more, or 99.9% or more of the concave part of the transferred surface profile. Transfer to the substrate layer is preferred.
- the metal fills most of the recesses in the insulating base layer, when the surface of the insulating base layer is measured by XPS, the total peak intensity of the main peaks of the spectrum of metal atoms is higher than the peak intensity of the main peak of the spectrum of C1s. will also grow.
- the main peak is the peak with the highest intensity among multiple peaks of the metal element.
- Cu is 2p3 orbital
- Sn is 3d5 orbital
- Ag is 3d5 orbital
- Zn is 2p3 orbital
- Al is 2p orbital
- Ti is 2p3 orbital
- Bi is 4f7 orbital
- Cr is 2p3 orbital
- Fe is 2p3 orbital
- Co is 2p3
- the main peak is the 2p3 orbital of Ni, the 3d5 orbital of Pd, the 4f7 orbital of Au, and the 4f7 orbital of Pt.
- the peak intensity of the spectrum referred to here means the height in the vertical axis direction of the XPS spectrum data.
- the ratio of Cu2p3 to the total atoms on the surface of the insulating base layer from which the copper member is peeled off, measured by X-ray photoelectron spectroscopy (XPS), is 1.0 atom% or more, 1.8 atom% or more, and 2.8 atom% or more. , 3.0 atom % or more, 4.0 atom % or more, 5.0 atom % or more, or 6.0 atom %.
- the ratio of the surface atomic composition percentage of Cu2p3 / the surface atomic composition percentage of C1s is 0.010 or more, 0.015 or more, 0.020 or more, 0 It is preferably 0.025 or more, 0.030 or more, 0.035 or more, 0.040 or more, 0.045 or more, 0.050 or more, or 0.10 or more.
- the total atomic composition percentage of the metal atoms on the surface of the peeled insulating base layer measured by X-ray photoelectron spectroscopy (XPS) is 1.0 atom. % or more, 1.5 atom % or more, 1.8 atom % or more, 2.8 atom % or more, 3.0 atom % or more, 4.0 atom % or more, 5.0 atom % or more, or 6.0 atom %.
- the value of the ratio of (total atomic composition percentage of metal atoms on the surface of the peeled insulating base layer):(atomic composition percentage of C1s on the surface of the peeled insulating base layer) is 0.010. 0.015 or more, 0.020 or more, 0.025 or more, 0.030 or more, 0.035 or more, 0.040 or more, 0.045 or more, 0.050 or more, or 0.10 or more preferable.
- the amount of substances derived from the insulating base layer detected from the surface of the copper member peeled off from the insulating base layer is preferably below the detection limit or, if detected, is a small amount. This is because, in that case, when the copper member is peeled off, breakage in the insulating base material layer can be sufficiently suppressed.
- the method for detecting substances derived from the insulating base layer is not particularly limited, and a method suitable for the target substance may be used. For example, in the case of organic substances, attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR method) ("Infrared and Raman Spectroscopy: Principles and Spectral Interpretation" by Peter Larkin).
- the FT - IR method is an infrared spectroscopic method in which the substance to be measured is irradiated with infrared rays, and the compound is identified and / or quantified using the infrared absorption spectrum.
- the N ratio is preferably 10 or less and 9 or less, more preferably 8 or less and 7 or less, and preferably no peak derived from the resin substrate is detected.
- the ratio of Ra after peeling to Ra before bonding on the surface of the copper member on which the layer having the protrusions is formed is less than 100%, less than 96%, less than 95%, less than 94%, less than 93%, and 92%. preferably less than, less than 91%, less than 90%, less than 80%, less than 70%, less than 65% or less than 60%.
- a smaller ratio means that the metal forming the layer having protrusions transferred to the insulating base layer.
- the ratio of the surface area after peeling to the surface area before bonding of the copper member on which the layer having the convex portion is formed is less than 100%, less than 98%, less than 97%, less than 96%, less than 95%, less than 94%. , less than 93%, less than 92%, less than 91%, less than 90%, less than 80% or less than 75%.
- a smaller ratio means that the metal forming the layer having protrusions transferred to the insulating base layer.
- the surface area can be measured using a confocal microscope or an atomic force microscope.
- ⁇ E * ab between the surface of the copper member before thermocompression bonding and the surface of the copper member after peeling is 13 or more, 15 or more, 20 or more, 25 or more, 30 or more, or 35 or more. It means that the larger the difference, the more the metal forming the protrusions transferred to the insulating base layer.
- the adhesiveness between the resin substrate and the seed layer is enhanced by forming irregularities that serve as anchors in the resin.
- relatively large unevenness was formed on the surface to ensure adhesion, but this caused copper to precipitate deep from the resin surface layer, so when the seed layer was etched and removed, a small amount of copper remained. tended to A deep etching process was necessary because this trace amount of remaining copper could cause a short circuit between wirings.
- the effect of increasing adhesion by unevenness forming treatment and electroless copper plating film is that selectivity to resin substrates is high, and sufficient adhesion effect can be obtained only in some cases such as ABF (Ajinomoto Build-Up Film). It is only a resin base material.
- an ultra-thin copper foil with a carrier is used, but the thickness of the ultra-thin copper foil layer must be 1.5 ⁇ m or more from the viewpoint of handling, etc.
- roughening treatment of 1 ⁇ m or more is performed. ing. By forming the roughened seed layer on the resin, the adhesion between the resin substrate and the seed layer is enhanced. At that time, since it is necessary to remove the copper layer with a thickness of several ⁇ m including the ultra-thin copper foil layer and the roughened portion, a deep etching treatment was required.
- the seed layer obtained by the method of the present disclosure has a smaller surface roughness than the case where the surface is roughened by desmear treatment in the conventional SAP method or the case where the ultra-thin copper foil with a carrier is roughened in the conventional MSAP method. Therefore, it is possible to avoid problems such as residual copper after etching, pattern skipping due to side etching in fine patterns, and transmission loss of high-frequency signals due to unevenness.
- the surface roughness is small, fine unevenness is densely present, so that the insulating base material and copper are sufficiently adhered to each other.
- the resist may contain, for example, a material that is cured or dissolved by exposure to light, and is not particularly limited, but is preferably formed of a dry film resist (DFR), a positive liquid resist, or a negative liquid resist.
- DFR dry film resist
- DFR preferably contains a binder polymer that contributes to film formability, a monomer that undergoes a photopolymerization reaction upon UV irradiation (for example, an acrylic ester-based or methacrylic ester-based monomer), and a photopolymerization initiator.
- a dry film having a three-layer structure of cover form/photoresist/carrier film is preferably used for forming the DFR.
- a DFR, which is a resist can be formed on the structure by laminating the photoresist on the structure while peeling off the cover film, and then peeling off the carrier film after the lamination.
- Liquid resists include novolak resins that are soluble in organic solvents.
- the resist can be formed by coating the surface of the structure, drying it, and then dissolving or curing the resist by light irradiation.
- the thickness of the resist is not particularly limited, it is preferably 1 ⁇ m to 200 ⁇ m.
- the surface of the seed layer may be plated to form a second seed layer.
- the method of plating treatment is not particularly limited, and may be electrolytic plating or electroless plating.
- a film may be formed by a plating method.
- the second seed layer refers to a metal thin film formed by plating.
- the thickness of the second seed layer is not particularly limited, and may be about 0.02 to 2 ⁇ m. .
- the method of copper plating treatment is not particularly limited, and plating treatment can be performed using a known method.
- the method of removing the resist is not particularly limited, and known methods such as a method using fuming nitric acid or sulfuric acid-hydrogen peroxide mixture, and a dry ashing method using O 2 plasma or the like can be used.
- Step of Removing Seed Layer The method for removing the seed layer is not particularly limited, and known methods such as quick etching and flash etching using a sulfuric acid-hydrogen peroxide-based etchant can be used.
- Example 1 potassium carbonate 10 g / L; KBE-903 (3-aminopropyltriethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.) 1 vol%
- Example 3 contains potassium carbonate 10 g/L; potassium hydrogen carbonate 0.06 g/L
- Examples 4 to 6 contain 10 g/L of potassium hydroxide
- Example 7 contains 10 g/L of potassium hydroxide
- KBM-603 N-2-(aminoethyl)-3-aminopropyltrimethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.) 5 vol%
- Example 8 is a solution of potassium hydroxide 10 g/L
- BTA benzotriazole
- Comparative Example 2 is a solution of potassium carbonate 10 g/L
- Comparative Example 3 used a solution of 10 g/L
- Comparative Example 3 contains, as an oxidizing agent, sodium chlorite 60.5 g/L; potassium hydroxide 9.1 g/L; potassium carbonate 3.1 g/L; KBM-403 (3-glycidoxypropyltrimethoxysilane; Shin-Etsu Silicone Co., Ltd.) 2.1 g/L solution was used. Examples 1, 2, 7, and 8 were immersed in the oxidizing agent at 73° C. for 6 minutes, and Examples 3 to 6 and Comparative Examples 2 and 3 were immersed in the oxidizing agent at 73° C. for 2 minutes.
- Example 4 was treated at 45° C. for 10 seconds with a solution of 47.2 g/L of tin(II) chloride dihydrate and 1 mL/L of hydrochloric acid.
- Example 5 was treated at 45° C. for 60 seconds using a solution of 47.2 g/L of ammonium chloride.
- Example 6 was treated at 45° C. for 60 seconds using a 6.5 mL/L 50% citric acid solution.
- a laminate sample was obtained by laminating prepreg on a test piece and thermocompression bonding in a vacuum using a vacuum high pressure press.
- the resin base material is R5670KJ (manufactured by Panasonic)
- the temperature and pressure are increased to 2.94 MPa and 210° C. for 120 minutes after thermocompression bonding while heating to 110° C. under a pressure of 0.49 MPa. It was thermocompression bonded by holding.
- the resin base material is R5680J (manufactured by Panasonic) after heat-pressing while heating to 110 ° C. under a pressure of 0.5 MPa, the temperature and pressure are increased, and held for 75 minutes at 3.5 MPa and 195 ° C. It was thermocompression bonded by doing.
- the resin substrate is NX9255 (manufactured by Park Electrochemical)
- it is heated to 260°C while pressurizing at 0.69 MPa, and the pressure is increased to 1.5 MPa and heated to 385°C. It was thermocompression bonded by holding for 1 minute.
- the resin substrate is R1551GG (manufactured by Panasonic)
- it is heated under a pressure of 1 MPa, and after reaching 100 ° C., it is held at that temperature for 10 minutes, and then further heated under a pressure of 3.3 MPa to 180 ° C. After the temperature was reached, the temperature was maintained for 50 minutes for thermocompression bonding.
- the resin substrate is CT-Z (manufactured by Kuraray Co., Ltd.), it is heated under a pressure of 0 MPa, held at 260° C. for 15 minutes, further heated while being pressurized at 4 MPa, and held at 300° C. for 10 minutes. crimped.
- the copper member was peeled off from the resin substrate according to the 90° peeling test (Japanese Industrial Standards (JIS) C5016) for these laminate samples. Visual observation results are shown in Figure 2-1. Photographs of the surfaces of the resin side and the copper foil side after peeling off are shown in Fig. 2-2 for representative combinations.
- Example 1 since the composite copper foil was not plated, only Cu atoms were transferred and detected on the resin substrate side. In Examples 2 and 3, since Ni plating was performed, Cu atoms and Ni atoms were transferred and detected on the resin side.
- the ratio of C1s was smaller in all the examples than in the comparative example. In Examples, it is considered that the ratio of C1s on the surface was relatively decreased due to the transfer of cupric oxide or cuprous oxide.
- FT-IR/ATR Method Analysis of Composite Copper Foil Surface after Transfer by Attenuated Total Reflection Absorption Fourier Transform Infrared Spectroscopy (FT-IR/ATR Method)> (1) Method After thermal compression using R1551GG (epoxy), R5670KJ, R5680J (all PPE), NX9255 (PTFE), or CT-Z (LCP) as the resin substrate, and peeling off Each composite copper foil test piece was analyzed by the FT-IR/ATR method under the following measurement conditions. Measurement conditions Specrtum 100 made by Parkin Elmer ATR method Crystal: Germanium Resolution: 4 Number of scans: 4 Pressure (force gauge): 40 ⁇ 5 [N] Spectral display: Absorbance
- R1551GG When using R1551GG as a resin base material, it is around 1200 cm -1 , when using R5670KJ and R5680J, it is around 1190 cm -1 , when using NX9255, it is around 1232 cm -1, and when CT - Z is used, it is 1741 cm -1 .
- the maximum peak detectable wavelength was taken to be around 1 (the arrows in FIGS. 4 to 8 indicate the maximum peak detectable wavelength).
- the S/N ratio was calculated using the noise value (N) as the difference between the maximum and minimum values of the peaks detected at a wavelength of 3800-3850 cm ⁇ 1 .
- the metal on the surface of the composite copper foil hardly transferred, and cohesive failure of the resin occurred when the composite copper foil was peeled off from the resin substrate, and the destroyed resin adhered to the surface of the composite copper foil. This is because a peak corresponding to the resin-derived organic matter was detected.
- the metal on the surface of the composite copper foil was transferred to the resin base material, almost no resin adhered to the composite copper foil after the composite copper foil was peeled off from the resin base material. No peaks with a corresponding S/N ratio of 10 or greater were detected.
- the strength of the protrusions formed by the layer containing copper oxide is greater than the strength of the resin base material, so the metal on the surface of the composite copper foil does not transfer and cohesive failure of the resin occurs.
- the strength of the protrusions formed by the layer containing copper oxide is lower than the strength of the resin base material, the metal on the surface of the composite copper foil is transferred, so there is almost no adhesion of the resin.
- a copper clad laminate R-5775 manufactured by Panasonic
- 18 ⁇ m copper foil is laminated on both sides of a substrate having a thickness of 0.5 mm
- GX13 manufactured by Ajinomoto Fine Techno
- the composite copper foil was peeled off by hand, and the fine irregularities formed on the composite copper foil were transferred onto the resin base material to form a seed layer on the resin base material.
- a commercially available photosensitive dry film was attached on the formed seed layer, exposed through a mask, and developed with 0.8% sodium hydrogen carbonate to form a plating resist.
- electrolytic copper plating was performed at a current density of 1 A/dm 2 at 30° C. for 30 minutes to form an electrolytic copper plating film with a thickness of 15 ⁇ m.
- the seed layer under the plating resist was dissolved and removed by etching using a mixed solution of sulfuric acid and hydrogen peroxide to obtain a laminated wiring circuit board ( Figure 9).
- a laminated wiring circuit board can be obtained by going through.
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Abstract
Description
[金属元素の表面原子組成百分率(Atom%)の合計]/[C1sの表面原子組成百分率(Atom%)]
が0.03以上、または0.04以上であってもよい。前記銅部材が引き剥がされた前記樹脂基材の表面に対し、X線光電子分光法(XPS)によって、Survey spectrum分析を行ったとき、Cu2p3とNi2p3の表面原子組成百分率の合計が3.0atom%以上または1.5atom%以上であってもよい。前記銅部材が引き剥がされた前記樹脂基材の表面に対し、X線光電子分光法(XPS)によって、Survey spectrum分析を行ったとき、Cu2p3の表面原子組成百分率が2.8atom%以上または1.0atom%以上であってもよい。前記表面に凸部を有する銅部材が、1)材料となる銅部材の表面をシランカップリング剤または防腐剤で部分コートする工程、及び、2)前記部分コートされた前記表面を酸化処理することにより銅酸化物を含む層を形成する工程によって形成されてもよい。前記表面に凸部を有する銅部材が、1)材料となる銅部材の表面を酸化処理することにより銅酸化物を含む層を形成する工程、及び、2)前記酸化処理された前記表面を、前記銅酸化物を溶解させる溶解剤で処理する工程、によって形成されてもよい。前記溶解剤が、塩化Ni、塩化亜鉛、塩化鉄、塩化クロム、クエン酸アンモニウム、塩化アンモニウム、塩化カリウム、硫酸アンモニウム、硫酸ニッケルアンモニウム、エチレンジアミン四酢酸、ジエタノールグリシン、L-グルタミン酸二酢酸・四ナトリウム、エチレンジアミン-N,N’-ジコハク酸、3-ヒドロキシ-2、2’-イミノジコハク酸ナトリウム、メチルグリシン2酢酸3ナトリウム、アスパラギン酸ジ酢酸4ナトリウム、N-(2-ヒドロキシエチル)イミノ二酢酸ジナトリウム及びグルコン酸ナトリウムからなる群から選択されてもよい。
本出願は、2021年3月25日付で出願した日本国特許出願特願2021-052381に基づく優先権を主張するものであり、当該基礎出願を引用することにより、本明細書に含めるものとする。
本明細書の開示の一実施形態は、絶縁基材層と銅の積層体の製造方法であって、絶縁基材層と、表面に凸部を有する銅部材とを貼り合わせる工程と、銅部材を引き剥がすことによって、凸部を絶縁基材層表面に転移させ、シード層を形成する工程と、シード層の表面上の所定の場所にレジストを形成する工程と、シード層の表面であってレジストが積層していない領域を銅めっき処理することによって、銅を積層する工程と、レジストを除去する工程と、レジストの除去によって露出したシード層を除去する工程と、を含む、製造方法である。なお、本明細書で、シード層とは、引き剥がされた銅部材の表面と、銅部材の凸部によって絶縁基材層に形成された凹部の最底部を含むように構成される面との間に形成される層をいい(図1B)、従って、その凹部、および凹部に転移した銅部材由来の金属は、その層の中に含まれる。凹部の最底部は、複数ある凹部の底部のうち、引き剥がされた銅部材の表面から最も遠い底部をいい、凹部の最底部を含むように構成される面は、引き剥がされた銅部材の表面と平行である。
<銅部材>
銅部材の表面は、微細な凸部を有する。
銅部材の表面の算術平均粗さ(Ra)は0.03μm以上が好ましく、0.05μm以上がより好ましく、また、0.3μm以下であることが好ましく、0.2μm以下であることがより好ましい。
銅酸化物を含む層は、銅部材の表面に形成され、酸化銅(CuO)及び/又は亜酸化銅(Cu2O)を含む。この銅酸化物を含む層は、銅部材表面を酸化処理することにより、形成することができる。この酸化処理によって、銅部材表面が粗面化される。
、亜酸化銅は1×106~1×107(Ωm)であるため、銅酸化物を含む層は導電性が低く、例え、樹脂基材に転移した銅酸化物を含む層の量が多くても、本発明に係る銅部材を用いてプリント配線基板や半導体パッケージ基板の回路を形成する際、表皮効果による伝送損失が起こりにくい。
シランカップリング剤または防腐剤による処理は、銅部材表面を部分的に(例えば、1%、5%、10%、20%、30%、40%、50%、60%、70%、80%又は90%以上で、100%未満)コートすることが好ましく、そのためには、0.1%、0.5%、1%又は2%以上の濃度で、室温で30秒、1分又は2分以上反応させることが好ましい。
絶縁基材層の基材は、凹凸が形成された銅部材の表面を絶縁基材層に貼り合わせたとき、銅部材の凹凸形状を含む表面プロファイルが樹脂基材に転写されるものであれば特に限定されないが、樹脂基材が好ましい。樹脂基材は、樹脂を主成分として含有する材料であるが、樹脂の種類は特に限定されず、熱可塑性樹脂であっても、熱硬化性樹脂であってもよく、ポリフェニレンエーテル(PPE)、エポキシ、ポリフェニレンオキシド(PPO)、ポリベンゾオキサゾール(PBO)、ポリテトラフルオロエチレン(PTFE)、液晶ポリマー(LCP)、熱可塑性ポリイミド(TPI)、フッ素樹脂、ポリエーテルイミド、ポリエーテルエーテルケトン、ポリシクロオレフィン、ビスマレイミド樹脂、低誘電率ポリイミド、シアネート樹脂、またはこれらの混合樹脂が例示できる。樹脂基材はさらに無機フィラーやガラス繊維を含んでいてもよい。使用される絶縁基材層の比誘電率は5.0以下が好ましく、4.0以下がより好ましく、3.8以下がさらに好ましい。
凹凸が形成された銅部材の表面を絶縁基材層に貼り合わせると、銅部材の凹凸形状を含む表面プロファイルが樹脂基材に転写される。従って、絶縁基材層表面には、銅部材表面の凸部に相補する凹部、また凹部に相補する凸部が形成される。
貼り合わせる方法は特に限定されないが、熱圧着(thermal press fitting)であることが好ましい。樹脂基材を銅部材の表面に熱圧着するには、例えば、樹脂基材と銅部材を密着させて積層した後、所定の条件で熱処理すればよい。所定の条件(例えば、温度、圧力、時間など)として、各基材メーカーの推奨条件を用いてもよい。所定の条件とは、例えば以下のような条件が考えられる。
1-1)樹脂基材が、R-1551(Panasonic製)の場合、
1MPaの圧力下で加熱し、100℃に到達後、その温度で5~10分保持し;
その後3.3MPaの圧力下でさらに加熱し、170~180℃に到達後、その温度で50分間保持することで熱圧着する。
1MPaの圧力下で加熱し、130℃到達後、その温度で10分保持し;その後2.9MPaの圧力下でさらに加熱し、200℃到達後、その温度で70分間保持することで熱圧着する。
0.4MPaの圧力下で加熱し、100℃到達後、圧力を2.4~2.9MPaに上げてさらに加熱し、195℃到達後、その温度で50分間保持することで熱圧着する。
2-1)樹脂基材が、R5620(Panasonic製)の場合、
0.5MPaの圧力下で100℃になるまで加熱しながら熱圧着した後、温度と圧力を上げ、2.0~3.0MPa、200~210℃で、120分間保持することでさらに熱圧着する。
0.49MPaの圧力下で110℃になるまで加熱しながら熱圧着した後、温度と圧力を上げ、2.94MPa、210℃で120分間保持することで熱圧着する。
3-1)樹脂基材が、NX9255(パークエレクトロケミカル製)の場合、0.69MPaで加圧しながら260℃になるまで加熱し、1.03~1.72MPaに圧力をあげて385℃になるまで加熱し、385℃で10分間保持することで熱圧着する。
絶縁基材層に銅部材を貼り合わせた後に、絶縁基材層から銅部材を所定の条件で引き剥がすと、銅部材の表面の凸部が絶縁基材層に転移し、絶縁基材層の表面にシード層を形成する。従って、絶縁基材層の表面は平坦になる。
銅部材を引き剥がした後、シード層の表面上の所定の場所にレジストを形成する。レジストが形成される位置は、後に、回路となる銅が積層されない部分である。
次に、シード層の表面であってレジストが積層していない領域を銅めっき処理することによって、銅を積層する。この積層された銅が、後に回路として機能する。
銅めっき処理の方法は特に限定されず、公知の方法を用いて、めっき処理ができる。
レジストの除去方法は、特に限定されず、発煙硝酸や硫酸過水を用いる方法や、O2プラズマ等を利用するドライアッシング法など、公知の方法を用いることができる。
シード層の除去方法は、特に限定されず、例えば硫酸-過酸化水素系のエッチング剤を用いたクイックエッチングやフラッシュエッチングなど、公知の方法を用いることができる。
実施例1~9、比較例2~3は、古河電気工業株式会社製の銅箔(DR-WS、厚さ:18μm)のシャイニー面(光沢面。反対面と比較したときに平坦である面。)を用いた。比較例4は、古河電気工業株式会社製の銅箔(FV-WS、厚さ:18μm)のマット面を用い、未処理のまま試験片とした。
まず、銅箔を以下に記載の溶液で、25℃1分間浸漬した。すなわち、
実施例1及び2は、炭酸カリウム10g/L;KBE-903(3-アミノプロピルトリエトキシシラン;信越シリコーン社製)1vol%、
実施例3は、炭酸カリウム10g/L;炭酸水素カリウム0.06g/L、
実施例4~6は、水酸化カリウム10g/L、
実施例7は、水酸化カリウム10g/L;KBM-603(N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン;信越シリコーン社製)5vol%、
実施例8は、水酸化カリウム10g/L;BTA(ベンゾトリアゾール)1wt%、 比較例2は、炭酸カリウム10g/Lの溶液、
比較例3は、炭酸カリウム10g/Lの溶液;炭酸水素カリウム0.06g/L、を用いた。
前処理を行った銅箔を、酸化剤に浸漬して酸化処理を行った。
実施例1、2、7、8及び比較例2は、酸化剤として、亜塩素酸ナトリウム60g/L;水酸化カリウム20.6g/L;炭酸カリウム40.2g/Lの溶液を用いた。
実施例3~6は、酸化剤として亜塩素酸ナトリウム46.3g/L;水酸化カリウム12.3g/L;KBM-403(3-グリシドキシプロピルトリメトキシシラン;信越シリコーン社製)2.1g/Lの溶液を用いた。
比較例3は、酸化剤として、亜塩素酸ナトリウム60.5g/L;水酸化カリウム9.1g/L;炭酸カリウム3.1g/L;KBM-403(3-グリシドキシプロピルトリメトキシシラン;信越シリコーン社製)2.1g/Lの溶液を用いた。
実施例1、2、7、及び8は酸化剤に73℃で6分間浸漬し、実施例3~6、比較例2及び3は酸化剤に73℃で2分間浸漬した。
酸化処理後、実施例4~6は、以下のように溶解剤を用いてめっき前処理を行った。
実施例4は、塩化スズ(II)・二水和物47.2g/L;塩酸1mL/Lの溶液を用い、45℃で10秒処理した。
実施例5は、塩化アンモニウム47.2g/Lの溶液を用い、45℃で60秒処理した。
実施例6は、50%クエン酸溶液6.5mL/Lの溶液を用い、45℃で60秒処理した。
酸化処理後、実施例2、3及び比較例3は、第1のNi電解めっき液(硫酸ニッケル255g/L;塩化ニッケル49g/L;クエン酸ナトリウム20g/L)を用いて電解めっきを行った。実施例4~6は、めっき前処理後、第2のNi電解めっき液(硫酸ニッケル255g/L;クエン酸ナトリウム20g/L)を用いて電解めっきを行った。実施例3は電解めっき前にNi電解めっき液に1分間浸漬させた。実施例2は50℃で電流密度0.5A/dm2×116秒(=58C/dm2銅箔面積)で電解めっきを行った。実施例3~6、及び比較例3は50℃で電流密度0.5A/dm2×45秒(=22.5C/dm2銅箔面積)で電解めっきを行った。
(1)方法
実施例1~8及び比較例2~4の試験片に対し、プリプレグとして、R5670KJ(Panasonic製)、R5680J(Panasonic製)、CT-Z(クラレ製)、NX9255(パークエレクトロケミカル製)、及びR1551GG(Panasonic製)を用いて、樹脂基材の引き剥がし試験を行った。
引き剥がした後の樹脂基材の表面の元素分析を行った。具体的には、得られた樹脂基材を、QuanteraSXM(ULVAC-PHI製)を用いて以下の条件で分析を行った。陰性対照として何も処理していない樹脂基材(R5670KJ;MEGTRON6)を分析した(比較例1)。
まず、以下の条件で元素を検出した。
X線光源: 単色化Al Kα(1486.6eV)
X線ビーム径: 100μm(25w15kV)
パスエネルギー: 280eV,1eVステップ
ポイント分析: φ100μm
積算回数 8回
結果を表2及び図3に示す。
実施例において、転移した銅原子に由来するCu2p3のスペクトルのピーク強度が樹脂基材に起因するC1sのスペクトルのピーク強度よりも大きいのに対して、比較例はCu2p3のスペクトルのピークが検出されないか、その強度がC1sのスペクトルのピーク強度よりも小さかった。これは、比較例においては、銅原子が、樹脂基材にほとんど転移していないか、XPSで検出できる樹脂基材表層部分にはほとんど存在していないことを示す。
(1)方法
実施例1~8及び比較例2~4の複合銅箔試験片について、熱圧着前と引き剥がし後の表面積を、共焦点顕微鏡 OPTELICS H1200(レーザーテック株式会社製)を用いて算出した。測定条件として、モードはコンフォーカルモード、スキャンエリアは100μm×100μm、Light sourceはBlue、カットオフ値は1/5
とした。オブジェクトレンズはx100、コンタクトレンズはx14、デジタルズームはx1、Zピッチは10nmの設定とし、3箇所のデータを取得し、表面積は3箇所の平均値とした。
表3に記載のように、熱圧着前と引き剥がし後では、実施例ではRa及び表面積が減少したのに対し、比較例では逆に増加した。これは実施例では、複合銅箔の凸部全部または一部が樹脂側に転移したのに対して、比較例では逆に樹脂の一部が複合銅箔に転移したことを示している。
(1)方法
熱圧着前と引き剥がし後の各複合銅箔試験片の銅箔表面の色差(L*、a*、b*)を測定し、得られた値から、以下の式に従い、ΔE*abを算出した。
ΔE*ab = [(ΔL*)2 + (Δa*)2 + (Δb*)2 ]1/2
表4に記載のように、熱圧着前と引き剥がし後で、実施例ではΔE*abが15以上なのに対して、比較例では15未満であった。これは、実施例では銅酸化物を含む層に含まれる金属が樹脂基材に転移するため、銅部材の色変化が大きくなるのに対して、比較例では銅酸化物を含む層はそのまま銅部材に残るため、銅部材の色変化は小さくなるため、銅酸化物を含む層に含まれる金属が多く転移するほど、それらの差が大きくなるからである。実際、図2の写真においても、引き剥がし後に、実施例では樹脂側の着色が大きいが、比較例では樹脂側はほぼ白いままである。
(1)方法
樹脂基材として、R1551GG(エポキシ系)、R5670KJ、R5680J(以上、PPE系)、NX9255(PTFE系)、またはCT-Z(LCP系)を用いて熱圧着し、引き剥がした後の各複合銅箔試験片をFT-IR/ATR法により以下の測定条件で解析した。
測定条件
Parkin Elmer製 Specrtum100
ATR法
クリスタル:ゲルマニウム
分解能:4
スキャン数:4回
圧力(フォースゲージ):40±5 [N]
スペクトル表示:吸光度
複合銅箔と熱圧着する時と同じ条件で樹脂基材のみを加熱及び加圧処理後、樹脂基材をFT-IRで測定し、樹脂由来のピークがない任意の波長を50cm-1の範囲で選定した。本実施例では、3800-3850cm-1を樹脂由来のピークがない波長とした。
さらに、波長範囲700-4000cm-1において、最大ピークを検出した波長を同定した。樹脂基材としてR1551GGを用いた場合は1200cm-1付近、R5670KJおよびR5680Jを用いた場合は1190cm-1付近、NX9255を用いた場合は1232cm-1付近、CT-Zを用いた場合は、1741cm-1付近を最大ピーク検出波長とした(図4~8の矢印が最大ピーク検出波長を示す)。
第1の実施例における実施例3の複合銅箔を用いて、回路の形成を行った。
まず、古河電気工業株式会社製の銅箔(DR-WS、厚さ:18μm)のシャイニー面(光沢面。反対面と比較したときに平坦である面。)を用い、下記条件にて処理を行うことで複合銅箔を作製した。
銅箔を炭酸カリウム10g/L;炭酸水素カリウム0.06g/Lの溶液を用い、25℃1分間浸漬した。
前処理を行った銅箔を、酸化剤に浸漬して酸化処理を行った。
酸化剤として亜塩素酸ナトリウム46.3g/L;水酸化カリウム12.3g/L;KBM-403(3-グリシドキシプロピルトリメトキシシラン;信越シリコーン社製)2.1g/Lの溶液を用い、溶液に73℃で2分間浸漬した。
酸化処理後、Ni電解めっき液(硫酸ニッケル255g/L;塩化ニッケル49g/L;クエン酸ナトリウム20g/L)を用いて電解めっきを行った。電解めっき前にNi電解めっき液に1分間浸漬させた。50℃で電流密度0.5A/dm2×45秒(=22.5C/dm2銅箔面積)で電解めっきを行った。
Claims (19)
- 絶縁基材層と銅の積層体の製造方法であって、
前記絶縁基材層と、表面に凸部を有する銅部材とを貼り合わせる工程と、
前記銅部材を引き剥がすことによって、前記凸部を前記絶縁基材層表面に転移させ、シード層を形成する工程と、
前記シード層の表面上の所定の場所にレジストを形成する工程と、
前記シード層の表面であって前記レジストが積層していない領域を銅めっき処理することによって、前記銅を積層する工程と、
前記レジストを除去する工程と、
前記レジストの除去によって露出した前記シード層を除去する工程と、
を含む、製造方法。 - 前記銅部材の前記表面の前記凸部は、化学処理によって、前記銅部材の表面に形成された、請求項1に記載の製造方法。
- 前記絶縁基材層の表面には、デスミア処理によって凸部が形成されない、請求項1または2に記載の製造方法。
- 前記銅めっき処理が電解銅めっき処理である、請求項1~3のいずれか1項に記載の製造方法。
- 前記シード層を形成する工程と、前記レジストを形成する工程との間に、前記シード層の表面を無電解めっき処理する工程を行う、請求項1~4のいずれか1項に記載の製造方法。
- 熱圧着によって、前記絶縁基材層と、前記銅部材とが貼り合わせられる、請求項1~5のいずれか1項に記載の製造方法。
- 前記絶縁基材層から引き剥がした前記銅部材の表面を、減衰全反射吸収フーリエ変換赤外分光法(FT-IR/ATR法)を用いて解析したとき、波長範囲700-4000cm-1において、検出される樹脂基材由来の物質に対応するピークのS/N比が10以下である、請求項6に記載の製造方法。
- 前記ピークのS/N比が7以下である、請求項7に記載の製造方法。
- 前記銅部材が引き剥がされた前記樹脂基材の表面に対し、X線光電子分光法(XPS)によって、Survey spectrum分析を行ったとき、得られたX線光電子分光スペクトルにおいて、前記銅部材に含まれる金属原子が、前記銅部材が引き剥がされた前記樹脂基材の表面から検出される、請求項6に記載の製造方法。
- 前記銅部材が引き剥がされた前記樹脂基材の表面から検出される金属元素のメインピークの強度の合計がC1sのピーク強度よりも大きい、請求項9に記載の製造方法。
- 前記XPSによる測定から算出される
[金属元素の表面原子組成百分率(Atom%)の合計]/[C1sの表面原子組成百分率(Atom%)]
が0.03以上である、請求項8または9に記載の樹脂基材の製造方法。 - 前記XPSによる測定から算出される
[金属元素の表面原子組成百分率(Atom%)の合計]/[C1sの表面原子組成百分率(Atom%)]
が0.04以上である、請求項8または9に記載の樹脂基材の製造方法。 - 前記銅部材が引き剥がされた前記樹脂基材の表面に対し、X線光電子分光法(XPS)によって、Survey spectrum分析を行ったとき、Cu2p3とNi2p3の表面原子組成百分率の合計が3.0atom%以上である、請求項6に記載の樹脂基材の製造方法。
- 前記銅部材が引き剥がされた前記樹脂基材の表面に対し、X線光電子分光法(XPS)によって、Survey spectrum分析を行ったとき、Cu2p3とNi2p3の表面原子組成百分率の合計が1.5atom%以上である、請求項6に記載の樹脂基材の製造方法。
- 前記銅部材が引き剥がされた前記樹脂基材の表面に対し、X線光電子分光法(XPS)によって、Survey spectrum分析を行ったとき、Cu2p3の表面原子組成百分率が2.8atom%以上である、請求項6に記載の樹脂基材の製造方法。
- 前記銅部材が引き剥がされた前記樹脂基材の表面に対し、X線光電子分光法(XPS)によって、Survey spectrum分析を行ったとき、Cu2p3の表面原子組成百分率が1.0atom%以上である、請求項6に記載の樹脂基材の製造方法。
- 前記表面に凸部を有する銅部材が、
1)材料となる銅部材の表面をシランカップリング剤または防腐剤で部分コートする工程、及び
2)前記部分コートされた前記表面を酸化処理することにより銅酸化物を含む層を形成する工程
によって形成される、請求項1~16のいずれか1項に記載の製造方法。 - 前記表面に凸部を有する銅部材が、
1)材料となる銅部材の表面を酸化処理することにより銅酸化物を含む層を形成する工程、及び
2)前記酸化処理された前記表面を、前記銅酸化物を溶解させる溶解剤で処理する工程、によって形成される、請求項1~17のいずれか1項に記載の製造方法。 - 前記溶解剤が、塩化カリウム、塩化Ni、塩化亜鉛、塩化鉄、塩化クロム、クエン酸アンモニウム、塩化アンモニウム、硫酸アンモニウム、硫酸ニッケルアンモニウム、エチレンジアミン四酢酸、ジエタノールグリシン、L-グルタミン酸二酢酸・四ナトリウム、エチレンジアミン-N,N’-ジコハク酸、3-ヒドロキシ-2、2’-イミノジコハク酸ナトリウム、メチルグリシン2酢酸3ナトリウム、アスパラギン酸ジ酢酸4ナトリウム、N-(2-ヒドロキシエチル)イミノ二酢酸ジナトリウム及びグルコン酸ナトリウムからなる群から選択される、請求項18に記載の製造方法。
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JP6806405B1 (ja) * | 2020-04-27 | 2021-01-06 | ナミックス株式会社 | 複合銅部材 |
JP2021052381A (ja) | 2019-09-20 | 2021-04-01 | 株式会社リコー | シート搬送装置、画像読取装置及び画像形成装置 |
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2022
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- 2022-03-23 KR KR1020237027933A patent/KR20230160790A/ko unknown
- 2022-03-23 CN CN202280009670.2A patent/CN116745462A/zh active Pending
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- 2022-03-23 JP JP2023509261A patent/JPWO2022202921A1/ja active Pending
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JP2000036660A (ja) * | 1998-07-17 | 2000-02-02 | Hitachi Chem Co Ltd | ビルドアップ多層配線板の製造方法 |
JP2002176242A (ja) | 2000-12-05 | 2002-06-21 | Nikko Materials Co Ltd | 電子回路用銅箔及び電子回路の形成方法 |
JP2005223226A (ja) | 2004-02-06 | 2005-08-18 | Murata Mfg Co Ltd | 複合多層基板 |
JP2010267891A (ja) | 2009-05-18 | 2010-11-25 | Fujikura Ltd | プリント配線基板及びその製造方法 |
WO2014080959A1 (ja) * | 2012-11-20 | 2014-05-30 | Jx日鉱日石金属株式会社 | キャリア付き銅箔 |
WO2015040998A1 (ja) * | 2013-09-20 | 2015-03-26 | 三井金属鉱業株式会社 | 銅箔、キャリア箔付銅箔及び銅張積層板 |
WO2017056534A1 (ja) * | 2015-09-30 | 2017-04-06 | 三井金属鉱業株式会社 | 粗化処理銅箔、銅張積層板及びプリント配線板 |
WO2019244541A1 (ja) * | 2018-06-20 | 2019-12-26 | ナミックス株式会社 | 粗化処理銅箔、銅張積層板及びプリント配線板 |
JP2021052381A (ja) | 2019-09-20 | 2021-04-01 | 株式会社リコー | シート搬送装置、画像読取装置及び画像形成装置 |
JP6806405B1 (ja) * | 2020-04-27 | 2021-01-06 | ナミックス株式会社 | 複合銅部材 |
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EP4317532A1 (en) | 2024-02-07 |
CN116745462A (zh) | 2023-09-12 |
US20240179848A1 (en) | 2024-05-30 |
KR20230160790A (ko) | 2023-11-24 |
JPWO2022202921A1 (ja) | 2022-09-29 |
TW202248460A (zh) | 2022-12-16 |
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