CN114657610A - Preparation method of strippable ultrathin carrier copper foil - Google Patents
Preparation method of strippable ultrathin carrier copper foil Download PDFInfo
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- CN114657610A CN114657610A CN202210311750.5A CN202210311750A CN114657610A CN 114657610 A CN114657610 A CN 114657610A CN 202210311750 A CN202210311750 A CN 202210311750A CN 114657610 A CN114657610 A CN 114657610A
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- Prior art keywords
- copper foil
- layer
- ultra
- preparation
- carrier
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 239000011889 copper foil Substances 0.000 title claims abstract description 205
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000010410 layer Substances 0.000 claims abstract description 127
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000012044 organic layer Substances 0.000 claims abstract description 23
- 230000004888 barrier function Effects 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- -1 polydithio-dipropyl Polymers 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000001856 Ethyl cellulose Substances 0.000 claims description 18
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 18
- 229910001431 copper ion Inorganic materials 0.000 claims description 18
- 238000004070 electrodeposition Methods 0.000 claims description 18
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 18
- 229920001249 ethyl cellulose Polymers 0.000 claims description 18
- 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 17
- 238000000151 deposition Methods 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 15
- 238000007788 roughening Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 238000007747 plating Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 claims description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 3
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical class CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 150000001282 organosilanes Chemical class 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000004891 communication Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000008367 deionised water Substances 0.000 description 33
- 229910021641 deionized water Inorganic materials 0.000 description 33
- 239000000243 solution Substances 0.000 description 24
- 238000004140 cleaning Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000003064 anti-oxidating effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 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 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 2
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 2
- KUNICNFETYAKKO-UHFFFAOYSA-N sulfuric acid;pentahydrate Chemical compound O.O.O.O.O.OS(O)(=O)=O KUNICNFETYAKKO-UHFFFAOYSA-N 0.000 description 2
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a preparation method of a strippable ultrathin carrier copper foil, which provides a key material for a 5G communication high-frequency high-speed printed circuit board. The strippable ultrathin carrier copper foil sequentially comprises a carrier copper foil with the thickness of 18 micrometers, an immersion-plated metal layer, an organic barrier layer, a stripping layer, an ultrathin copper foil layer and a coarsening layer, wherein the immersion-plated metal layer can reduce the isoelectric point of a copper surface, enhance the binding force between the carrier copper foil and the organic layer and meet the requirement on stripping strength; the organic layer and the metal layer are jointly used as the stripping layer, so that the problems that poor electric conduction and uneven thickness are easily caused when the ultrathin copper foil layer is electrodeposited by a single organic layer, and a carrier is easily separated before use can be solved. The thickness of the ultra-thin carrier copper foil prepared by the invention is about 5 mu m, the ultra-thin carrier copper foil can be successfully stripped, and no copper powder or stripping layer residue exists on the surface.
Description
Technical Field
The invention belongs to the field of electronic information materials, and particularly relates to a strippable ultrathin carrier copper foil and a preparation method thereof.
Background
Under the large environment of rapid development of the current 5G industry, the PCB industry is affected by the rapid development, and communication, mobile phones, servers, data storage, automobiles and the like can become the optimal subdivision racetracks of the PCB in the future in five years from the downstream application industry of the PCB, so that the demand growth of high-end PCB products such as corresponding multilayer boards, HDIs, flexible boards, IC packaging substrates and the like is very obvious; meanwhile, from the upstream of the industrial chain, the electrolytic copper foil which is indispensable in the industrial chain is a key material of a 5G communication high-frequency high-speed printed circuit board, and the electrolytic copper foil plays an increasingly important role in the manufacturing links of a raw material copper-clad plate or a PCB.
The ultra-thin copper foil is a hot point in the development direction and market demand of the electrolytic copper foil in future, the requirement on the ultra-thin copper foil is higher and higher, and the thickness of the electrolytic copper foil is gradually developed to 12 micrometers, 9 micrometers, 5 micrometers and even thinner at present. However, since the ultra-thin copper foil has low mechanical strength, it is difficult to completely peel off the cathode roll during the preparation process, and the copper foil is easily curled, wrinkled or torn during the transportation process, thereby affecting the subsequent application of the copper foil. Therefore, the Japanese enterprises abandon the conventional method for manufacturing the copper foil and creatively provide the preparation technology of the ultra-thin carrier copper foil, and the problems of transportation and storage can be solved due to the support of the carrier.
Among them, the 18 μm electrolytic copper foil as a carrier foil, carboxybenzotriazole as a release layer, nickel as an auxiliary metal layer, and an extra thin copper foil having a thickness of 3 μm electrodeposited on a nickel layer are mentioned in the japanese patent application No. CN201680017908.0 by mitsui metal mining corporation, and introduction of such an auxiliary metal layer can suppress interdiffusion of copper in the carrier copper foil and the extra thin copper layer at the time of high-temperature hot press molding to secure stability of peel strength, but the bonding force between nickel and copper is strong, the carrier copper foil is easily peeled from between an organic layer and the nickel layer, and the organic layer is poor in conductivity, and it is difficult to electroplate the nickel layer. Researchers in China also spend much effort and time trying to overcome this problem. Huang Ju and He Gui Rong, Jiangxi Ridgeon university, in article electrochemical mechanism research on preparation of carrier ultra-thin copper foil and forming process of stripping layer thereof and research on strippable ultra-thin copper foil supported by 35 micron copper foil, respectively, research on depositing alloy on 35 micron carrier copper foil or using organic matter as stripping layer, preparing ultra-thin copper foil by adopting pyrophosphate and sulfate electroplating solution to deposit copper for three times, and introducing rare earth elements to increase deposition amount of metal on the organic layer so as to research influence of different stripping layers, process parameters and additives on stripping strength of the ultra-thin copper foil, wherein the electro-deposition copper process is complex, the rare earth metal cost is high, and the method is inconvenient to be promoted in factories. In order to achieve localization and autonomy, and also to achieve a breakthrough in greater performance, researchers are required to have the ability to develop products and processes autonomously. Based on this, the problem to be solved urgently in the field of electrolytic copper foil preparation at present is considered to find a preparation method of an ultrathin carrier copper foil, which is thinner, more stable in peel strength, lower in cost and simple in process.
Disclosure of Invention
The invention aims to solve the technical problems of unstable peeling strength, incomplete copper foil peeling, wrinkling, curling and the like of the existing ultrathin copper foil, provides a preparation method of an ultrathin carrier copper foil,
the ultrathin carrier copper foil comprises a 18-micron carrier copper foil, an easily-stripped composite stripping layer and an ultrathin copper foil layer, wherein the composite stripping layer comprises a metal layer, an organic barrier layer and a stripping layer, and researches show that the organic barrier layer is generally one or two of monocarboxylic acid, a sulfur-containing compound, a nitrogen-containing compound and the like, is simple and convenient to use and cannot cause environmental pollution; it is shown in the literature that lowering the isoelectric point of the oxide on the metal surface is helpful for the bonding of the metal layer and the organic layer, and to prevent the peeling phenomenon of the carrier copper foil from the organic layer and the intermediate layer, a metal with good conductivity and lower than the isoelectric point (9.1) of copper oxide should be selected, so as to lower the isoelectric point of the copper surface, and at the same time, the copper foil is required to be well bonded, and the peeling strength is stable, such as iron, titanium, tin, manganese and the like. The composite stripping layer can solve the problem that metal possibly existing in a single inorganic layer is remained on the surface of the ultrathin copper foil, and the metal adopted by the invention is different from chromium adopted for preparing a carrier copper foil as a stripping layer, so that the pollution to the environment and the loss of the human health are avoided. The surfaces of all layers of the ultrathin carrier copper foil are uniform and flat, the performance is stable, the stripping layer has good conductivity, the ultrathin carrier copper foil is favorable for forming the ultrathin copper foil, no stripping layer metal residue exists on the surface of the ultrathin copper foil, and the problems that the ultrathin copper foil is difficult to form uniform thickness when a single organic layer is used as the stripping layer and is difficult to strip after the ultrathin copper foil is diffused to the stripping layer during high-temperature lamination can be solved.
In order to solve the technical problem, the invention provides a preparation method of an ultrathin carrier copper foil for a 5G high-frequency high-speed PCB, which comprises the following steps:
in order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a strippable ultrathin carrier copper foil comprises the following steps of sequentially including a carrier copper foil 4 with the thickness of 12-35 mu m, a stripping layer 3, an ultrathin copper foil layer 2 and a coarsening layer 1 from bottom to top, wherein the composite stripping layer 3 sequentially includes a gold-dipped metal layer 3c, an organic barrier layer 3b and a stripping layer 3a from bottom to top:
(1) preparation of immersion-plated metal layer
The carrier copper foil after surface treatment is dipped with a layer of metal with the isoelectric point lower than 9.1, the dipped metal is oxidized or hydroxylated after being washed, and then coated with a layer of organosilane and dried;
(2) preparation of organic barrier layer
Soaking the copper foil treated in the step in an organic solution of at least one of benzotriazole, carboxyl benzotriazole, thiazole, 2, 4-triazole, oleic acid, 2-benzimidazole thiol, 2-mercaptobenzothiazole and linolenic acid compounds;
(3) preparation of the Release layer
Electrodepositing the copper foil treated in the step in an electrolyte containing one element of iron, nickel, zinc, aluminum, titanium and tungsten, wherein the anode is an iridium tantalum coating titanium electrode;
(4) preparation of ultra-thin copper foil
Placing the copper foil treated in the above steps in an electroplating bath containing copper ions and concentrated sulfuric acid for copper electrodeposition, and adding Cl into copper sulfate electrolyte-Polyethylene glycol, sodium polydithio-dipropyl sulfonate and ethyl cellulose, wherein the anode is an iridium tantalum coating titanium electrode;
(5) preparation of the roughened layer
And (3) placing the copper foil treated in the step into a plating bath containing copper ions and concentrated sulfuric acid for surface roughening treatment, adding sodium polydithio-dipropyl sulfonate and ethyl cellulose into a copper sulfate electrolyte, and taking an iridium-tantalum coating titanium electrode as an anode.
Preferably, the metal with the medium potential point lower than 9.1 in the step (1) is selected from one of iron, titanium, tin and manganese.
Preferably, the ultra-thin copper foil has a thickness of 4 to 6 μm.
Preferably, the concentration of the organic solution in the step (2) is 0.05 to 10g/L, and an organic layer having a thickness of 100nm to 2 μm is adsorbed.
Preferably, the release layer in step (3) has a temperature of 25-60 deg.C and a current density of 5-30A/dm2And performing electrodeposition in a plating bath at a pH of 1-6 to form a release layer having a thickness of 300nm-3 μm.
Preferably, in the step (4), the concentration of copper ions is 50-90g/L, the concentration of sulfuric acid is 90-140g/L, and 50-100mg/L of Cl is added into the copper sulfate electrolyte-10-200mg/L of polyethylene glycol, 2-20mg/L of sodium polydithio-dipropyl sulfonate and 0.1-1mg/L of ethyl cellulose.
Preferably, the step (4) of ultra-thin copperThe foil is prepared at a temperature of 25-70 deg.C and a current density of 30-100A/dm2Is carried out under the conditions of (1) and the deposition time is 5-30 s.
Preferably, in the step (5), the concentration of copper ions is 10-20g/L, the concentration of sulfuric acid is 90-120g/L, and 20mg/L of sodium polydithio dipropyl sulfonate and 5mg/L of ethyl cellulose are added into the copper sulfate electrolyte.
Preferably, the surface of the copper foil in the step (5) is roughened at a temperature of 20 to 35 ℃ and a current density of 20 to 45A/dm2Is carried out under the condition of (1) and the deposition time is 10-30 s.
Preferably, the method further comprises the following steps before the step (1):
preparation of a cathode: selecting a double-sided copper foil for manufacturing a printed circuit board as a carrier copper foil, and carrying out microetching treatment and acid pickling treatment on the smooth surface of the carrier copper foil to obtain an oxide-free and clean copper foil surface, wherein all the surface treatment is finished on the smooth surface of the carrier copper foil;
and/or further comprising after step (5):
and after the roughening treatment, sequentially carrying out antioxidant treatment and drying treatment on the copper foil.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the prior art, the invention provides that the organic layer and the metal layer are jointly used as the stripping layer, the defects of the single stripping layer can be overcome, the problems of poor conductivity and uneven copper foil thickness easily caused by electrodeposition of the single organic layer on the ultra-thin copper foil layer can be solved, more importantly, the stripping resistance strength is generally low when the organic layer is used as the stripping layer, and the ultra-thin copper foil is likely to be separated from a carrier before use;
(2) when the ultra-thin copper foil is applied to high-frequency signal transmission, the bonding force between the carrier copper foil and the organic layer can be enhanced by adding a layer of immersion plating metal, the requirement on peeling strength is met, and meanwhile, when the ultra-thin carrier copper foil is laminated at high temperature, the peeling layer can be prevented from diffusing to the carrier copper foil layer, so that the peeling of the ultra-thin copper foil is facilitated;
(3) the invention has better compatibility with the existing process route for preparing the electronic copper foil in factories, the cost for technical transformation in factories is low, the invention can be flexibly adjusted according to market conditions to adapt to market changes, the competitive advantage of electronic copper foil enterprises in China is improved, and the capability of the domestic existing copper foil manufacturing technology for coping with competition and challenge brought by 5G communication is further improved;
(4) in the actual use process, the ultrathin carrier copper foil provided by the invention contains arsenic, chromium, lead and other substances which are not used and generate harm to the environment and human bodies all the time, responds to the national establishment of resource-saving and environment-friendly society, and can ensure that the discharged pollutants can all stably reach the discharge standard and the pollutant discharge total amount control index regulated by the country or the place, thereby meeting the basic requirements of the national laws and regulations on the environment and sustainable development.
Drawings
FIG. 1 is a schematic view of an ultra-thin carrier copper foil structure employing an embodiment of the present invention;
FIG. 2 is a 10000 XSEM image of the surface of an ultra-thin carrier copper foil after peeling, wherein (a) - (c) are 10000 XSEM images of the surface of the copper foil after treatment in examples 1-3, respectively;
in the drawings, the components represented by the respective reference numerals are listed below:
1 is a coarsening layer, 2 is an ultrathin copper foil, 3 is a composite stripping layer, 3a is a stripping layer, 3b is an organic layer, 3c is an immersion-plated metal layer, and 4 is a carrier copper foil.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
A preparation method of a strippable ultrathin carrier copper foil comprises the steps that the copper foil sequentially comprises a carrier copper foil 4 with the thickness of 12-35 mu m, a stripping layer 3, an ultrathin copper foil layer 2 and a coarsening layer 1 from bottom to top, the composite stripping layer 3 sequentially comprises a gold-dipped metal layer 3c, an organic barrier layer 3b and a stripping layer 3a from bottom to top, and the preferred thickness of the ultrathin copper foil is 4-6 mu m.
The preparation method comprises the following steps:
(1) preparation of a cathode: selecting a double-sided copper foil for manufacturing a printed circuit board as a carrier copper foil, and carrying out microetching treatment and acid pickling treatment on the smooth surface of the carrier copper foil to obtain an oxide-free and clean copper foil surface, wherein all the surface treatment is finished on the smooth surface of the carrier copper foil;
(2) preparation of immersion-plated metal layer
The carrier copper foil after surface treatment is dipped with a layer of metal with the isoelectric point lower than 9.1, the dipped metal is oxidized or hydroxylated after being washed, and then coated with a layer of organosilane and dried; the metal with the isoelectric point lower than 9.1 is selected from one of iron, titanium, tin and manganese.
(3) Preparation of organic barrier layer
Soaking the copper foil treated in the step into an organic solution of at least one of benzotriazole, carboxyl benzotriazole, thiazole, 2, 4-triazole, oleic acid, 2-benzimidazole thiol, 2-mercaptobenzothiazole and linolenic acid compounds; the concentration of the organic solution is 0.05-10g/L, and an organic layer with the thickness of 100nm-2 μm is adsorbed.
(4) Preparation of the Release layer
The copper foil treated in the step is subjected to electrodeposition in electrolyte containing one element of iron, nickel, zinc, aluminum, titanium and tungsten, electrolyte containing elements of chromium, molybdenum, cobalt and the like used by some Japanese enterprises is abandoned, and in order to avoid the occurrence of adverse phenomena such as blistering and wrinkling of a stripping interface, the anode is an iridium-tantalum coating titanium electrode.
Preferably, the peeling layer has a temperature of 25-60 deg.C and a current density of 5-30A/dm2And performing electrodeposition in a plating bath at a pH of 1-6 to form a release layer having a thickness of 300nm-3 μm.
(5) Preparation of ultra-thin copper foil
Placing the copper foil treated in the steps in an electroplating bath containing copper ions and concentrated sulfuric acid for copper electrodeposition, and adding Cl into copper sulfate electrolyte-Polyethylene glycol, polydithio-dipropylSodium alkane sulfonate and ethyl cellulose, wherein the anode is an iridium tantalum coating titanium electrode;
preferably, the concentration of copper ions is 50-90g/L, the concentration of sulfuric acid is 90-140g/L, and 50-100mg/L Cl is added into the copper sulfate electrolyte-10-200mg/L of polyethylene glycol, 2-20mg/L of sodium polydithio-dipropyl sulfonate and 0.1-1mg/L of ethyl cellulose.
Preferably, the ultra-thin copper foil is prepared at a temperature of 25 to 70 ℃ and a current density of 30 to 100A/dm2Is carried out under the condition of (1) and the deposition time is 5-30 s.
(6) Preparation of the roughened layer
And (3) placing the copper foil treated in the step into a plating bath containing copper ions and concentrated sulfuric acid for surface roughening treatment, adding sodium polydithio-dipropyl sulfonate and ethyl cellulose into copper sulfate electrolyte, and taking an iridium tantalum coating titanium electrode as an anode.
Preferably, the concentration of copper ions is 10-20g/L, the concentration of sulfuric acid is 90-120g/L, and 20mg/L of sodium polydithio dipropyl sulfonate and 5mg/L of ethyl cellulose are added into the copper sulfate electrolyte.
Preferably, the surface of the copper foil in the step (5) is roughened at a temperature of 20 to 35 ℃ and a current density of 20 to 45A/dm2The deposition time under the direct current condition is 10-30s or the deposition is carried out with the same thickness by pulse deposition.
(7) And after the roughening treatment, sequentially carrying out antioxidant treatment and drying treatment on the copper foil.
Further, the microetching treatment specifically comprises the steps of immersing the copper foil cleaned by the deionized water into a mixed solution of 5 wt% of sodium persulfate and 5 wt% of dilute sulfuric acid for 10-30s, and cleaning the residual microetching solution on the surface of the copper foil by the deionized water.
Further, the acid washing treatment is specifically that the copper foil cleaned by deionized water is immersed in a dilute sulfuric acid solution with the mass fraction of 10 wt% for 10-30s, and then the deionized water is used for cleaning away the acid liquor remaining on the surface of the copper foil.
Further, the anti-oxidation treatment is specifically that the copper foil cleaned by deionized water is immersed in 0.1 wt% benzotriazole solution for 10-30 s;
and the drying treatment is specifically to place the copper foil cleaned by the deionized water into a drying oven for low-temperature drying until the surface is dried.
Example 1
A preparation method of a strippable ultrathin carrier copper foil comprises the following steps:
(1) preparation of a cathode: a piece of 18-micron double-sided copper foil with the width of 100mm multiplied by 50mm for manufacturing a printed circuit board is cut by scissors, wherein one side is a rough side, and the other side is a smooth side, and the surface treatment of all the following embodiments is finished on the smooth side; and sequentially carrying out micro-etching treatment and acid washing treatment on the copper foil to achieve the purpose of removing surface oxides and impurities, and cleaning the copper foil by using deionized water for later use.
(2) Preparation of immersion-plated metal layer
And (3) plating a metal layer on the surface of the carrier copper foil by dipping: immersing a clean carrier copper foil into a mixed solution of 20g/L stannous chloride, 80g/L hydrochloric acid and 50g/L sodium hypophosphite, soaking for 1min at 60 ℃, washing with deionized water, immersing into a hydrogen peroxide solution for 1min at 30 ℃, activating, washing with water again, coating a layer of silane coupling agent, and drying to obtain the carrier copper foil with an immersion coating;
(3) preparation of organic barrier layer
Adsorbing an organic layer on the surface of the immersion-plated metal layer: soaking the copper foil subjected to dip plating treatment in 5g/L benzotriazole solution for treatment for 30 s;
(4) preparation of the Release layer
Deposition of a release layer on the organic layer: preparing an electrolytic solution formula for electrodepositing nickel: 215g/L nickel sulfate hexahydrate, 17g/L sodium chloride, 40g/L boric acid, 5g/L anhydrous sodium sulfate, 35g/L magnesium sulfate heptahydrate and 0.075g/L lauryl sodium sulfate are continuously stirred until complete dissolution is achieved, and the pH value of the solution is adjusted to be 5; at a working temperature of 50 ℃ and a current density of 10A/dm2Under the condition of (1), performing direct current electrodeposition for 9 s; and forming a peeling layer having a thickness of 300nm to 3 μm.
(5) Preparation of ultra-thin copper foil
Depositing an ultrathin copper foil layer on the surface of the stripping layer: preparing an electrolytic solution formula of the electrodeposited copper:copper sulfate pentahydrate with copper ion concentration of 50g/L, concentrated sulfuric acid of 90g/L and Cl of 50mg/L-10mg/L of polyethylene glycol, 2mg/L of sodium polydithio-dipropyl sulfonate and 0.55mg/L of ethyl cellulose; at a working temperature of 45 ℃ and a current density of 65A/dm2Under the condition of (1), performing direct current electrodeposition for 15 s;
(6) preparation of the roughened layer
Roughening the surface of the ultrathin copper foil: preparing an electrolyte formula for surface roughening treatment of the ultrathin copper foil: copper sulfate pentahydrate with copper ion concentration of 15g/L, concentrated sulfuric acid of 105g/L, sodium polydithio-dipropyl sulfonate of 20mg/L and ethyl cellulose of 5 mg/L; at a working temperature of 30 ℃ and a current density of 35A/dm2Under the condition of (2), D.C. deposition is carried out for 10 s.
Step (4) - (6) need to be washed by deionized water before and after surface treatment;
(7) and after the roughening treatment, sequentially carrying out antioxidant treatment and drying treatment on the copper foil.
Further, the microetching treatment specifically comprises the steps of immersing the copper foil cleaned by the deionized water into a mixed solution of 5 wt% of sodium persulfate and 5 wt% of dilute sulfuric acid for 10-30s, and cleaning the residual microetching solution on the surface of the copper foil by the deionized water.
Further, the acid washing treatment is specifically that the copper foil cleaned by deionized water is immersed in a dilute sulfuric acid solution with the mass fraction of 10 wt% for 10-30s, and then the deionized water is used for cleaning away the acid liquor remaining on the surface of the copper foil.
Further, the anti-oxidation treatment is to immerse the copper foil cleaned by the deionized water into a benzotriazole solution with the mass fraction of 0.1 wt% for 10-30 s;
and the drying treatment is specifically to place the copper foil cleaned by the deionized water into a drying oven for low-temperature drying until the surface is dried.
Example 2
A preparation method of a strippable ultrathin carrier copper foil comprises the following steps:
(1) preparation of a cathode: a piece of 18-micron double-sided copper foil with the width of 100mm multiplied by 50mm for manufacturing a printed circuit board is cut by scissors, wherein one side is a rough side, and the other side is a smooth side, and the surface treatment of all the following embodiments is finished on the smooth side; and sequentially carrying out microetching treatment and pickling treatment on the copper foil to achieve the purpose of removing surface oxides and impurities, and then cleaning the copper foil by using deionized water for later use.
(2) Preparation of immersion-plated metal layer
And (3) plating a metal layer on the surface of the carrier copper foil by dipping: immersing a clean carrier copper foil into a mixed solution of 20g/L stannous chloride, 80g/L hydrochloric acid and 50g/L sodium hypophosphite, soaking for 1min at 60 ℃, washing with deionized water, immersing into a hydrogen peroxide solution for 1min at 30 ℃, activating, washing with water again, coating a layer of silane coupling agent, and drying to obtain the carrier copper foil with an immersion coating;
(3) preparation of organic barrier layer
Adsorbing an organic layer on the surface of the immersion-plated metal layer: soaking the copper foil after dip plating treatment in 0.05g/L carboxyl benzotriazole solution for treatment for 2 min;
(4) preparation of the Release layer
Deposition of a release layer on the organic layer: preparing an electrolytic solution formula for electrodepositing zinc: continuously stirring 350g/L zinc sulfate heptahydrate, 3g/L polyethylene glycol and 2g/L octadecyl dimethyl benzyl ammonium chloride until the zinc sulfate heptahydrate, the polyethylene glycol and the octadecyl dimethyl benzyl ammonium chloride are completely dissolved, and adjusting the pH value of the solution to 1; at a working temperature of 50 ℃ and a current density of 3A/dm2Under the condition of (1), performing direct current electrodeposition for 10 s; and forming a peeling layer having a thickness of 300nm to 3 μm.
(5) Preparation of ultra-thin copper foil
Depositing an ultrathin copper foil layer on the surface of the stripping layer: preparing an electrolytic solution formula of electrodeposited copper: copper sulfate pentahydrate with copper ion concentration of 90g/L, concentrated sulfuric acid of 140g/L and Cl of 75mg/L-105mg/L of polyethylene glycol, 11mg/L of sodium polydithio-dipropyl sulfonate and 0.1mg/L of ethyl cellulose; at a working temperature of 25 ℃ and a current density of 100A/dm2D, performing direct current electrodeposition for 8 s;
(6) preparation of the roughened layer
Roughening the surface of the ultrathin copper foil: preparing an electrolyte formula for surface roughening treatment of the ultrathin copper foil: copper ion concentration of 10g/LCopper sulfate pentahydrate, 120g/L concentrated sulfuric acid, 20mg/L sodium polydithio-dipropyl sulfonate and 5mg/L ethyl cellulose; at a working temperature of 20 ℃ and a current density of 20A/dm2Under the condition of (1), pulse electrodeposition is carried out for 1min, and the pulse duty ratio is 50 percent;
step (4) - (6) need to be washed by deionized water before and after surface treatment;
(7) and after the roughening treatment, sequentially carrying out antioxidant treatment and drying treatment on the copper foil.
Further, the microetching treatment specifically comprises the steps of immersing the copper foil cleaned by the deionized water into a mixed solution of 5 wt% of sodium persulfate and 5 wt% of dilute sulfuric acid for 10-30s, and cleaning the residual microetching solution on the surface of the copper foil by the deionized water.
Further, the acid washing treatment is specifically that the copper foil cleaned by deionized water is immersed in a dilute sulfuric acid solution with the mass fraction of 10 wt% for 10-30s, and then the deionized water is used for cleaning away the acid liquor remaining on the surface of the copper foil.
Further, the anti-oxidation treatment is specifically that the copper foil cleaned by deionized water is immersed in 0.1 wt% benzotriazole solution for 10-30 s;
and the drying treatment is specifically to place the copper foil cleaned by the deionized water into a drying oven for low-temperature drying until the surface is dried.
Example 3
A preparation method of a strippable ultrathin carrier copper foil comprises the following steps:
(1) preparation of a cathode: a piece of 18-micron double-sided copper foil with the width of 100mm multiplied by 50mm for manufacturing a printed circuit board is cut by scissors, wherein one side is a rough side, and the other side is a smooth side, and the surface treatment of all the following embodiments is finished on the smooth side; and sequentially carrying out micro-etching treatment and acid washing treatment on the copper foil to achieve the purpose of removing surface oxides and impurities, and cleaning the copper foil by using deionized water for later use.
(2) Preparation of immersion-plated metal layer
And (3) plating a metal layer on the surface of the carrier copper foil by dipping: soaking a clean carrier copper foil into a mixed solution of 5g/L ferrous sulfate, 15g/L sodium citrate, 10g/L lactic acid and 20g/L sodium hypophosphite in sequence, soaking for 1min at 60 ℃, washing with deionized water, soaking into a hydrogen peroxide solution for 1min at 30 ℃, activating, washing with water again, coating a layer of silane coupling agent, and drying to obtain a carrier copper foil with a dip coating layer;
(3) preparation of organic barrier layer
Adsorbing an organic layer on the surface of the immersion-plated metal layer: soaking the copper foil subjected to the dip plating treatment in a thiazole solution of 10g/L for treatment for 10 s;
(4) preparation of the Release layer
Deposition of a release layer on the organic layer: preparing an electrolytic solution formula for electrodepositing nickel: 215g/L nickel sulfate hexahydrate, 17g/L sodium chloride, 40g/L boric acid, 5g/L anhydrous sodium sulfate, 35g/L magnesium sulfate heptahydrate and 0.075g/L lauryl sodium sulfate are continuously stirred until complete dissolution is achieved, and the pH value of the solution is adjusted to be 5; at a working temperature of 50 ℃ and a current density of 5A/dm2Under the condition of (1), DC electrodeposition is carried out for 36 s;
(5) preparation of ultra-thin copper foil
Depositing an ultrathin copper foil layer on the surface of the stripping layer: preparing an electrolytic solution formula of the electrodeposited copper: copper sulfate pentahydrate with copper ion concentration of 70g/L, concentrated sulfuric acid of 125g/L and Cl of 100mg/L-200mg/L of polyethylene glycol, 20mg/L of sodium polydithio-dipropyl sulfonate and 1mg/L of ethyl cellulose; at a working temperature of 70 ℃ and a current density of 30A/dm2D, performing direct current electrodeposition for 30s under the condition;
(6) preparation of the roughened layer
Roughening the surface of the ultrathin copper foil: preparing an electrolyte formula for surface roughening treatment of the ultrathin copper foil: copper sulfate pentahydrate with copper ion concentration of 20g/L, concentrated sulfuric acid of 90g/L, sodium polydithio dipropyl sulfonate of 20mg/L and ethyl cellulose of 5 mg/L; at a working temperature of 35 ℃ and a current density of 50A/dm2Under the condition (1), pulse electrodeposition is carried out for 1.3min, and the pulse duty ratio is 25%.
Step (4) - (6) need to be washed by deionized water before and after surface treatment;
(7) and after the roughening treatment, sequentially carrying out antioxidant treatment and drying treatment on the copper foil.
Further, the microetching treatment specifically comprises the steps of immersing the copper foil cleaned by the deionized water into a mixed solution of 5 wt% of sodium persulfate and 5 wt% of dilute sulfuric acid for 10-30s, and cleaning the residual microetching solution on the surface of the copper foil by the deionized water.
Further, the acid cleaning treatment is to immerse the copper foil cleaned by the deionized water into a dilute sulfuric acid solution with the mass fraction of 10 wt% for 10-30s, and then clean the residual acid solution on the surface of the copper foil by the deionized water.
Further, the anti-oxidation treatment is to immerse the copper foil cleaned by the deionized water into a benzotriazole solution with the mass fraction of 0.1 wt% for 10-30 s;
and the drying treatment is specifically to place the copper foil cleaned by the deionized water into a drying oven for low-temperature drying until the surface is dried.
Performance testing
In order to more clearly show the effects of the preparation formulations and the plating processes of the different examples on the peeling condition and the roughness of the ultra-thin copper foil, peeling strength and surface roughness tests were performed on the untreated carrier copper foil, i.e., the green foil, and the copper foils of examples 1 to 3. The above copper foil samples were laminated on a prepreg at a pressure of 60kN and a lamination temperature of 175 ℃ to prepare a desired laminate, and the laminated samples were cut into strips of 15mm × 100mm, subjected to a peeling test using a 90-degree peel strength tester, and pre-peeled by about 20mm, with the peeling speed set to 10mm/min, 3 times per sample, and averaged. And the surface roughness of the copper foil was measured using a 3D laser microscope, and the measurement results are shown in table 1.
TABLE 1
The test results show that the carrier and the ultra-thin copper foil in the embodiments 1 to 3 of the invention have good peeling effect, and can successfully realize peeling, so that the prepared ultra-thin copper foil has higher tensile strength, the surface roughness of the copper foil is improved, the bonding force with a prepreg can be improved, and the signal transmission requirement of the ultra-low profile processing copper foil in the 5G era can be met.
In order to detect whether the metal layer remains on the surface of the ultra-thin copper foil after stripping and observe the morphology of the stripping interface, the surface micro-morphology and the crystal morphology are characterized by a scanning electron microscope, and the result is shown in fig. 2. As can be seen from fig. 2, no fine copper crystals are generated in the micro-topography, which illustrates that the method for manufacturing the ultra-thin copper foil according to the embodiment of the present invention is feasible.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a strippable ultrathin carrier copper foil is characterized by comprising the following steps: the copper foil sequentially comprises a carrier copper foil (4) with the thickness of 12-35 mu m, a stripping layer (3), an ultra-thin copper foil layer (2) and a coarsening layer (1) from bottom to top, the composite stripping layer (3) sequentially comprises an immersion-plated metal layer (3c), an organic barrier layer (3b) and a stripping layer (3a), and the preparation method comprises the following preparation steps:
(1) preparation of immersion-plated metal layer
The carrier copper foil after surface treatment is dipped with a layer of metal with isoelectric point lower than 9.1, the dipped metal is oxidized or hydroxylated after being washed, and then is coated with a layer of organosilane, and is dried;
(2) preparation of organic barrier layer
Soaking the copper foil treated in the step into an organic solution of at least one of benzotriazole, carboxyl benzotriazole, thiazole, 2, 4-triazole, oleic acid, 2-benzimidazole thiol, 2-mercaptobenzothiazole and linolenic acid compounds;
(3) preparation of the Release layer
Carrying out electrodeposition on the copper foil treated in the step in electrolyte containing one element of iron, nickel, zinc, aluminum, titanium and tungsten, wherein the anode is an iridium tantalum coating titanium electrode;
(4) preparation of ultra-thin copper foil
Placing the copper foil treated in the above steps in an electroplating bath containing copper ions and concentrated sulfuric acid for copper electrodeposition, and adding Cl into copper sulfate electrolyte-Polyethylene glycol, sodium polydithio-dipropyl sulfonate and ethyl cellulose, wherein the anode is an iridium tantalum coating titanium electrode;
(5) preparation of the roughened layer
And (3) placing the copper foil treated in the step into a plating bath containing copper ions and concentrated sulfuric acid for surface roughening treatment, adding sodium polydithio-dipropyl sulfonate and ethyl cellulose into a copper sulfate electrolyte, and taking an iridium-tantalum coating titanium electrode as an anode.
2. The method for manufacturing a peelable ultra-thin carrier copper foil according to claim 1, characterized in that: the metal with the medium potential point lower than 9.1 in the step (1) is selected from one of iron, titanium, tin and manganese.
3. The method for manufacturing a peelable ultra-thin carrier copper foil according to claim 1, wherein: the thickness of the ultra-thin copper foil is 4-6 μm.
4. The method for manufacturing a peelable ultra-thin carrier copper foil according to claim 1, characterized in that: the concentration of the organic solution in the step (2) is 0.05-10g/L, and an organic layer with the thickness of 100nm-2 μm is adsorbed.
5. The method for manufacturing a peelable ultra-thin carrier copper foil according to claim 1, characterized in that: the stripping layer in the step (3) has the temperature of 25-60 ℃ and the current density of 5-30A/dm2And performing electrodeposition in a plating bath at a pH of 1-6 to form a release layer having a thickness of 300nm-3 μm.
6. The method for manufacturing a peelable ultra-thin carrier copper foil according to claim 1, characterized in that: in the step (4), the concentration of copper ions is 50-90g/L, the concentration of sulfuric acid is 90-140g/L, and 50-100mg/L Cl is added into the copper sulfate electrolyte-10-200mg/L of polyethylene glycol, 2-20mg/L of sodium polydithio-dipropyl sulfonate and 0.1-1mg/L of ethyl cellulose.
7. The method for manufacturing a peelable ultra-thin carrier copper foil according to claim 1, wherein: the ultra-thin copper foil in the step (4) is prepared at the temperature of 25-70 ℃ and the current density of 30-100A/dm2Is carried out under the conditions of (1) and the deposition time is 5-30 s.
8. The method for manufacturing a peelable ultra-thin carrier copper foil according to claim 1, characterized in that: in the step (5), the concentration of copper ions is 10-20g/L, the concentration of sulfuric acid is 90-120g/L, and 20mg/L sodium polydithio dipropyl sulfonate and 5mg/L ethyl cellulose are added into copper sulfate electrolyte.
9. The method for manufacturing a peelable ultra-thin carrier copper foil according to claim 1, characterized in that: the surface of the copper foil is roughened at the temperature of 20-35 ℃ and the current density of 20-45A/dm in the step (5)2Is carried out under the condition of (1) and the deposition time is 10-30 s.
10. The method for manufacturing a peelable ultra-thin carrier copper foil according to claim 1, characterized in that: before step (1), the method also comprises the following steps:
preparation of a cathode: selecting a double-sided copper foil for manufacturing a printed circuit board as a carrier copper foil, and carrying out microetching treatment and acid pickling treatment on the smooth surface of the carrier copper foil to obtain an oxide-free and clean copper foil surface, wherein all the surface treatment is finished on the smooth surface of the carrier copper foil;
and/or further comprising after step (5):
and after the roughening treatment, sequentially carrying out antioxidant treatment and drying treatment on the copper foil.
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| CN202210311750.5A CN114657610A (en) | 2022-03-28 | 2022-03-28 | Preparation method of strippable ultrathin carrier copper foil |
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| CN202210311750.5A CN114657610A (en) | 2022-03-28 | 2022-03-28 | Preparation method of strippable ultrathin carrier copper foil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115233262A (en) * | 2022-08-01 | 2022-10-25 | 九江德福科技股份有限公司 | Preparation method of ultra-thin copper foil with carrier |
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Application publication date: 20220624 |