CN116240591A - Ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil and preparation method and application thereof - Google Patents
Ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil and preparation method and application thereof Download PDFInfo
- Publication number
- CN116240591A CN116240591A CN202211455743.9A CN202211455743A CN116240591A CN 116240591 A CN116240591 A CN 116240591A CN 202211455743 A CN202211455743 A CN 202211455743A CN 116240591 A CN116240591 A CN 116240591A
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- China
- Prior art keywords
- sulfate
- copper foil
- sodium
- content
- copper
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 229
- 239000011889 copper foil Substances 0.000 title claims abstract description 217
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000005275 alloying Methods 0.000 claims abstract description 78
- 239000011888 foil Substances 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 238000009713 electroplating Methods 0.000 claims abstract description 31
- 238000002444 silanisation Methods 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 88
- 239000000654 additive Substances 0.000 claims description 54
- 230000000996 additive effect Effects 0.000 claims description 52
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 40
- -1 polydithio-dipropyl Polymers 0.000 claims description 39
- 238000009472 formulation Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 32
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 29
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 29
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 29
- 229910052708 sodium Inorganic materials 0.000 claims description 29
- 239000011734 sodium Substances 0.000 claims description 29
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 238000007788 roughening Methods 0.000 claims description 27
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 26
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 26
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 26
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 25
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 25
- 229910001431 copper ion Inorganic materials 0.000 claims description 25
- 239000011684 sodium molybdate Substances 0.000 claims description 24
- 235000015393 sodium molybdate Nutrition 0.000 claims description 24
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 24
- 230000003746 surface roughness Effects 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 22
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 22
- 102000008186 Collagen Human genes 0.000 claims description 21
- 108010035532 Collagen Proteins 0.000 claims description 21
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 21
- 229920001436 collagen Polymers 0.000 claims description 21
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 claims description 21
- 239000001509 sodium citrate Substances 0.000 claims description 21
- 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 claims description 21
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 21
- 108010010803 Gelatin Proteins 0.000 claims description 20
- 239000008139 complexing agent Substances 0.000 claims description 20
- 239000008273 gelatin Substances 0.000 claims description 20
- 229920000159 gelatin Polymers 0.000 claims description 20
- 235000019322 gelatine Nutrition 0.000 claims description 20
- 235000011852 gelatine desserts Nutrition 0.000 claims description 20
- 238000007747 plating Methods 0.000 claims description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 20
- 235000011083 sodium citrates Nutrition 0.000 claims description 19
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 19
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 12
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 12
- 229940044175 cobalt sulfate Drugs 0.000 claims description 12
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 12
- 238000007654 immersion Methods 0.000 claims description 12
- 229920001184 polypeptide Polymers 0.000 claims description 11
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 11
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 11
- 241000283690 Bos taurus Species 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002639 bone cement Substances 0.000 claims description 10
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006884 silylation reaction Methods 0.000 claims description 10
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 150000002362 hafnium Chemical class 0.000 claims description 8
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002751 molybdenum Chemical class 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 150000003657 tungsten Chemical class 0.000 claims description 8
- 150000003754 zirconium Chemical class 0.000 claims description 8
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 7
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 7
- 210000000988 bone and bone Anatomy 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 7
- 239000001630 malic acid Substances 0.000 claims description 7
- 235000011090 malic acid Nutrition 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 7
- SMCXOVXKVFUJTC-UHFFFAOYSA-N CCC(N(C)C)S(O)(=O)=S Chemical compound CCC(N(C)C)S(O)(=O)=S SMCXOVXKVFUJTC-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 6
- FLWXWKDFOLALOB-UHFFFAOYSA-H dysprosium(3+);trisulfate Chemical compound [Dy+3].[Dy+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FLWXWKDFOLALOB-UHFFFAOYSA-H 0.000 claims description 6
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 claims description 6
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 6
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims description 5
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 5
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940085605 saccharin sodium Drugs 0.000 claims description 5
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 4
- 229960004642 ferric ammonium citrate Drugs 0.000 claims description 4
- 239000004313 iron ammonium citrate Substances 0.000 claims description 4
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 4
- 239000010985 leather Substances 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 239000001508 potassium citrate Substances 0.000 claims description 4
- 229960002635 potassium citrate Drugs 0.000 claims description 4
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 4
- 235000011082 potassium citrates Nutrition 0.000 claims description 4
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 4
- 229960001790 sodium citrate Drugs 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 4
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000467 phytic acid Substances 0.000 claims description 3
- 229940068041 phytic acid Drugs 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- DJZHPOJZOWHJPP-UHFFFAOYSA-N magnesium;dioxido(dioxo)tungsten Chemical compound [Mg+2].[O-][W]([O-])(=O)=O DJZHPOJZOWHJPP-UHFFFAOYSA-N 0.000 claims description 2
- 229960003975 potassium Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229940116298 l- malic acid Drugs 0.000 claims 4
- 239000003292 glue Substances 0.000 claims 2
- 229940099690 malic acid Drugs 0.000 claims 2
- 239000003446 ligand Substances 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 55
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- 238000002161 passivation Methods 0.000 description 28
- 238000003756 stirring Methods 0.000 description 25
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- 230000000052 comparative effect Effects 0.000 description 16
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 description 13
- 229960001763 zinc sulfate Drugs 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- NPAWNPCNZAPTKA-UHFFFAOYSA-M sodium;propane-1-sulfonate Chemical compound [Na+].CCCS([O-])(=O)=O NPAWNPCNZAPTKA-UHFFFAOYSA-M 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 230000002500 effect on skin Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
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Abstract
The invention relates to the technical field of electrolytic copper foil, in particular to an ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil, and a preparation method and application thereof. The preparation method of the copper foil comprises the following steps: (1) Electro-deposition is carried out on the electrolytic green foil by using electroplating solution to obtain ultra-low profile 5G green foil; (2) Coarsening the ultra-low profile 5G copper foil in coarsening liquid to obtain coarsened copper foil; (3) Placing the roughened copper foil into a curing liquid for curing to obtain a cured copper foil; (4) Placing the solidified copper foil into an alloying solution for alloying treatment to obtain an alloyed copper foil; (5) And placing the alloyed copper foil into a silanization preparation liquid for silanization treatment to obtain the copper foil. The preparation method of the ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil provided by the invention has the advantages that the prepared ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil is flat in surface, uniform in alloy distribution, free of cracking phenomenon and suitable for industrial popularization.
Description
Technical Field
The invention relates to the technical field of electrolytic copper foil, in particular to an ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil, and a preparation method and application thereof.
Background
The 5G wireless communication technology has the advantages of wide coverage area, low time delay, high reliability, higher hot spot capacity and the like, and has extremely wide application prospect. The core conductor base material in 5G communication is copper foil, which is required to have low surface roughness, good temperature resistance and strong peeling resistance in order to improve signal transmission performance, because:
in the 5G wireless communication technology, the surface roughness of the copper foil is high, so that skin effect is easy to cause, high-frequency high-speed transmission signals are seriously lost, and the signal transmission rate is seriously influenced. In addition, when a high-frequency high-speed signal is input into the PCB circuit, a large amount of heat is generated, so that the temperature of the PCB circuit is increased, and therefore, the copper foil needs to have good temperature resistance, otherwise, the problems of short circuit, open circuit and the like are caused. To improve heat resistance of a PCB circuit substrate, a high heat resistance inorganic material is generally added to the PCB circuit substrate. This results in a decrease in the resin content of the substrate, so that the bonding force of the copper foil to the substrate is decreased. And the binding force between the copper foil and the substrate can be further reduced due to the repeated thermal shock experienced by the PCB circuit substrate in the preparation process, so that the copper foil is easy to peel off and fall off in the use process, and the PCB circuit substrate is damaged.
The current copper foil production method generally comprises the steps of preparing a raw foil through electrodeposition, and then modifying and optimizing the raw foil. However, the conventional electroplating solution for electrolytic green foil has poor stability, less times of electroplating and low use efficiency. Moreover, the copper foil prepared by the method has the common problems of high surface roughness, low heat-resistant temperature and poor peeling strength.
Disclosure of Invention
The invention aims to solve the problems of poor stability, high surface roughness, low heat-resistant temperature and poor peeling strength of an electroplating solution for electrolytic green foil in the prior art, and provides an ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil, and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a plating solution for electrolytic green foil, wherein the plating solution comprises: copper sulfate with the content of 60-90g/L calculated by copper ion, hydrogen chloride with the content of 10-30ppm calculated by chlorine ion, sulfuric acid with the content of 80-130g/L, additive I with the content of 5-30mg/L and additive II with the content of 5-25 mg/L;
wherein the additive I is selected from one or more of 2-mercaptobenzimidazole, ethylene thiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate and dimethylaminothio-propane sulfonate; the additive II is selected from amino group-containing compounds.
The second aspect of the invention provides an alloying formulation, wherein the alloying formulation comprises 50-200g/L of an alloy source and 50-200g/L of a complexing agent;
wherein the alloy source is soluble metal salt, and the soluble metal salt is selected from two or more of nickel salt, tungsten salt, zirconium salt, hafnium salt, cobalt salt, molybdenum salt and rare earth sulfate; the complexing agent is one or more selected from citrate, ammonium sulfate, succinic acid, malic acid, saccharin sodium and sodium dodecyl sulfate.
The third aspect of the invention provides an application of the alloying solution in the second aspect of the invention in preparing copper foil, preferably in preparing ultra-low profile high temperature resistant 5G high frequency high speed copper foil.
In a fourth aspect, the present invention provides a method for preparing a copper foil, wherein the method comprises the steps of:
(1) Electro-deposition is carried out on the electrolytic green foil by using electroplating solution to obtain ultra-low profile 5G green foil;
(2) Coarsening the ultralow-profile 5G copper foil in coarsening liquid to obtain coarsened copper foil;
(3) Placing the roughened copper foil into a curing liquid for curing to obtain a cured copper foil;
(4) Placing the solidified copper foil into an alloying solution for alloying treatment to obtain an alloyed copper foil;
(5) And placing the alloyed copper foil into a silanization preparation liquid for silanization treatment to obtain the copper foil.
A fifth aspect of the present invention provides a copper foil, wherein the copper foil has a surface roughness Ra of 0.2 μm or less and a surface roughness Rz of 1.3 μm or less; the PPO substrate has the peeling strength of more than or equal to 0.5N/mm at 200 ℃ and the peeling strength attenuation rate of less than or equal to 8 percent after being subjected to tin immersion at 288 ℃ for 5 min.
In a fifth aspect, the present invention provides an application of the copper foil according to the fourth aspect of the present invention in 5G high frequency and high speed communication.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
1) The electroplating solution for electrolytic green foil provided by the invention has the advantages that the additive I and the additive II have synergistic effect, so that the stability of the electroplating solution can be obviously improved, the preparation times of the ultra-low profile green foil can be increased from the conventional 1-2 times to more than 3 times, for example, the preparation times can be up to 4-5 times;
2) The alloying liquid provided by the invention is applied to the preparation of raw foil, so that not only can the reduction of the conductivity of the copper foil caused by oxidative discoloration at high temperature be avoided, but also the copper foil can have smaller (tin-dipping) attenuation rate, the connection strength of the copper foil and a base material at high temperature is enhanced, and the falling off is avoided;
3) The ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil provided by the invention can be kept at 400 ℃ for 15min without color change, and has good high-temperature resistance;
4) The ultra-low profile high temperature resistant 5G high frequency high speed copper foil provided by the invention has the advantages that the PPO base material test peel strength is more than or equal to 0.5N/mm at 200 ℃, the peel strength attenuation rate is less than or equal to 8% after tin immersion at 288 ℃ for 5min, and the bonding strength between the copper foil and a substrate at high temperature is high;
5) The ultra-low profile high temperature resistant 5G high frequency high speed copper foil provided by the invention has small surface roughness, ra is less than or equal to 0.2 mu m, and surface roughness Rz is less than or equal to 1.0 mu m;
6) According to the preparation method of the ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil, provided by the invention, the fluctuation range of the surface roughness Rz of the copper foil can be controlled within +/-0.1, the prepared ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil has a flat surface, the alloy is uniformly distributed, the cracking phenomenon is avoided, and the problems of high surface roughness, low heat-resistant temperature and poor peeling strength of the copper foil are solved;
7) The preparation method of the ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil provided by the invention is simple to operate, low in additive consumption and low in cost, and is suitable for industrial popularization.
Drawings
FIG. 1 is an SEM image at 20000 magnification of the green foil prepared in step (1) of example 1;
FIG. 2 is an SEM image at 10000 times of the copper foil prepared in the step (5) of example 1;
FIG. 3 is an EDS characterization graph of the copper foil prepared in example 1;
fig. 4 is an EDS characterization graph of the copper foil prepared in comparative example 5.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, all solvents of the solutions are water, preferably deionized water.
A first aspect of the present invention provides a plating solution for electrolytic green foil, wherein the plating solution comprises: copper sulfate with the content of 60-90g/L calculated by copper ion, hydrogen chloride with the content of 10-30ppm calculated by chlorine ion, sulfuric acid with the content of 80-130g/L, additive I with the content of 5-30mg/L and additive II with the content of 5-25 mg/L;
wherein the additive I is selected from one or more of 2-mercaptobenzimidazole, ethylene thiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate and dimethylaminothio-propane sulfonate; the additive II is selected from amino group-containing compounds.
In general, when a green foil is produced by using a plating solution, the surface roughness of the obtained green foil increases gradually with the increase of the number of plating steps, and thus the number of ultra-low profile green foils that can be produced by using a conventional plating solution for electrolytic green foil is relatively small. However, in the invention, the inventor of the invention discovers that the synergistic effect of the additive I and the additive II can obviously improve the stability of the electroplating solution, increase the preparation times of the ultra-low profile raw foil, and improve the preparation times of the ultra-low profile raw foil from the conventional 1-2 times to more than 3 times, for example, can reach 4-5 times. Wherein, the ultra-low profile in the present invention means HVLP3, that is, copper foil surface roughness Rz satisfies 0.5 < rz.ltoreq.1.0 μm in accordance with the regulations in Japanese JIS standard.
In a preferred embodiment, the electrolytic foil-forming plating solution comprises: copper sulfate with a content of 60-75g/L calculated by copper ion, hydrogen chloride with a content of 15-25ppm calculated by chlorine ion, sulfuric acid with a content of 100-125g/L, additive I with a content of 10-20mg/L and additive II with a content of 15-20 mg/L.
In a preferred embodiment, the additive I is selected from any one of 2-mercaptobenzimidazole, ethylenethiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate, dimethylaminothio propane sulfonate.
In a preferred embodiment, the additive I is selected from any two of 2-mercaptobenzimidazole, ethylenethiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate, dimethylaminothio propane sulfonate.
In a preferred embodiment, the additive I is 2-mercaptobenzimidazole and ethylenethiourea, preferably in a mass ratio of 1:0.5-1.5 of 2-mercaptobenzimidazole and ethylene thiourea, or the additive I is 3-mercapto-1-propane sodium sulfonate and ethylene thiourea, and the preferable mass ratio is 1:0.5-1.5 of 3-mercapto-1-propane sodium sulfonate and ethylene thiourea.
In a preferred embodiment, the additive II is selected from one or more of bovine hide polypeptide, collagen, gelatin, bone glue, triisopropanolamine; further selected from any two of cow leather polypeptide, collagen, gelatin and bone gelatin.
In the present invention, the bovine hide polypeptide, collagen, gelatin and bone gelatin are conventional additives in the art, and the present invention is not particularly limited thereto. Preferably, the bovine hide polypeptide, collagen, gelatin and bone gelatin have a gel strength of 100-300Bloom, respectively, alone.
The second aspect of the invention provides an alloying formulation, wherein the alloying formulation comprises 50-200g/L of an alloy source and 50-200g/L of a complexing agent;
wherein the alloy source is a soluble metal salt selected from two or more of nickel salt, tungsten salt, zirconium salt, hafnium salt, cobalt salt, molybdenum salt, and optionally rare earth salt; the complexing agent comprises one or more of citrate and ammonium sulfate, and optionally succinic acid, optionally malic acid, optionally saccharin sodium, and optionally sodium dodecyl sulfate.
In the invention, the alloying liquid is used in preparing the copper foil, and the metals in the nickel salt, tungsten salt, zirconium salt, hafnium salt, cobalt salt and molybdenum salt in the alloying liquid finally enter the copper foil and are uniformly distributed on the surface of the copper foil, so that the high temperature resistance of the copper foil can be obviously improved. The metal in the rare earth salt does not enter the copper foil basically, but the rare earth salt can promote the metal elements in the nickel salt, the tungsten salt, the zirconium salt, the hafnium salt, the cobalt salt and the molybdenum salt to enter the copper foil, and the distribution of the metal elements in the nickel salt, the tungsten salt, the zirconium salt, the hafnium salt, the cobalt salt and the molybdenum salt on the surface of the copper foil is more uniform.
In a preferred embodiment, the soluble metal salt is selected from two or more of nickel sulfate, sodium tungstate, zirconium sulfate, hafnium sulfate, cobalt sulfate, sodium molybdate, and optionally one or more of cerium sulfate, lanthanum sulfate, praseodymium sulfate, dysprosium sulfate, europium sulfate, cerium nitrate, lanthanum nitrate, praseodymium nitrate, dysprosium nitrate, europium nitrate; further preferred are any two, three or four of nickel sulfate, sodium tungstate, hafnium sulfate and cerium sulfate; still more preferred are nickel sulfate, sodium tungstate, hafnium sulfate, and cerium sulfate.
In a preferred embodiment, the citrate is selected from one or more of sodium citrate, potassium citrate, ferric ammonium citrate.
In a preferred embodiment, the alloying formulation comprises: 80-150g/L of alloy source and 90-130g/L of complexing agent.
In a preferred embodiment, the concentration of the soluble metal salt in the alloying formulation is independently selected from 10-80g/L.
In a preferred embodiment, the complexing agent comprises 60-120g/L, preferably 70-100g/L, citrate, 10-30g/L, preferably 15-25g/L, ammonium sulfate, 0-5g/L, preferably 0.5-2.5g/L, succinic acid, 0-5g/L, preferably 0.5-2.5g/L, malic acid, 0-5g/L, preferably 0.5-2.5g/L, sodium saccharin, 0-5g/L, preferably 0.5-2.5g/L sodium lauryl sulfate.
In a preferred embodiment, the alloying formulation comprises: 10-30g/L nickel sulfate, 50-70g/L sodium tungstate, 20-40g/L hafnium sulfate, 10-30g/L cerium sulfate, 90-110g/L sodium citrate, 10-25g/L ammonium sulfate, 1-2g/L sodium dodecyl sulfate.
The third aspect of the invention provides an application of the alloying solution in preparing copper foil.
In a fourth aspect, the present invention provides a method for preparing a copper foil, wherein the method comprises the steps of:
(1) Electro-deposition is carried out on the electrolytic green foil by using electroplating solution to obtain ultra-low profile 5G green foil;
(2) Coarsening the ultralow-profile 5G copper foil in coarsening liquid to obtain coarsened copper foil;
(3) Placing the roughened copper foil into a curing liquid for curing to obtain a cured copper foil;
(4) Placing the solidified copper foil into an alloying solution for alloying treatment to obtain an alloyed copper foil;
(5) And placing the alloyed copper foil into a silanization preparation liquid for silanization treatment to obtain the copper foil.
In the step (1) of the process,
in a preferred embodiment, the electrolytic foil-forming plating solution comprises: copper sulfate with the content of 60-90g/L calculated by copper ion, hydrogen chloride with the content of 10-30ppm calculated by chlorine ion, sulfuric acid with the content of 80-130g/L, additive I with the content of 5-30mg/L and additive II with the content of 5-25 mg/L;
wherein the additive I is selected from one or more of 2-mercaptobenzimidazole, ethylene thiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate and dimethylaminothio-propane sulfonate; the additive II is selected from amino group-containing compounds.
In a preferred embodiment, the electrolytic foil-forming plating solution comprises: copper sulfate with a content of 60-75g/L calculated by copper ion, hydrogen chloride with a content of 15-25ppm calculated by chlorine ion, sulfuric acid with a content of 100-125g/L, additive I with a content of 10-20mg/L and additive II with a content of 15-20 mg/L.
In a preferred embodiment, the additive I is selected from any one of 2-mercaptobenzimidazole, ethylenethiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate, dimethylaminothio propane sulfonate.
In a preferred embodiment, the additive I is selected from any two of 2-mercaptobenzimidazole, ethylenethiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate, dimethylaminothio propane sulfonate.
In a preferred embodiment, the additive I is 2-mercaptobenzimidazole and ethylenethiourea, preferably in a mass ratio of 1:0.5-1.5 of 2-mercaptobenzimidazole and ethylene thiourea, or the additive I is 3-mercapto-1-propane sodium sulfonate and ethylene thiourea, and the preferable mass ratio is 1:0.5-1.5 of 3-mercapto-1-propane sodium sulfonate and ethylene thiourea.
In a preferred embodiment, the additive II is selected from one or more of bovine hide polypeptide, collagen, gelatin, bone glue, triisopropanolamine; further selected from any two of cow leather polypeptide, collagen, gelatin and bone gelatin.
In a preferred embodiment, the bovine hide polypeptide, collagen, gelatin, bone gelatin have a gel strength of 100-300Bloom, respectively, alone.
In a preferred embodiment, the operating conditions of the electrodeposition include: the current density is 20-35A/dm 2 Preferably 20-30A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the electroplating solution is room temperature, preferably 15-35 ℃; the circulation flow rate of the electroplating solution is 200-300L/min, preferably 210-280L/min.
Wherein, in the invention, when the electroplating solution is electrodeposited, the anode plate is selected from pure copper plates, and the cathode plate is selected from titanium plates. The pure copper plate and the titanium plate have meanings known in the art, and the present invention is not particularly limited thereto.
In a preferred embodiment, the thickness of the ultra low profile 5G green foil is 10-40 μm, preferably 10-20 μm; ra is less than or equal to 0.15 mu m, preferably 0.09-0.1 mu m; rz is less than or equal to 0.95 mu m, preferably 0.80-0.91 mu m. Wherein, in the present invention, ra and Rz are measured by GBT 5230-2020.
In the step (2) of the process,
in a preferred embodiment, the roughening solution includes: copper sulfate with the content of 5-30g/L, sulfuric acid with the content of 80-130g/L and inorganic additive with the content of 0.05-3 g/L; the inorganic additive is selected from one or more of soluble rare earth salt, tungstate and molybdate.
In the invention, the soluble rare earth salt in the roughening solution can uniformly distribute copper particles deposited and generated in the roughening process on the surface of the raw foil, and the soluble rare earth salt can refine copper particles generated in the roughening process, so that the roughness of the surface of the copper foil is increased in a small range, the surface area ratio of the copper foil is increased, and the peeling resistance of the copper foil is enhanced.
In a preferred embodiment, the roughening solution includes: copper sulfate with the content of 10-25g/L, sulfuric acid with the content of 90-110g/L and inorganic additive with the content of 1-2.5g/L based on copper ions.
In a preferred embodiment, the soluble rare earth salt is selected from one or more of cerium sulfate, lanthanum sulfate, praseodymium sulfate, dysprosium sulfate, europium sulfate, cerium nitrate, lanthanum nitrate, praseodymium nitrate, dysprosium nitrate, europium nitrate.
In a preferred embodiment, the tungstate is selected from one or more of lithium tungstate, sodium tungstate, ammonium tungstate, magnesium tungstate, potassium tungstate.
In a preferred embodiment, the molybdate is selected from one or more of ammonium molybdate, lithium molybdate, potassium molybdate.
In a preferred embodiment, the inorganic additive is selected from two or three of soluble rare earth salts, tungstates, molybdates. For example, it may be a soluble rare earth salt and tungstate, a soluble rare earth salt and molybdate, a tungstate and molybdate, or a soluble rare earth salt, tungstate and molybdate.
In a preferred embodiment, the inorganic additives are cerium nitrate and sodium tungstate; further preferably, the mass ratio of cerium nitrate to sodium tungstate is 1:5-10. Wherein, in the invention, when cerium nitrate and sodium tungstate are 1:5-10, the peel strength of the prepared copper foil can be further improved.
In a preferred embodiment, the coarsening operating conditions include: the current density is 10-40A/dm 2 Preferably 15-30A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the coarsening liquid is room temperature, preferably 15-35 ℃; coarsening time is 2-15s, preferably 3-10s; the circulating flow rate of the coarsening liquid is 200-350L/min, preferably 200-250L/min.
In the invention, through roughening treatment, the surface area ratio of the copper foil can be increased, and meanwhile, the copper foil has low profile and high peeling strength.
In the step (3) of the process,
in a preferred embodiment, the curing formulation comprises: copper sulfate with the copper ion content of 30-70g/L and sulfuric acid with the copper ion content of 80-120 g/L; further preferably, the curing formulation comprises: copper sulfate with the content of 40-60g/L and sulfuric acid with the content of 90-100g/L calculated by copper ions. In the present invention, the peeling resistance of the copper foil can be further increased by the curing treatment.
In a preferred embodiment, the operating conditions for curing include: the current density is 20-40A/dm 2 Preferably 20-35A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the curing liquid is room temperature, preferably 15-35 ℃; the curing time is 5 to 10s, preferably 6 to 8s; the circulation flow rate of the curing liquid is 200-350L/min, preferably 250-300L/min.
In the step (4) of the method,
in a preferred embodiment, the alloying formulation comprises: the alloying solution comprises 50-500g/L of alloy source and 50-200g/L of complexing agent; wherein the alloy source is a soluble metal salt selected from two or more of nickel salt, tungsten salt, zirconium salt, hafnium salt, cobalt salt, molybdenum salt, and optionally rare earth salt; the complexing agent comprises one or more of citrate and ammonium sulfate, and optionally succinic acid, optionally malic acid, optionally saccharin sodium, and optionally sodium dodecyl sulfate.
In a preferred embodiment, the soluble metal salt is selected from two or more of nickel sulfate, sodium tungstate, zirconium sulfate, hafnium sulfate, cobalt sulfate, sodium molybdate, and optionally one or more of cerium sulfate, lanthanum sulfate, praseodymium sulfate, dysprosium sulfate, europium sulfate, cerium nitrate, lanthanum nitrate, praseodymium nitrate, dysprosium nitrate, europium nitrate, more preferably any two, three or four of nickel sulfate, sodium tungstate, hafnium sulfate, cerium sulfate, still more preferably nickel sulfate, sodium tungstate, hafnium sulfate, and cerium sulfate.
In a preferred embodiment, the citrate is selected from one or more of sodium citrate, potassium citrate, ferric ammonium citrate.
In a preferred embodiment, the alloying formulation comprises: the alloying solution comprises 80-150g/L of alloy source and 90-130g/L of complexing agent.
In a preferred embodiment, the concentration of the soluble metal salt in the alloying formulation is independently selected from 10-80g/L.
In a preferred embodiment, the complexing agent comprises 60-120g/L, preferably 70-100g/L, citrate, 10-30g/L, preferably 15-25g/L, ammonium sulfate, 0-5g/L, preferably 0.5-2.5g/L, succinic acid, 0-5g/L, preferably 0.5-2.5g/L, malic acid, 0-5g/L, preferably 0.5-2.5g/L, sodium saccharin, 0-5g/L, preferably 0.5-2.5g/L sodium lauryl sulfate.
In a preferred embodiment, the alloying formulation comprises: 10-30g/L nickel sulfate, 50-70g/L sodium tungstate, 20-40g/L hafnium sulfate, 10-30g/L cerium sulfate, 90-110g/L sodium citrate, 10-25g/L ammonium sulfate, 1-2g/L sodium dodecyl sulfate.
In a preferred embodiment, the operating conditions of the alloying treatment include: the current density is 2-10A/dm 2 Preferably 3-8A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the alloying solution is room temperature, preferably 15-35 ℃; the alloying time is 2 to 15s, preferably 5 to 10s.
In the invention, the stability of the copper foil at high temperature can be improved through alloying treatment, so that not only can the reduction of the conductivity of the copper foil caused by oxidative discoloration at high temperature be avoided, but also the copper foil can have smaller (tin-immersed) attenuation rate, the connection strength of the copper foil and a base material at high temperature is enhanced, and the falling-off is avoided.
In the step (5) of the process,
in a preferred embodiment, the silylated formulation comprises a silane coupling agent and a pH adjuster; wherein the pH value of the silanization preparation liquid is 3-7, preferably 4-6; the content of the silane coupling agent is 1-5mL/L, preferably 2-4mL/L.
In a preferred embodiment, the silane coupling agent is selected from one or more of KH550, KH560, KH570, KH 590.
In a preferred embodiment, the pH adjuster is selected from acetic acid and/or phytic acid.
In a preferred embodiment, the silylation treatment comprises immersing the alloyed copper foil in the silylating formulation at room temperature for 3-15s, preferably 5-10s.
In the invention, the high-temperature oxidation resistance of the copper foil can be improved and the peeling resistance of the copper foil can be enhanced through silanization treatment.
In a preferred embodiment, the silylation treatment is completed and then baked to provide an alloyed copper foil. Wherein the temperature of the drying is 80-160 ℃, and the drying time is 5-20s.
In the invention, the moisture on the surface of the copper foil can be sufficiently removed by drying, so that the oxidation resistance of the copper foil is prevented from being influenced.
In a preferred embodiment, to further improve the high temperature resistance and the peeling resistance of the copper foil, the method further comprises placing the alloyed copper foil into a passivation solution to perform passivation treatment to obtain a passivated copper foil before the silylation treatment of the alloyed copper foil, and then subjecting the passivated copper foil to the silylation treatment.
In a preferred embodiment, the passivating formulation comprises one or more of sodium molybdate, zinc sulfate and citric acid, and optionally, cerium sulfate and/or ethylenediamine; wherein the concentration of sodium molybdate, zinc sulfate and citric acid in the passivation solution is independently selected from 5-60g/L respectively, and the concentration of cerium sulfate and ethylenediamine is independently selected from 0-10g/L respectively.
In a preferred embodiment, the passivating formulation comprises: 10-30g/L sodium molybdate, 5-15g/L zinc sulfate, 30-50g/L citric acid and 1-3g/L ethylenediamine.
In a preferred embodiment, the total concentration of the components in the passivating formulation is from 40 to 100g/L, preferably from 60 to 80g/L.
In a preferred embodiment, the operating conditions of the passivation process include: the current density is 2-5A/dm 2 Preferably 3-5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the passivation solution is room temperature, preferably 15-35 ℃.
The fifth aspect of the present invention provides a copper foil, wherein the copper foil has a surface roughness Ra of 0.2 μm or less and a surface roughness Rz of 1 μm or less; the PPO substrate has the peeling strength of more than or equal to 0.5N/mm at 200 ℃ and the peeling strength attenuation rate of less than or equal to 8 percent after being subjected to tin immersion at 288 ℃ for 5 min.
In a preferred embodiment, the copper foil has a surface roughness Ra of 0.1 to 0.16 μm, preferably 0.1 to 0.12 μm; the surface roughness Rz is 0.8-1 μm, preferably 0.92-0.97 μm; the PPO substrate has a peel strength of 0.6-1.1N/mm, preferably 0.8-0.9N/mm, when tested at 200 ℃; the peel strength decay rate is 2.5-6%, preferably 4.5-5% after 5min of tin immersion at 288 ℃.
In a preferred embodiment, the copper foil has a surface area ratio of 1.4 to 1.9, preferably 1.7 to 1.8; the surface contact angle is 80-100 °, preferably 83-85 °; the thickness is 12-45. Mu.m, preferably 15-25. Mu.m.
Wherein, in the present invention, the surface area ratio refers to the ratio of the contour surface area to the plane area of the copper foil. The surface area ratio is high, so that the copper foil has good peeling resistance and small surface contact angle, and the copper foil has good wettability.
In a preferred embodiment, the surface of the copper foil contains a modified metal selected from two or more of nickel, tungsten, zirconium, hafnium, cobalt, and molybdenum, and is uniformly distributed on the surface of the copper foil.
In a preferred embodiment, the modified metal is contained in an amount of 20 to 40% by mass, preferably 25 to 35% by mass, based on the mass of the copper foil.
In the invention, the mass content of the modified metal in the copper foil is tested through EDS characterization, 4 test points are selected on the copper foil at will, the content of the modified metal element at the 4 test points is tested respectively, and then the average value is taken as a test result.
A fifth aspect of the present invention provides an application of the copper foil according to the fourth aspect of the present invention in 5G high frequency and high speed communication.
Wherein, 5G high frequency and high speed refer to a frequency band with an operating frequency above 6 GHz. The copper foil provided by the invention is an ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil, has the advantages of low surface roughness, good high-temperature resistance and strong peeling resistance, can meet the application requirements of the 5G high-frequency high-speed copper foil, and can be applied to 5G high-frequency high-speed communication.
The present invention will be described in detail by examples. Wherein, the collagen has a gel strength of 100Bloom, the bone gel has a gel strength of 150Bloom, and the gelatin has a gel strength of 100Bloom.
Example 1
(1) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring by a magnetic stirrer, and adding hydrochloric acid after the copper sulfate pentahydrate is completely dissolved for continuous stirring; then adding 2-mercaptobenzimidazole, ethylene thiourea, collagen and bone glue, and uniformly mixing to obtain electroplating solution for electrolytic green foil;
wherein, in the electroplating solution for electrolytic foil production, the content of copper sulfate is 70g/L based on copper ions, the content of hydrogen chloride is 20ppm based on chloride ions, the content of sulfuric acid is 120g/L, the content of 2-mercaptobenzimidazole is 5mg/L, the content of ethylene thiourea is 5mg/L, the content of collagen is 10mg/L, and the content of bone glue is 10mg/L;
placing the electrolyte into an electrolytic tank, and performing electrodeposition at room temperature by taking a pure copper plate as an anode plate and a titanium plate as a cathode plate to obtain ultra-low profile 5G green foil; wherein the current density is 20A/dm 2 The circulation flow rate of the electroplating solution is 250L/min;
(2) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by a magnetic stirrer, and adding cerium nitrate and sodium tungstate after the copper sulfate pentahydrate is completely dissolved to obtain coarsening liquid; wherein, in the coarsening solution, the content of copper sulfate is 10g/L, the content of sulfuric acid is 100g/L, the content of cerium nitrate is 0.2g/L, and the content of sodium tungstate is 1.5g/L;
Placing the ultra-low profile 5G raw foil into a roughening solution, and roughening at room temperature to obtain roughened raw foil; wherein the current density is 20A/dm 2 The circulating flow rate of the roughening solution is 250L/min, and the roughening time is 5s;
(3) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by using a magnetic stirrer, and uniformly stirring the copper sulfate pentahydrate to obtain a solidification preparation liquid; wherein, in the curing liquid, the content of copper sulfate is 40g/L and the content of sulfuric acid is 100g/L based on copper ions;
placing the roughened copper foil into a curing solution, and curing at room temperature to obtain a cured copper foil; wherein the current density is 20A/dm 2 The circulation flow rate of the curing liquid is 300L/min, and the curing time is 6s;
(4) Dissolving nickel sulfate, sodium tungstate, hafnium sulfate and cerium sulfate in deionized water, then adding sodium citrate, ammonium sulfate and sodium dodecyl sulfate, and uniformly mixing to obtain an alloying solution; wherein, in the alloying liquid, the content of nickel sulfate is 20g/L, the content of sodium tungstate is 60g/L, the content of hafnium sulfate is 30g/L, the content of cerium sulfate is 20g/L, the content of sodium citrate is 100g/L, the content of ammonium sulfate is 15g/L, and the content of sodium dodecyl sulfate is 1.5g/L;
Placing the solidified copper foil into an alloying solution, and performing alloying treatment at room temperature to obtain an alloyed copper foil; wherein the current density is 3A/dm 2 Alloying time is 5s;
dissolving sodium molybdate, zinc sulfate, citric acid and ethylenediamine in deionized water, and uniformly mixing to obtain a passivation solution; wherein, in the passivation solution, the content of sodium molybdate is 20g/L, the content of zinc sulfate is 8g/L, the content of citric acid is 40g/L, and the content of ethylenediamine is 2g/L;
the passivated copper foil is put into passivation solution, and passivation is carried out at room temperature to obtain the passivated copper foil; wherein the current density is 2.5A/dm 2 ；
(5) And (3) silanization treatment:
dissolving KH570 in deionized water, uniformly mixing, and adding acetic acid to adjust the pH value to 4 to obtain silanization preparation liquid; wherein, the content of KH570 in the silanization preparation liquid is 2mL/L;
immersing the passivated copper foil in silanization liquid, soaking for 5s at room temperature, then placing the immersed copper foil in a constant temperature and constant humidity drying box, and drying for 20s at 160 ℃ to obtain the copper foil.
Example 2
(1) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring by a magnetic stirrer, and adding hydrochloric acid after the copper sulfate pentahydrate is completely dissolved for continuous stirring; then adding 3-mercapto-1-propane sodium sulfonate, ethylene thiourea, collagen and gelatin, and uniformly mixing to obtain electroplating solution for electrolytic green foil;
Wherein, in the electroplating solution for electrolytic foil production, the content of copper sulfate is 80g/L based on copper ions, the content of hydrogen chloride is 15ppm based on chloride ions, the content of sulfuric acid is 120g/L, the content of 3-mercapto-1-propane sodium sulfonate is 10mg/L, the content of ethylene thiourea is 5mg/L, the content of collagen is 5mg/L, and the content of gelatin is 10mg/L;
placing the electrolyte into an electrolytic tank, and performing electrodeposition at room temperature by taking a pure copper plate as an anode plate and a titanium plate as a cathode plate to obtain ultra-low profile 5G green foil; wherein the current density is 20A/dm 2 The circulation flow rate of the electroplating solution is 250L/min;
(2) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by a magnetic stirrer, and adding lanthanum nitrate and sodium molybdate after the copper sulfate pentahydrate is completely dissolved to obtain coarsening liquid; wherein, in the coarsening solution, the content of copper sulfate is 10g/L, the content of sulfuric acid is 120g/L, the content of lanthanum nitrate is 0.2g/L and the content of sodium molybdate is 1g/L;
placing the ultra-low profile 5G raw foil into a roughening solution, and roughening at room temperature to obtain roughened raw foil; wherein the current density is 20A/dm 2 The circulating flow rate of the roughening solution is 250L/min, and the roughening time is 5s;
(3) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by using a magnetic stirrer, and uniformly stirring the copper sulfate pentahydrate to obtain a solidification preparation liquid; wherein, in the curing liquid, the content of copper sulfate is 50g/L and the content of sulfuric acid is 100g/L based on copper ions;
placing the roughened copper foil into a curing solution, and curing at room temperature to obtain a cured copper foil; wherein the current density is 20A/dm 2 The circulation flow rate of the curing liquid is 300L/min, and the curing time is 6s;
(4) Dissolving sodium tungstate, cobalt sulfate and cerium sulfate in deionized water, then adding sodium citrate and ammonium sulfate, and uniformly mixing to obtain an alloying solution; wherein, in the alloying liquid, the content of sodium tungstate is 70g/L, the content of cobalt sulfate is 50g/L, the content of cerium sulfate is 20g/L, the content of sodium citrate is 90g/L, and the content of ammonium sulfate is 20g/L;
placing the solidified copper foil into an alloying solution, and performing alloying treatment at room temperature to obtain an alloyed copper foil; wherein the current density is 3A/dm 2 Alloying time is 5s;
dissolving sodium molybdate, zinc sulfate and citric acid in deionized water, and uniformly mixing to obtain a passivation solution; wherein, in the passivation solution, the content of sodium molybdate is 20g/L, the content of zinc sulfate is 8g/L, and the content of citric acid is 40g/L;
The passivated copper foil is put into passivation solution, and passivation is carried out at room temperature to obtain the passivated copper foil; wherein the current density is 2.5A/dm 2 ；
(5) And (3) silanization treatment:
dissolving KH570 in deionized water, uniformly mixing, and adding phytic acid to adjust the pH value to 6 to obtain silanization preparation liquid; wherein, the content of KH570 in the silanization preparation liquid is 4mL/L;
immersing the passivated copper foil in silanization liquid, soaking for 5s at room temperature, then placing the immersed copper foil in a constant temperature and constant humidity drying box, and drying for 20s at 160 ℃ to obtain the copper foil.
Example 3
(1) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring by a magnetic stirrer, and adding hydrochloric acid after the copper sulfate pentahydrate is completely dissolved for continuous stirring; then adding sodium polydithio-dipropyl sulfonate and triisopropanolamine, and uniformly mixing to obtain electroplating solution for electrolytic green foil;
wherein, in the electroplating solution for electrolytic foil production, the content of copper sulfate is 80g/L based on copper ions, the content of hydrogen chloride is 20ppm based on chloride ions, the content of sulfuric acid is 110g/L, the content of sodium polydithio-dipropyl sulfonate is 10mg/L, and the content of triisopropanolamine is 15mg/L;
placing the electrolyte into an electrolytic tank, taking a pure copper plate as an anode plate, and a titanium plate as a cathode plate, and performing electrodeposition at room temperature to obtain an ultralow wheel Profile 5G green foil; wherein the current density is 20A/dm 2 The circulation flow rate of the electroplating solution is 300L/min;
(2) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by a magnetic stirrer, and adding cerium nitrate and sodium tungstate after the copper sulfate pentahydrate is completely dissolved to obtain coarsening liquid; wherein, in the coarsening solution, the content of copper sulfate is 20g/L, the content of sulfuric acid is 130g/L, the content of cerium nitrate is 0.5g/L, and the content of sodium tungstate is 1.5g/L;
placing the ultra-low profile 5G raw foil into a roughening solution, and roughening at room temperature to obtain roughened raw foil; wherein the current density is 20A/dm 2 The circulating flow rate of the roughening solution is 300L/min, and the roughening time is 3s;
(3) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by using a magnetic stirrer, and uniformly stirring the copper sulfate pentahydrate to obtain a solidification preparation liquid; wherein, in the curing liquid, the content of copper sulfate is 60g/L and the content of sulfuric acid is 100g/L based on copper ions;
placing the roughened copper foil into a curing solution, and curing at room temperature to obtain a cured copper foil; wherein the current density is 20A/dm 2 The circulation flow rate of the curing liquid is 300L/min, and the curing time is 6s;
(4) Dissolving nickel sulfate, cobalt sulfate and cerium sulfate in deionized water, then adding sodium citrate, ammonium sulfate and succinic acid, and uniformly mixing to obtain an alloying solution; wherein, in the alloying liquid, the content of nickel sulfate is 40g/L, the content of cobalt sulfate is 60g/L, the content of cerium sulfate is 20g/L, the content of sodium citrate is 90g/L, the content of ammonium sulfate is 20g/L, and the content of succinic acid is 10g/L;
placing the solidified copper foil into an alloying solution, and performing alloying treatment at room temperature to obtain an alloyed copper foil; wherein the current density is 3A/dm 2 Alloying time is 5s;
dissolving sodium molybdate, zinc sulfate and citric acid in deionized water, and uniformly mixing to obtain a passivation solution; wherein, in the passivation solution, the content of sodium molybdate is 20g/L, the content of zinc sulfate is 8g/L, and the content of citric acid is 40g/L;
the passivated copper foil is put into passivation solution, and passivation is carried out at room temperature to obtain the passivated copper foil; wherein the current density is 2.5A/dm 2 ；
(5) And (3) silanization treatment:
dissolving KH570 in deionized water, uniformly mixing, and adding acetic acid to adjust the pH value to 4 to obtain silanization preparation liquid; wherein, the content of KH570 in the silanization preparation liquid is 2mL/L;
Immersing the passivated copper foil in silanization liquid, soaking for 5s at room temperature, then placing the immersed copper foil in a constant temperature and constant humidity drying box, and drying for 20s at 160 ℃ to obtain the copper foil.
Example 4
The same as in example 2, except that the passivation treatment was omitted.
Example 5
(1) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring by a magnetic stirrer, and adding hydrochloric acid after the copper sulfate pentahydrate is completely dissolved for continuous stirring; then adding N, N-dimethyl-dithioformamide sodium propane sulfonate and collagen, and uniformly mixing to obtain electroplating solution for electrolytic green foil;
wherein, in the electroplating solution for electrolytic foil production, the content of copper sulfate is 70g/L based on copper ions, the content of hydrogen chloride is 20ppm based on chloride ions, the content of sulfuric acid is 120g/L, the content of N, N-dimethyl-dithioformamide sodium propane sulfonate is 15mg/L, and the content of collagen is 20mg/L;
placing the electrolyte into an electrolytic tank, and performing electrodeposition at room temperature by taking a pure copper plate as an anode plate and a titanium plate as a cathode plate to obtain ultra-low profile 5G green foil; wherein the current density is 20A/dm 2 The circulation flow rate of the electroplating solution is 250L/min;
(2) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by a magnetic stirrer, and adding lanthanum nitrate and sodium molybdate after the copper sulfate pentahydrate is completely dissolved to obtain coarsening liquid; wherein, in the coarsening solution, the content of copper sulfate is 10g/L, the content of sulfuric acid is 100g/L, the content of lanthanum nitrate is 0.1g/L, and the content of sodium molybdate is 2.0g/L;
Placing the ultra-low profile 5G raw foil into a roughening solution, and roughening at room temperature to obtain roughened raw foil; wherein the current density is 20A/dm 2 The circulating flow rate of the roughening solution is 250L/min, and the roughening time is 5s;
(3) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by using a magnetic stirrer, and uniformly stirring the copper sulfate pentahydrate to obtain a solidification preparation liquid; wherein, in the curing liquid, the content of copper sulfate is 40g/L and the content of sulfuric acid is 100g/L based on copper ions;
placing the roughened copper foil into a curing solution, and curing at room temperature to obtain a cured copper foil; wherein the current density is 20A/dm 2 The circulation flow rate of the curing liquid is 300L/min, and the curing time is 6s;
(4) Dissolving nickel sulfate, sodium tungstate and hafnium sulfate in deionized water, then adding sodium citrate and ammonium sulfate, and uniformly mixing to obtain an alloying solution; wherein, in the alloying solution, the content of nickel sulfate is 30g/L, the content of sodium tungstate is 60g/L, the content of hafnium sulfate is 40g/L, the content of sodium citrate is 90g/L, and the content of ammonium sulfate is 15g/L;
placing the solidified copper foil into an alloying solution, and performing alloying treatment at room temperature to obtain an alloyed copper foil; wherein the current density is 3A/dm 2 Alloying time is 5s;
dissolving sodium molybdate, zinc sulfate and citric acid in deionized water, and uniformly mixing to obtain a passivation solution; wherein, in the passivation solution, the content of sodium molybdate is 20g/L, the content of zinc sulfate is 8g/L, and the content of citric acid is 40g/L;
the passivated copper foil is put into passivation solution, and passivation is carried out at room temperature to obtain the passivated copper foil; wherein the current density is 2.5A/dm 2 ；
(5) And (3) silanization treatment:
dissolving KH570 in deionized water, uniformly mixing, and adding acetic acid to adjust the pH value to 4 to obtain silanization preparation liquid; wherein, the content of KH570 in the silanization preparation liquid is 2mL/L;
immersing the passivated copper foil in silanization liquid, soaking for 5s at room temperature, then placing the immersed copper foil in a constant temperature and constant humidity drying box, and drying for 20s at 160 ℃ to obtain the copper foil.
Example 6
(1) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring by a magnetic stirrer, and adding hydrochloric acid after the copper sulfate pentahydrate is completely dissolved for continuous stirring; adding dimethylaminothiopropane sulfonate, collagen and bone glue, and uniformly mixing to obtain electroplating solution for electrolytic green foil;
wherein, in the electroplating solution for electrolytic foil production, the content of copper sulfate is 70g/L based on copper ions, the content of hydrogen chloride is 20ppm based on chloride ions, the content of sulfuric acid is 130g/L, the content of sodium dimethylaminothiopropane sulfonate is 20mg/L, the content of collagen is 5mg/L, and the content of bone glue is 15mg/L;
Placing the electrolyte into an electrolytic tank, and performing electrodeposition at room temperature by taking a pure copper plate as an anode plate and a titanium plate as a cathode plate to obtain ultra-low profile 5G green foil; wherein the current density is 20A/dm 2 The circulation flow rate of the electroplating solution is 250L/min;
(2) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by a magnetic stirrer, and adding sodium molybdate and sodium tungstate after the copper sulfate pentahydrate is completely dissolved to obtain coarsening liquid; wherein, in the coarsening solution, the content of copper sulfate is 10g/L, the content of sulfuric acid is 120g/L, the content of sodium molybdate is 0.1g/L, and the content of sodium tungstate is 1.5g/L based on copper ions;
placing the ultra-low profile 5G raw foil into a roughening solution, and roughening at room temperature to obtain roughened raw foil; wherein the current density is 20A/dm 2 The circulating flow rate of the roughening solution is 250L/min, and the roughening time is 5s;
(3) Weighing copper sulfate pentahydrate, dissolving the copper sulfate pentahydrate in deionized water, adding sulfuric acid when stirring the copper sulfate pentahydrate by using a magnetic stirrer, and uniformly stirring the copper sulfate pentahydrate to obtain a solidification preparation liquid; wherein, in the curing liquid, the content of copper sulfate is 40g/L and the content of sulfuric acid is 120g/L based on copper ions;
placing the roughened copper foil into a curing solution, and curing at room temperature to obtain a cured copper foil; wherein,, The current density was 20A/dm 2 The circulation flow rate of the curing liquid is 300L/min, and the curing time is 6s;
(4) Dissolving cobalt sulfate, sodium tungstate and lanthanum sulfate in deionized water, then adding sodium citrate, ammonium sulfate and sodium dodecyl sulfate, and uniformly mixing to obtain an alloying solution; in the alloying solution, the content of cobalt sulfate is 50g/L, the content of sodium tungstate is 70g/L, the content of lanthanum sulfate is 20g/L, the content of sodium citrate is 100g/L, the content of ammonium sulfate is 15g/L, and the content of sodium dodecyl sulfate is 1.5g/L;
placing the solidified copper foil into an alloying solution, and performing alloying treatment at room temperature to obtain an alloyed copper foil; wherein the current density is 3A/dm 2 Alloying time is 5s;
dissolving sodium molybdate, zinc sulfate and citric acid in deionized water, and uniformly mixing to obtain a passivation solution; wherein, in the passivation solution, the content of sodium molybdate is 20g/L, the content of zinc sulfate is 8g/L, and the content of citric acid is 40g/L;
the passivated copper foil is put into passivation solution, and passivation is carried out at room temperature to obtain the passivated copper foil; wherein the current density is 2.5A/dm 2 ；
(5) And (3) silanization treatment:
dissolving KH570 in deionized water, uniformly mixing, and adding acetic acid to adjust the pH value to 4 to obtain silanization preparation liquid; wherein, the content of KH570 in the silanization preparation liquid is 2mL/L;
Immersing the passivated copper foil in silanization liquid, soaking for 5s at room temperature, then placing the immersed copper foil in a constant temperature and constant humidity drying box, and drying for 20s at 160 ℃ to obtain the copper foil.
Comparative example 1
The same as in example 1, except that the alloying treatment in step (4) was omitted.
Comparative example 2
The same as in example 2, except that cobalt sulfate, sodium tungstate, sodium citrate and ammonium sulfate were omitted from the alloying formulation in step (4) in an amount of 70g/L, 90g/L, and 20g/L, respectively.
Comparative example 3
The same as in example 2, except that sodium tungstate was omitted, cobalt sulfate was contained in an amount of 50g/L, sodium citrate was contained in an amount of 90g/L, and ammonium sulfate was contained in an amount of 20g/L in the alloying formulation in step (4).
Comparative example 4
The same as in example 2, except that the silylation treatment in step (5) was omitted, and the passivated copper foil was dried to obtain a copper foil.
Comparative example 5
The same as in example 1, except that sodium citrate and ammonium sulfate were not added to the alloying formulation of step (4).
Test example 1
Referring to example 1, a plating solution a for electrolytic green foil was prepared.
Referring to example 1, 2-mercaptobenzimidazole and ethylenethiourea were omitted, and a plating solution B for electrolytic green foil was prepared.
Referring to example 1, collagen and bone glue were omitted, and plating solution C for electrolytic green foil was prepared.
The electrolytic green foils thus prepared were electrodeposited with the plating solutions a to C a plurality of times in accordance with the electrolytic conditions in example 1, green foils were prepared, and each of the green foils thus obtained was subjected to a roughness test, and the specific test results are shown in table 1:
TABLE 1
As is clear from Table 1, the plating solution for electrolytic green foil provided by the invention has good plating solution stability, and at least four ultra-low profile green foils can be prepared. However, the green foil prepared by the electrolytic green foil plating solution B cannot meet the requirement of ultra-low profile, the green foil prepared by the electrolytic green foil plating solution C can meet the requirement of ultra-low profile in the former two times, but the surface roughness Rz value of the green foil is greatly increased after the third time, and the stability of the plating solution is obviously reduced.
Test example 2
The green foils prepared in examples 1-7 were subjected to performance testing and the results are shown in table 2:
TABLE 2
| Thickness/. Mu.m | Ra/μm | Rz/μm | |
| Example 1 | 18 | 0.092 | 0.831 |
| Example 2 | 18 | 0.095 | 0.843 |
| Example 3 | 18 | 0.097 | 0.901 |
| Example 4 | 18 | 0.098 | 0.850 |
| Example 5 | 18 | 0.097 | 0.951 |
| Example 6 | 18 | 0.100 | 0.977 |
As is clear from Table 2, the raw foil obtained in examples 1 to 6 had surface roughness Rz values of less than 1.0 μm, which satisfied the indexes of the ultra-low profile copper foil.
Test example 3
The copper foils prepared in examples 1 to 6 and comparative examples 1 to 5 were subjected to performance test, and the results are shown in Table 3:
Wherein Ra and Rz are tested as per pass GBT5230-2020 using a Mahr PS 10 coarser machine; the surface area ratio is tested by adopting a 3D laser confocal microscope; contact angles were measured using a Dataphysics fully automatic contact angle meter.
The PPO substrate peel strength test method at 200 ℃ comprises the following steps: the copper foil and PPO resin are placed in a plate pressing machine, the plate is pressed for 4 hours at 200 ℃ and 10MPa, 30wt% ferric chloride is used for etching after the plate pressing is finished, and a Kb 1211 anti-stripping tester is used for testing the stripping strength after 5 minutes of etching.
Attenuation rate (wicking) test method: placing copper foil and PPO resin into a plate pressing machine, pressing the plate at 200 ℃ for 4 hours under 10MPa, etching the copper foil by using 30wt% ferric chloride for 5 minutes after the pressing, placing the etched sample into molten tin at 288 ℃ for 5 minutes, taking out the sample, using a Kb 1211 anti-stripping tester for carrying out stripping strength test to obtain a stripping strength value after tin immersion, calculating the attenuation rate by using the stripping strength value after tin immersion and the stripping strength test result of a PPO substrate without tin immersion at 200 ℃, and specifically calculating the formula: (200 ℃ non-tin-immersion PPO substrate peel strength-288 ℃ tin-immersion PPO substrate peel strength)/200 ℃ non-tin-immersion PPO substrate peel strength.
The high temperature resistance test method comprises the following steps: copper is easily oxidized by oxygen in air to appear purple at high temperature. The copper foil was placed in a muffle furnace at 400 ℃ for 15min, and then the color change of the copper foil before and after the treatment was observed. If the copper foil does not change color, the high temperature resistance of the copper foil is good; if the copper foil changes color, it means that the high temperature resistance of the copper foil is poor. Wherein, the deeper the copper foil changes color, the worse the high temperature resistance of the copper foil.
TABLE 3 Table 3
From the test results of examples 1 to 6, the method of the invention can be used for preparing the ultralow-profile high-temperature-resistant 5G high-frequency high-speed copper foil with small roughness, good high-temperature resistance and high bonding strength.
As is clear from comparative examples 2 and 4, the passivation treatment can further improve the peel strength of the copper foil at high temperature (200 ℃ C.), reduce the wicking decay rate of the copper foil, that is, the passivation treatment can improve the peel resistance of the copper foil at high temperature.
It is apparent from comparative examples 1 and 1 that the high temperature oxidation resistance and the high temperature peeling resistance of the copper foil can be significantly improved by performing the alloying treatment during the preparation of the copper foil.
As is apparent from comparative example 2 and comparative examples 2 and 3, in the alloying formulation, except for the rare earth salt, a single metal in the alloy source improves the high temperature oxidation resistance and the high temperature peeling resistance of the copper foil, but the modification effect is poor, and the high temperature oxidation resistance and the high temperature peeling resistance of the copper foil can be remarkably improved by the synergistic effect of the multiple metals.
As is apparent from comparative examples 2 and 4, the peel strength of the copper foil obtained without the silylation treatment at high temperature (200 ℃) in the preparation process was decreased from 0.82N/mm to 0.49N/mm, and the wicking decay rate was increased from 4.91% to 6.79%, compared with the copper foil obtained with the silylation treatment in the preparation process, indicating that the poor peel resistance of the copper foil at high temperature could be significantly improved by the silylation treatment in the preparation process.
As is clear from comparative examples 1 and 5, omitting the complexing agent in the alloying solution during the preparation process leads to a sharp increase in the wicking decay rate of the copper foil and a serious deterioration in the high-temperature oxidation resistance. This is probably because the copper foil prepared cannot have good high temperature resistance because the sodium tungstate and hafnium sulfate in the alloy source cannot be deposited on the surface of the copper foil basically successfully due to the fact that no complexing agent exists in the alloying solution.
Test example 4
SEM characterization of the green foil prepared in step (1) of example 1 and the copper foil prepared in step (5) was performed, and the results are shown in FIGS. 1 and 2, respectively. Wherein, fig. 1 is an SEM image of the green foil prepared in step (1) of example 1, and fig. 2 is an SEM image of the copper foil prepared in step (5) of example 1.
As can be seen from FIG. 1, the green foil prepared in step (1) of example 1 has a very flat surface, has a low surface roughness, and meets the requirements of ultra-low profile copper foil. As can be seen from fig. 2, after the treatment of the present technology, the surface of the copper foil prepared in step (5) of example 1 can form dense and uniform copper nodule particles. The copper nodule particles can increase the contact area between the copper foil and the base material, and are beneficial to improving the peeling strength performance of the copper foil.
Test example 5
EDS characterization was performed on the copper foils prepared in examples 1 to 6 and comparative examples 1 to 5, 4 test points were arbitrarily selected on the copper foil, the contents of the modified metal elements at the 4 test points were respectively tested, and the average value was taken as a test result, which is shown in Table 4:
TABLE 4 Table 4
The EDS characterization results of the copper foils prepared in example 1 and comparative example 5 are shown in fig. 3 to 4 and table 5, among others:
TABLE 5
As is clear from Table 5, in the copper foil prepared in example 1, the modified metal was not only successfully deposited on the surface of the copper foil, but also uniformly distributed on the surface of the copper foil. However, in the copper foil prepared in comparative example 5, tungsten and hafnium cannot be deposited on the surface of the copper foil, and nickel is not uniformly distributed on the surface of the copper foil although deposited, and thus the temperature resistance and the high temperature peeling resistance of the copper foil cannot be improved effectively.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. An electrolytic plating solution for green foil, characterized by comprising: copper sulfate with the content of 60-90g/L calculated by copper ion, hydrogen chloride with the content of 10-30ppm calculated by chlorine ion, sulfuric acid with the content of 80-130g/L, additive I with the content of 5-30mg/L and additive II with the content of 5-25 mg/L;
wherein the additive I is selected from one or more of 2-mercaptobenzimidazole, ethylene thiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate and dimethylaminothio-propane sulfonate; the additive II is selected from amino group-containing compounds.
2. The electrolytic green foil plating solution according to claim 1, wherein the additive II is one or more selected from the group consisting of a bovine hide polypeptide, collagen, gelatin, bone gelatin, triisopropanolamine;
Preferably, the glue strength of the cow leather polypeptide, collagen, gelatin and bone glue is respectively 100-300Bloom by itself.
3. An alloying solution, which is characterized by comprising 50-200g/L of alloy source and 50-200g/L of complexing agent;
wherein the alloy source is a soluble metal salt selected from two or more of nickel salt, tungsten salt, zirconium salt, hafnium salt, cobalt salt, molybdenum salt, and optionally rare earth salt; the complexing agent comprises one or more of citrate and ammonium sulfate, and optionally succinic acid, optionally malic acid, optionally saccharin sodium, and optionally sodium dodecyl sulfate.
4. An alloying formulation according to claim 3, wherein the soluble metal salt is selected from two or more of nickel sulfate, sodium tungstate, zirconium sulfate, hafnium sulfate, cobalt sulfate, sodium molybdate, and optionally one or more of cerium sulfate, lanthanum sulfate, praseodymium sulfate, dysprosium sulfate, europium sulfate, cerium nitrate, lanthanum nitrate, praseodymium nitrate, dysprosium nitrate, europium nitrate; further preferred are any two, three or four of nickel sulfate, sodium tungstate, hafnium sulfate and cerium sulfate; still more preferred are nickel sulfate, sodium tungstate, hafnium sulfate, and cerium sulfate;
Preferably, the citrate is selected from one or more of sodium citrate, potassium citrate and ferric ammonium citrate;
preferably, the alloying formulation comprises: 80-150g/L of alloy source and 90-130g/L of complexing agent;
preferably, in the alloying solution, the concentration of the soluble metal salt is independently selected from 10-80g/L;
preferably, the complexing agent comprises 60-120g/L, preferably 70-100g/L citrate, 10-30g/L, preferably 15-25g/L ammonium sulfate, 0-5g/L succinic acid, preferably 0.5-2.5g/L succinic acid, 0-5g/L malic acid, preferably 0.5-2.5g/L malic acid, 0-5g/L sodium saccharin, preferably 0.5-2.5g/L sodium lauryl sulfate, 0-5g/L sodium lauryl sulfate, preferably 0.5-2.5g/L sodium lauryl sulfate;
preferably, the alloying formulation comprises: 10-30g/L nickel sulfate, 50-70g/L sodium tungstate, 20-40g/L hafnium sulfate, 10-30g/L cerium sulfate, 90-110g/L sodium citrate, 10-25g/L ammonium sulfate, 1-2g/L sodium dodecyl sulfate.
5. Use of the alloying formulation of claim 3 or 4 in the preparation of copper foil.
6. A method for preparing a copper foil, comprising the steps of:
(1) Electro-deposition is carried out on the electrolytic green foil by using electroplating solution to obtain ultra-low profile 5G green foil;
(2) Coarsening the ultralow-profile 5G copper foil in coarsening liquid to obtain coarsened copper foil;
(3) Placing the roughened copper foil into a curing liquid for curing to obtain a cured copper foil;
(4) Placing the solidified copper foil into an alloying solution for alloying treatment to obtain an alloyed copper foil;
(5) And placing the alloyed copper foil into a silanization preparation liquid for silanization treatment to obtain the copper foil.
7. The process according to claim 6, wherein the copper sulfate is contained in an amount of 60 to 90g/L in terms of copper ion, the hydrogen chloride is contained in an amount of 10 to 30ppm in terms of chlorine ion, the sulfuric acid is contained in an amount of 80 to 130g/L, the additive I is contained in an amount of 10 to 30mg/L, and the additive II is contained in an amount of 5 to 25 mg/L;
wherein the additive I is selected from one or more of 2-mercaptobenzimidazole, ethylene thiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate and dimethylaminothio-propane sulfonate; the additive II is selected from amino group-containing compounds.
8. The preparation method according to claim 7, wherein the additive I is any two selected from 2-mercaptobenzimidazole, ethylene thiourea, sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium N, N-dimethyl-dithioformamide propane sulfonate and dimethylaminothio propane sulfonate;
Preferably, the additive I is 2-mercaptobenzimidazole and ethylene thiourea, or the additive I is 3-mercapto-1-propane sodium sulfonate and ethylene thiourea;
preferably, the additive II is selected from one or more of cow leather polypeptide, collagen, gelatin, bone glue and triisopropanolamine;
preferably, the glue strength of the cowhide polypeptide, collagen, gelatin and bone glue is respectively 100-300Bloom independently;
preferably, the operating conditions of the electrodeposition include: the current density is 20-35A/dm 2 Preferably 20-35A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the electroplating solution is room temperature, preferably 15-35 ℃; the circulation flow rate of the electroplating solution is 200-300L/min, preferably 210-280L/min.
9. The production method according to any one of claims 6 to 8, wherein the roughening liquid comprises: copper sulfate with the content of 5-30g/L, sulfuric acid with the content of 80-130g/L and inorganic additive with the content of 0.05-3 g/L; wherein the inorganic additive is selected from one or more of soluble rare earth salts, tungstates and molybdates;
preferably, the soluble rare earth salt is selected from one or more of cerium sulfate, lanthanum sulfate, praseodymium sulfate, dysprosium sulfate, europium sulfate, cerium nitrate, lanthanum nitrate, praseodymium nitrate, dysprosium nitrate and europium nitrate;
Preferably, the tungstate is selected from one or more of lithium tungstate, sodium tungstate, ammonium tungstate, magnesium tungstate and potassium tungstate;
preferably, the molybdate is selected from one or more of ammonium molybdate, potassium molybdate and sodium molybdate;
preferably, the inorganic additive is selected from two or three of soluble rare earth salts, tungstates and molybdates;
preferably, the inorganic additive is cerium nitrate and sodium tungstate; further preferably, the mass ratio of cerium nitrate to sodium tungstate is 1:5-10;
preferably, the coarsening operating conditions include: the current density is 10-40A/dm 2 Preferably 15-30A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the coarsening liquid is room temperature, preferably 15-35 ℃; coarsening time is 2-15s, preferably 3-10s; the circulating flow rate of the coarsening liquid is 200-350L/min, preferably 200-250L/min.
10. The preparation method according to any one of claims 6 to 9, wherein the solidification formulation comprises: copper sulfate with the copper ion content of 30-70g/L and sulfuric acid with the copper ion content of 80-120 g/L;
preferably, the curing formulation comprises: copper sulfate with the content of 40-60g/L and sulfuric acid with the content of 90-100g/L calculated by copper ions;
the operating conditions for the curing include: the current density is 20-40A/dm 2 Preferably 20-35A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the curing liquid is room temperature, preferably 15-35 ℃; the curing time is 5 to 10s, preferably 6 to 8s; the circulation flow rate of the curing liquid is 200-350L/min, preferably 200-300L/min.
11. The production method according to any one of claims 6 to 10, wherein the alloying formulation comprises: the alloying solution comprises 50-500g/L of alloy source and 50-200g/L of complexing agent; wherein the alloy source is a soluble metal salt selected from two or more of nickel salt, tungsten salt, zirconium salt, hafnium salt, cobalt salt, molybdenum salt, rare earth sulfate, and optionally rare earth salt; the complexing agent comprises citrate and ammonium sulfate, and one or more of optional succinic acid, optional malic acid, optional saccharin sodium, and optional sodium dodecyl sulfate;
preferably, the soluble metal salt is selected from two or more of nickel sulfate, sodium tungstate, zirconium sulfate, hafnium sulfate, cobalt sulfate, sodium molybdate, cerium sulfate, lanthanum sulfate, praseodymium sulfate, dysprosium sulfate, europium sulfate; further preferably any two, three or four of nickel sulfate, sodium tungstate, hafnium sulfate and cerium sulfate, and still further preferably nickel sulfate, sodium tungstate, hafnium sulfate and cerium sulfate;
Preferably, the citrate is selected from one or more of sodium citrate, potassium citrate and ferric ammonium citrate;
preferably, the alloying formulation comprises: the alloying solution comprises 80-150g/L of alloy source and 90-130g/L of complexing agent;
preferably, in the alloying solution, the concentration of the soluble metal salt is independently selected from 10-80g/L;
preferably, the complexing agent comprises 60-120g/L, preferably 70-100g/L citrate, 10-30g/L, preferably 15-25g/L ammonium sulfate, 0-5g/L succinic acid, preferably 0.5-2.5g/L succinic acid, 0-5g/L malic acid, preferably 0.5-2.5g/L malic acid, 0-5g/L sodium saccharin, preferably 0.5-2.5g/L sodium lauryl sulfate, 0-5g/L sodium lauryl sulfate, preferably 0.5-2.5g/L sodium lauryl sulfate;
preferably, the alloying formulation comprises: 10-30g/L nickel sulfate, 50-70g/L sodium tungstate, 20-40g/L hafnium sulfate, 10-30g/L cerium sulfate, 90-110g/L sodium citrate, 10-25g/L ammonium sulfate, 1-2g/L sodium dodecyl sulfate;
preferably, the operating conditions of the alloying treatment include: the current density is 2-10A/dm 2 Preferably 3-8A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the alloying solution is room temperature, preferably 15-35 ℃; the alloying time is 2 to 15s, preferably 5 to 10s.
12. The preparation method according to any one of claims 6 to 11, wherein the silylated ligand solution comprises a silane coupling agent and a pH adjuster; wherein the pH value of the silanization preparation liquid is 3-7, preferably 4-6; the content of the silane coupling agent is 1-5mL/L, preferably 2-4mL/L;
preferably, the silane coupling agent is selected from one or more of KH550, KH560, KH570 and KH 590;
preferably, the pH adjuster is selected from acetic acid and/or phytic acid;
preferably, the silylation treatment comprises immersing the alloyed copper foil in the silylation formulation at room temperature for 3-15s, preferably 5-10s.
13. A copper foil is characterized in that the surface roughness Ra of the copper foil is less than or equal to 0.2 mu m, and the surface roughness Rz is less than or equal to 1 mu m; the PPO substrate has the test peel strength of more than or equal to 0.5N/mm at 200 ℃, and the peel strength attenuation rate after tin immersion at 288 ℃ for 5min is less than or equal to 8%;
preferably, the copper foil has a surface roughness Ra of 0.1 to 0.16 μm, preferably 0.1 to 0.12 μm; the surface roughness Rz is 0.8-1 μm, preferably 0.92-0.97 μm; the PPO substrate has a peel strength of 0.6-1.1N/mm, preferably 0.8-0.9N/mm, when tested at 200 ℃; the peeling strength attenuation rate is 2.5-6%, preferably 4.5-5% after tin immersion at 288 ℃ for 5 min;
Preferably, the surface area ratio of the copper foil is 1.4 to 1.9, preferably 1.7 to 1.8; the surface contact angle is 80-100 °, preferably 83-85 °; the thickness is 12-45. Mu.m, preferably 15-25. Mu.m.
14. The use of the copper foil of claim 13 in 5G high frequency high speed communications.
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