JPWO2012070589A1 - 表面処理銅箔 - Google Patents
表面処理銅箔 Download PDFInfo
- Publication number
- JPWO2012070589A1 JPWO2012070589A1 JP2012515831A JP2012515831A JPWO2012070589A1 JP WO2012070589 A1 JPWO2012070589 A1 JP WO2012070589A1 JP 2012515831 A JP2012515831 A JP 2012515831A JP 2012515831 A JP2012515831 A JP 2012515831A JP WO2012070589 A1 JPWO2012070589 A1 JP WO2012070589A1
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- layer
- zinc
- treated copper
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 354
- 239000011889 copper foil Substances 0.000 title claims abstract description 328
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 165
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 165
- 239000011701 zinc Substances 0.000 claims abstract description 165
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000460 chlorine Substances 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- 238000011282 treatment Methods 0.000 claims description 98
- 238000010438 heat treatment Methods 0.000 claims description 68
- 239000013078 crystal Substances 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 63
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 35
- 230000002265 prevention Effects 0.000 claims description 34
- 238000007788 roughening Methods 0.000 claims description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 26
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 230000003746 surface roughness Effects 0.000 claims description 20
- 229910052718 tin Inorganic materials 0.000 claims description 17
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- 229910052797 bismuth Inorganic materials 0.000 claims description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 15
- 229910052793 cadmium Inorganic materials 0.000 claims description 15
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 13
- 229910052738 indium Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 274
- 239000000523 sample Substances 0.000 description 63
- 230000000052 comparative effect Effects 0.000 description 47
- 238000007747 plating Methods 0.000 description 41
- 239000000243 solution Substances 0.000 description 35
- 238000004519 manufacturing process Methods 0.000 description 27
- 229910052802 copper Inorganic materials 0.000 description 23
- 239000010949 copper Substances 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- 238000004381 surface treatment Methods 0.000 description 19
- 239000011573 trace mineral Substances 0.000 description 17
- 235000013619 trace mineral Nutrition 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 16
- 239000011888 foil Substances 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 230000003449 preventive effect Effects 0.000 description 15
- 238000001035 drying Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000007773 negative electrode material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000013074 reference sample Substances 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 238000001887 electron backscatter diffraction Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 3
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002335 surface treatment layer Substances 0.000 description 3
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 3
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 3
- -1 3-aminopropoxy Chemical group 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- NHMJUOSYSOOPDM-UHFFFAOYSA-N cadmium cyanide Chemical compound [Cd+2].N#[C-].N#[C-] NHMJUOSYSOOPDM-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 2
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- CSJDJKUYRKSIDY-UHFFFAOYSA-N 1-sulfanylpropane-1-sulfonic acid Chemical compound CCC(S)S(O)(=O)=O CSJDJKUYRKSIDY-UHFFFAOYSA-N 0.000 description 1
- ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 1H-imidazole silane Chemical compound [SiH4].N1C=NC=C1 ZDDUSDYMEXVQNJ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 1
- ZDWPBMJZDNXTPG-UHFFFAOYSA-N 2h-benzotriazol-4-amine Chemical compound NC1=CC=CC2=C1NN=N2 ZDWPBMJZDNXTPG-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- KFSRINVVFGTVOA-UHFFFAOYSA-N 3-[butoxy(dimethoxy)silyl]propan-1-amine Chemical compound CCCCO[Si](OC)(OC)CCCN KFSRINVVFGTVOA-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- DUYKOAQJUCADEC-UHFFFAOYSA-N [SiH4].N1=NN=CC=C1 Chemical compound [SiH4].N1=NN=CC=C1 DUYKOAQJUCADEC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940026189 antimony potassium tartrate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- VMYXFDVIMUEKNP-UHFFFAOYSA-N trimethoxy-[5-(oxiran-2-yl)pentyl]silane Chemical compound CO[Si](OC)(OC)CCCCCC1CO1 VMYXFDVIMUEKNP-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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Abstract
Description
本件発明に係る表面処理銅箔は、銅箔の両面に防錆処理層を備える表面処理銅箔であって、当該防錆処理層は、亜鉛で構成し、且つ、いずれの面の亜鉛量も20mg/m2〜1000mg/m2の亜鉛層であり、当該銅箔は、炭素、硫黄、塩素、窒素から選ばれる1種又は2種以上の微量成分を含有し、これらの総含有量が100ppm以上であることを特徴とするものである。
本件発明に係る表面処理銅箔は、図1に模式的に示すように、銅箔の両面に防錆処理層を備える表面処理銅箔である。この図1には、銅箔2の片面側には、「防錆処理層3/クロメート処理層4/有機剤処理層5」の3層構成の表面処理層があり、反対面には「粗化処理層6/防錆処理層3/クロメート処理層4/有機剤処理層5」の4層構成の表面処理層がある状態を典型例として示している。なお、このときの粗化処理層は、微細銅粒子の集合体として示している。そして、図1における、粗化処理層6、クロメート処理層4及び有機剤処理層5は、要求特性に応じて設ける任意の表面処理層である。よって、層構成として多くのバリエーションが、本件発明に含まれることになる。なお、図面において、模式的に示した各層及び粗化状態は、説明を容易にするためのものであり、現実の製品の厚さ及び粗化状態を反映したものでないことを明記しておく。以下、本件発明に係る表面処理銅箔の構成が理解できるように、各項目毎に説明する。
本件発明に係る表面処理銅箔の製造方法は、上述に記載の表面処理銅箔の製造方法であって、銅箔の表面に対して、防錆処理層として「亜鉛層」又は「2層構造の亜鉛系複合層」を設ける防錆処理工程の他、必要に応じて、粗化処理及びその他の各種表面処理を施し、所定の条件で加熱する乾燥工程を備える。以下、工程毎に説明する。
銅箔: ここでは、三井金属鉱業株式会社製の厚さ15μmのVLP銅箔の製造に用いる表面処理を施していない電解銅箔を用いた。この電解銅箔は、常態引張強さが55.6kgf/mm2、陰極面側の表面粗さ(Ra)が0.22μm、析出面側の表面粗さ(Ra)が0.32μmのロープロファイル表面を備えるものである。そして、ここで用いた銅箔は、硫黄を19ppm、炭素を55ppm、窒素を10ppm、塩素を54ppm含有し、これら微量元素の総含有量が128ppmであった。
以下、評価項目及びその測定方法に関して述べる。この実施例1に係る実施試料1−1〜実施試料1−3の評価結果は、以下に述べる比較例1に係る比較試料1と対比可能なように表1に示す。
本比較例は、実施例1の防錆成分を、亜鉛量が、両面共に20mg/m2未満(表面処理銅箔の両面共に10mg/m2程度)である比較試料1を得た。その他の製造条件は、実施例1と同様であるため記載を省略する。
ここでの実施例1と比較例1との対比は、以下の表1を参照して行う。
銅箔: この実施例2で用いる銅箔は、以下に示す条件で作製した電解銅箔を用いた。先ず、硫酸系銅電解液として、硫酸銅溶液であって銅濃度80g/l、フリー硫酸濃度140g/lに調整した基本溶液を用い、下記の各添加剤濃度になるように調整した。即ち、添加剤として、メルカプト−1−プロパンスルホン酸のナトリウム塩 60.0ppm、ジアリルジメチルアンモニウムクロライド重合体(センカ(株)製ユニセンスFPA100L) 70.0ppm、N,N’ジエチルチオ尿素 7.0ppm、塩素濃度 60ppmを用いて実施試料2の電解銅箔を作製した。また、塩素濃度の調整には塩酸を用いた。そして、この電解銅箔の作製は、陰極として表面を#2000の研磨紙を用いて研磨を行ったチタン板電極を、陽極にはDSAを用いて、厚さ15μmの電解銅箔を作成した。
この比較例2では、箔中の微量元素の合計量が、100ppm以下の電解銅箔を選択して用いた。また、結晶粒径が1.0μmより大きい電解銅箔を選択して用いた。
表2を参照して、以下説明する。最初に実施試料のみに関して述べる。直ぐに理解できるのは、銅箔の亜鉛量が増加すると、350℃、400℃という高温の負荷を受けたときの耐軟化性能も、亜鉛量に比例して向上することが理解できる。
この比較例3は、実施例3で用いたVLP銅箔の製造に用いる電解銅箔に防錆処理を施すことなく、実施例3と同様の手順で表面処理銅箔を製造し、これを比較試料3とした。この評価結果は、実施例3と対比可能なように、表3に示す。
ここでは、以下に示す表3を参照しつつ、説明する。
以上の対比結果から、表面処理銅箔は、「炭素、硫黄、塩素又は窒素を含有し、少なくともこれらの総含有量が100ppm以上である銅箔」を用いることを前提として、この銅箔の両面にある防錆処理層は、「亜鉛又は2層構造の亜鉛系複合層で構成し、且つ、亜鉛量が20mg/m2〜1000mg/m2」の条件を満たすことが、高温負荷を受けたときの耐軟化性能を向上させるためには必須である。また、2層構造の亜鉛系複合層を採用した場合の異種金属の付着量は、1mg/m2〜200mg/m2であることが好ましい。以上に述べた条件を満たすことで、表面処理銅箔が「350℃×60分間の加熱処理を行った後の引張強さが40kgf/mm2以上」、「400℃×60分間の加熱処理を行った後の引張強さが35kgf/mm2以上」という良好な耐軟化性能を備えることが理解できる。
2 銅箔層
3 防錆処理層
4 クロメート処理層
5 有機剤処理層
6 粗化処理層(微細銅粒)
Claims (12)
- 銅箔の両面に防錆処理層を備える表面処理銅箔であって、
当該防錆処理層は、亜鉛で構成し、且つ、いずれの面の亜鉛量も20mg/m2〜1000mg/m2の亜鉛層であり、
当該銅箔は、炭素、硫黄、塩素、窒素から選ばれる1種又は2種以上の微量成分を含有し、これらの総含有量が100ppm以上であることを特徴とする表面処理銅箔。 - 前記銅箔の両面に配した亜鉛層を構成する総亜鉛量が40mg/m2〜2000mg/m2である請求項1に記載の表面処理銅箔。
- 前記銅箔と亜鉛層との間又は亜鉛層の表面に、スズ層、カドミウム層、アンチモン層、ビスマス層、インジウム層、鉛層のいずれか一種の異種金属層を配置した2層構造の亜鉛系複合層を防錆処理層とした請求項1又は請求項2に記載の表面処理銅箔。
- 前記異種金属層は、異種金属量が1mg/m2〜200mg/m2である請求項3に記載の表面処理銅箔。
- 前記銅箔は、常態の結晶粒径が1.0μm以下の電解銅箔である請求項1〜請求項4のいずれかに記載の表面処理銅箔。
- 前記銅箔は、常態の引張強さが50kgf/mm2以上の電解銅箔である請求項1〜請求項5のいずれかに記載の表面処理銅箔。
- 前記銅箔は、片面側又は両面側を粗化処理したものである請求項1〜請求項6のいずれかに記載の表面処理銅箔。
- 前記防錆処理層の表面に、クロメート処理層、有機剤処理層のいずれか一方又は双方を備える請求項1〜請求項7のいずれかに記載の表面処理銅箔。
- 前記有機剤処理層は、シランカップリング剤処理層、有機防錆処理層のいずれか一方又は双方からなるものである請求項8に記載の表面処理銅箔。
- 表面粗さ(Ra)が、0.1μm〜0.7μmである請求項1〜請求項9のいずれかに記載の表面処理銅箔。
- 不活性ガス雰囲気において、350℃×60分間の加熱処理を行った後の引張強さが40kgf/mm2以上である請求項1〜請求項10のいずれかに記載の表面処理銅箔。
- 不活性ガス雰囲気において、400℃×60分間の加熱処理を行った後の引張強さが35kgf/mm2以上である請求項1〜請求項11のいずれかに記載の表面処理銅箔。
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CN103221583A (zh) | 2013-07-24 |
KR20140140649A (ko) | 2014-12-09 |
KR101482898B1 (ko) | 2015-01-15 |
WO2012070591A1 (ja) | 2012-05-31 |
TWI432610B (zh) | 2014-04-01 |
CN103221584B (zh) | 2016-01-06 |
CN104651836B (zh) | 2018-11-02 |
EP2644753A1 (en) | 2013-10-02 |
JP5400960B2 (ja) | 2014-01-29 |
CN103221584A (zh) | 2013-07-24 |
EP2644754B1 (en) | 2016-05-11 |
US20130295407A1 (en) | 2013-11-07 |
KR20130121880A (ko) | 2013-11-06 |
WO2012070589A1 (ja) | 2012-05-31 |
KR20130131379A (ko) | 2013-12-03 |
TWI560047B (en) | 2016-12-01 |
TW201228818A (en) | 2012-07-16 |
MY162358A (en) | 2017-06-15 |
JP5714575B2 (ja) | 2015-05-07 |
CN104651836A (zh) | 2015-05-27 |
EP2644753B1 (en) | 2016-05-11 |
EP2644753A4 (en) | 2014-08-06 |
EP2644754A4 (en) | 2014-08-06 |
CN103221583B (zh) | 2015-05-13 |
JPWO2012070591A1 (ja) | 2014-05-19 |
EP2644754A1 (en) | 2013-10-02 |
US9138964B2 (en) | 2015-09-22 |
TW201231733A (en) | 2012-08-01 |
KR101593282B1 (ko) | 2016-02-11 |
US20130302635A1 (en) | 2013-11-14 |
MY163882A (en) | 2017-11-15 |
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