CN117626365A - Composite stripping layer for carrier ultrathin copper foil and application thereof - Google Patents
Composite stripping layer for carrier ultrathin copper foil and application thereof Download PDFInfo
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- CN117626365A CN117626365A CN202311684668.8A CN202311684668A CN117626365A CN 117626365 A CN117626365 A CN 117626365A CN 202311684668 A CN202311684668 A CN 202311684668A CN 117626365 A CN117626365 A CN 117626365A
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- copper foil
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- metal
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000011889 copper foil Substances 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 229920001661 Chitosan Polymers 0.000 claims abstract description 61
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011651 chromium Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000767 polyaniline Polymers 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 238000007747 plating Methods 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000009713 electroplating Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000004070 electrodeposition Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 10
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 9
- 239000005695 Ammonium acetate Substances 0.000 claims description 9
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 235000019257 ammonium acetate Nutrition 0.000 claims description 9
- 229940043376 ammonium acetate Drugs 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000006196 deacetylation Effects 0.000 claims description 8
- 238000003381 deacetylation reaction Methods 0.000 claims description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940097043 glucuronic acid Drugs 0.000 claims description 2
- AEMOLEFTQBMNLQ-AQKNRBDQSA-N D-glucopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-AQKNRBDQSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000002848 electrochemical method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 80
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 230000002265 prevention Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- 102000008186 Collagen Human genes 0.000 description 5
- 108010035532 Collagen Proteins 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 5
- 230000003064 anti-oxidating effect Effects 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- 229920001436 collagen Polymers 0.000 description 5
- 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 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 5
- 238000010297 mechanical methods and process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002101 Chitin Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- TUFHBDDWCJZWIF-UHFFFAOYSA-N 1,3-benzothiazole;sodium Chemical compound [Na].C1=CC=C2SC=NC2=C1 TUFHBDDWCJZWIF-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 125000003047 N-acetyl group Chemical group 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- MSWZFWKMSRAUBD-IVMDWMLBSA-N glucosamine group Chemical group OC1[C@H](N)[C@@H](O)[C@H](O)[C@H](O1)CO MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 235000016337 monopotassium tartrate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- -1 nitrogen-containing compound Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 229940086065 potassium hydrogentartrate Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
Abstract
The invention belongs to the technical field of preparation of ultrathin copper foil, and relates to a composite stripping layer for a carrier ultrathin copper foil and application thereof. The composite stripping layer comprises an organic coating and a metal coating; the organic coating is prepared from chitosan and polyaniline; the metal coating is a metal chromium coating. According to the invention, after the chitosan is grafted with the polyaniline, the adsorption performance of metal ions is greatly improved, and meanwhile, the conductivity of the organic coating is improved by means of the conductivity of the polyaniline. The chitosan and the aniline are loaded on the carrier copper foil by an electrochemical method, and then the chromium metal layer is deposited to obtain the composite stripping layer, and the composite stripping layer has strong chromium adsorption capacity, excellent conductivity, uniform thickness and easy stripping, and has wide application in the preparation of ultrathin copper foil.
Description
Technical Field
The invention belongs to the technical field of preparation of ultrathin copper foil, and relates to a composite stripping layer for a carrier ultrathin copper foil and application thereof.
Background
Copper foil for PCB circuit boards is being developed in a direction of being lighter and thinner, however, the thinner the copper foil is, the more easily wrinkling and tearing are caused during production and transportation. The ultra-thin copper foil can be prepared by adopting a carrier attaching mode. For example, copper or copper alloy is used as a carrier and an ultra-thin copper foil is prepared by electroplating, which is disclosed in patent application No. CN1159958C by Mitsui metal , japan. The carrier layer currently used is typically an 18-35 micron electrodeposited copper foil, and a release layer is formed on the carrier to deposit a 2-6 micron ultra-thin copper foil. When in use, the ultrathin copper foil is pressed with resin, so that the carrier copper foil layer is stripped; in this manufacturing process, the release layer is a key to manufacture the ultra-thin copper foil.
In the preparation process of the ultrathin copper foil, the stripping layer is mainly divided into an inorganic stripping layer, an organic stripping layer and a composite stripping layer. The inorganic stripping layer is mainly a metal or alloy layer, has good conductivity, but is difficult to strip. In the Chinese patent No. 108330517B, a plating solution of a carrier copper foil stripping layer and a preparation method of the stripping layer are disclosed, wherein potassium hydrogen tartrate, zinc sulfate and additives are used for preparing the plating solution, and carrier copper is immersed into the plating solution, so that a nano-scale composite galvanized layer stripping layer can be electroplated on the carrier copper foil, and the stripping layer is extremely thin and uniform; however, the bonding force with the copper foil is strong, the stripping layer effect after hot pressing is poor, and the galvanized layer is easy to damage the ultrathin copper foil.
The composite stripping layer is usually made of an organic layer and an inorganic layer, and is the focus of current research, wherein the organic stripping layer mainly comprises a nitrogen-containing compound, a sulfur-containing compound, carboxylic acid and the like, and is commonly used as benzotriazole, carboxyl benzotriazole and the like. The Chinese patent application CN112853408A discloses a preparation method of an ultrathin carrier-attached copper foil which is easy to strip and has a pure interface. The stripping layer is a composite stripping layer composed of an alloy layer and an organic layer. The organic layer is obtained by coating an organic liquid; the alloy layer is realized by electroplating at least one alloy liquid containing complexing agent and soluble sulfate (nickel sulfate, zinc sulfate, cobalt sulfate, titanium sulfate and ferric sulfate), and the composite stripping layer has the characteristics of stable stripping performance and easy stripping after high-temperature lamination; however, the organic release layer has poor conductivity, and uneven adsorption of organic substances causes uneven release.
The Chinese patent application CN107475698A discloses a preparation method of a stripping layer of Ni-Cr-B-P ultrathin copper foil. The stripping layer is prepared by adding a solution of nickel sulfate and chromium chloride into a solution of sodium hypophosphite, sodium fluoride, -base benzothiazole sodium and citric acid, then adjusting the pH value by alkali liquor and adopting a potassium borohydride chemical plating mode, and has the characteristics of good thermal stability, stable stripping strength, low industrialization cost and the like. However, the ultrathin copper foil is easy to partially or completely fall off from the carrier copper foil in the use process, so that the ultrathin copper foil is incomplete.
Chinese patent application CN115948773a discloses a composite release layer using crystalline nickel and amorphous chrome coating. The Van der Waals force between the amorphous chromium coating and the ultrathin copper foil is weak, the amorphous chromium coating is easy to peel, and the crystal grains are fine and smooth and the interface is pure. Chinese patent application CN113388868A discloses a method for self-peeling of copper foil by electrodepositing a layer of discrete Cr nuclei on the surface of the copper foil. Trivalent chromium is used to avoid the toxicity of hexavalent chromium, so the method is more environment-friendly. The Cr crystal nucleus can be deposited in a few seconds, the deposited stripping layer is uniformly distributed, and the method is simple and easy to operate. But trivalent chromium solutions have poor stability.
As described above, although many composite release layers have been studied, no release layer capable of completely stabilizing release has been studied. There is an urgent need to develop a peeling layer which is simple to operate, has good plating conductivity, is easy to peel off, and has little environmental pollution.
Disclosure of Invention
Aiming at the problems of poor conductivity, uneven stripping or difficult stripping of the composite stripping layer, incomplete stripping of the ultrathin copper foil after stripping and the like in the prior art, the invention provides a composite stripping layer for a carrier ultrathin copper foil and application thereof. After the chitosan is grafted with the polyaniline, the adsorption performance of metal ions is greatly improved, and meanwhile, the polyaniline has conductivity, so that the conductivity of the organic coating is greatly improved. And (3) using an electrochemical method to deposit the chitosan and the aniline on the carrier copper foil, and further depositing a nano chromium metal layer on the composite film to obtain the composite stripping layer.
The technical scheme of the invention is as follows:
the invention provides a composite stripping layer for a carrier ultrathin copper foil, which comprises an organic coating and a metal coating; the organic coating is prepared from chitosan and polyaniline; the metal coating is a metal chromium coating.
Further, the preparation method of the organic coating comprises the following steps:
s11: dissolving chitosan in an organic acid solution, adding ethanol, heating, stirring, dissolving, adding a cross-linking agent, and stirring to obtain chitosan pretreatment liquid;
s12: dissolving aniline in a phosphoric acid solution to obtain an aniline solution;
s13: adding chitosan pretreatment liquid into aniline solution to obtain electrodeposition liquid;
s14: immersing the carrier copper foil into electrodeposition liquid, and performing electrodeposition to obtain the copper foil.
Still further, the chitosan has a degree of deacetylation of 80-95% and a concentration of 5-20% (w/v) in the electrodeposition bath.
Still further, the cross-linking agent is any one of glutaraldehyde, dopamine, ethylene glycol diacid and glucuronic acid, and the concentration is 1-6wt%.
Further, the mass ratio of the chitosan to the cross-linking agent is 40-100:1.
still further, the aniline concentration is 0.2-0.5mol/L; the concentration of the acetic acid is 1-5wt%; the concentration of the phosphoric acid is 0.2-0.5mol/L.
Still further, the electrodeposition is a constant current method with a current density of 0.03-0.08mA/cm 2 The electrodeposition time is 6min-3h.
In some embodiments of the present invention, the carrier copper foil is subjected to pretreatment prior to electrodeposition, specifically comprising the following steps:
(1) Preparing an alkaline treatment liquid:
(2) Immersing the carrier copper foil into alkaline treatment liquid for treatment;
(3) Sequentially cleaning with ethanol and water to obtain the final product.
In the invention, the pretreatment of the carrier copper foil not only can remove grease and impurities on the surface of the base film, but also can introduce groups such as carboxyl and the like on the surface of the carrier copper foil to improve the adhesive force of the base film.
Further, the preparation method of the metal chromium coating comprises the following steps:
s21: adding chromium sulfate, boric acid, ammonium acetate and sodium dodecyl sulfate into water, stirring and dissolving to obtain metal electroplating solution;
s22: immersing the carrier copper foil of the electrodeposited organic coating into metal electroplating liquid, and carrying out electroplating treatment to obtain the copper foil.
Still further, the mass ratio of the chromium sulfate, the boric acid, the ammonium acetate and the sodium dodecyl sulfate is 20-100:60-80:10-40:0.01-0.1.
Still further, the plating temperature is 20-50 ℃; the current density is 0.5-1mA/cm 2 The electroplating time is 5-30s.
Further, the thickness of the organic coating is 100nm-1 μm.
Further, the thickness of the metal coating is 50-200nm.
The invention also provides application of the composite stripping layer in preparation of the ultrathin copper foil.
Compared with the prior art, the invention has the following beneficial effects:
(1) Chitosan has hydroxyl, amino, N-acetyl and other groups and can be mixed with metal ion Cr 3+ Coordination chelation can obtain a denser chromium coating, so that the binding force between a carrier and an ultrathin copper foil is obviously reduced, and the stripping performance is more excellent;
(2) The in-situ polymerization method forms a polyaniline layer on the surface of the carrier copper foil, so that the operation is simple and convenient; after grafting the chitosan with polyaniline, not only the Cr of the organic layer can be improved 3+ Is sucked by (a)The attaching capability can also improve the conductivity of the organic layer; in addition, the electrochemical film forming is adopted, so that the electric conductivity of the organic stripping layer can be improved, and the subsequent electroplating of the copper foil is facilitated;
(3) Trivalent chromium sulfate is used as the main component of the electroplating solution, so that the electroplating solution is safe and pollution-free.
Drawings
FIG. 1 is a schematic diagram of a carrier ultra-thin copper foil structure;
reference numerals: 1. a carrier copper foil layer; 2. an organic coating; 3. a metal plating layer; 4. an ultra-thin copper foil layer.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. The following is merely exemplary of the scope of the invention as claimed and many variations and modifications of the invention will be apparent to those skilled in the art in light of the disclosure, which are intended to be within the scope of the invention as claimed.
Example 1
A carrier ultra-thin copper foil (structure is shown in figure 1) comprises a carrier copper foil layer 1, an organic coating layer 2, a metal plating layer 3 and an ultra-thin copper foil layer 4.
The preparation process comprises the following steps:
1. pretreatment of a carrier copper foil:
preparing KOH and NaHCO 3 In an aqueous ethanol solution (wherein, the KOH concentration is 2M, naHCO) 3 The concentration is 0.5M, and the volume ratio of ethanol to water is 2: 1) Immersing the carrier copper foil into the solution, and treating for 5min; and taking out the carrier copper foil, and cleaning the carrier copper foil by ethanol and water in sequence.
2. Preparing an organic coating:
(1) Dissolving 20g of chitosan (deacetylation degree 95%) in 90mL of acetic acid solution with concentration of 5wt%, adding 10mL of absolute ethyl alcohol, heating to 50 ℃, and stirring for 1h to carry out complete acidolysis on the chitosan; adding 4g of glutaraldehyde crosslinking agent with the weight percentage of 5% (the mass ratio of chitosan to glutaraldehyde is 100:1) and continuously stirring for 2 hours to obtain chitosan pretreatment liquid;
(2) Mixing 50mL of aniline (0.3M) and 50mL of phosphoric acid (0.3M) to obtain a mixed solution;
(3) Adding the chitosan pretreatment solution in the step (1) into the mixed solution in the step (2) to obtain an electrodeposition solution (wherein the concentration of chitosan is 10% (w/v));
(4) Adopting constant current deposition method to set current density at 0.05mA/cm 2 Electrodepositing for 30min to obtain a carrier copper foil loaded with the organic coating;
(5) The carrier copper foil loaded with the organic coating is respectively washed by absolute ethyl alcohol and deionized water, and dried at the temperature of 100 ℃.
3. Preparing a metal coating:
(1) Adding chromium sulfate, boric acid, ammonium acetate and sodium dodecyl sulfate into 100mL of water according to the mass ratio of 50:70:30:0.05, and stirring for dissolution to obtain metal plating solution;
(2) Heating the metal plating solution to 50 ℃, and immersing the material dried in the second step into the metal plating solution; the current density was set to 0.5mA/cm 2 The electroplating time is 30s, and the plating solution is obtained.
4. Preparing an ultrathin copper foil layer:
(1) 7.83g of copper sulfate pentahydrate, 0.0005mg of collagen, 0.0005mg of hydroxyethyl cellulose and 0.0015mg of sodium chloride are taken and added into 100mL of water to obtain a copper plating solution;
(2) Raising the temperature of the plating solution to 50 ℃, immersing the cleaned material obtained in the step three into copper plating solution, and setting the current density to 400mA/cm 2 The electroplating time is 20s, and the plating solution is obtained.
5. And (3) oxidation prevention treatment:
immersing the material obtained in the step four into an anti-oxidation liquid (mixed liquid of 1g/L benzotriazole and 1g/L benzoic acid), immersing for 5s, squeezing the liquid by a water accumulating roller, drying by hot air at 100 ℃, and winding.
6. And (3) pressing:
and pressing the composite copper foil subjected to the oxidation prevention treatment with a PCB (printed circuit board) for 1h at 180 ℃, solidifying, and then stripping and removing the carrier copper foil by a mechanical method to obtain the ultrathin copper foil.
Example 2
A carrier ultra-thin copper foil having the same structure as in example 1;
the preparation process comprises the following steps:
the preparation process comprises the following steps:
1. pretreatment of a carrier copper foil:
preparing KOH and NaHCO 3 In an aqueous ethanol solution (wherein, the KOH concentration is 1M, naHCO) 3 Concentration is 1M, volume ratio of ethanol to water is 1: 1) Immersing the carrier copper foil into the solution, and treating for 5min; and taking out the carrier copper foil, and cleaning the carrier copper foil by ethanol and water in sequence.
2. Preparing an organic coating:
(1) Dissolving 10g of chitosan (deacetylation degree 95%) in 90mL of acetic acid solution with concentration of 1wt%, adding 10mL of absolute ethyl alcohol, heating to 50 ℃, and stirring for 1h to carry out complete acidolysis on the chitosan; adding 4g of glutaraldehyde crosslinking agent with the weight percentage of 5% (the mass ratio of chitosan to glutaraldehyde is 50:1) and continuously stirring for 2 hours to obtain chitosan pretreatment liquid;
(2) Mixing 50mL of aniline (0.2M) and 50mL of phosphoric acid (0.2M) to obtain a mixed solution;
(3) Adding the chitosan pretreatment solution in the step (1) into the mixed solution in the step (2) to obtain an electrodeposition solution (wherein the concentration of chitosan is 5% (w/v));
(4) Adopting constant current deposition method to set current density at 0.05mA/cm 2 Electrodepositing for 30min to obtain a carrier copper foil loaded with the organic coating;
(5) The carrier copper foil loaded with the organic coating is respectively washed by absolute ethyl alcohol and deionized water, and dried at the temperature of 100 ℃.
3. Preparing a metal coating:
(1) Adding chromium sulfate, boric acid, ammonium acetate and sodium dodecyl sulfate into 100mL of water according to the mass ratio of 100:60:10:0.01, and stirring for dissolution to obtain metal plating solution;
(2) Heating the metal plating solution to 50 ℃, and immersing the material dried in the second step into the metal plating solution; the current density was set to 0.5mA/cm 2 The electroplating time is 30s, and the plating solution is obtained.
4. Preparing an ultrathin copper foil layer:
(1) 7.83g of copper sulfate pentahydrate, 0.0005mg of collagen, 0.0005mg of hydroxyethyl cellulose and 0.0015mg of sodium chloride are taken and added into 100mL of water to obtain a copper plating solution;
(2) Raising the temperature of the plating solution to 50 ℃, immersing the cleaned material obtained in the step three into copper plating solution, and setting the current density to 400mA/cm 2 The electroplating time is 20s, and the plating solution is obtained.
5. And (3) oxidation prevention treatment:
immersing the material obtained in the step four into an anti-oxidation liquid (mixed liquid of 1g/L benzotriazole and 1g/L benzoic acid), immersing for 5s, squeezing the liquid by a water accumulating roller, drying by hot air at 100 ℃, and winding.
6. And (3) pressing:
and pressing the composite copper foil subjected to the oxidation prevention treatment with a PCB (printed circuit board) for 1h at 180 ℃, solidifying, and then stripping and removing the carrier copper foil by a mechanical method to obtain the ultrathin copper foil.
Example 3
A carrier ultra-thin copper foil having the same structure as in example 1;
the preparation process comprises the following steps:
the preparation process comprises the following steps:
1. pretreatment of a carrier copper foil:
preparing KOH and KHCO 3 (wherein, the KOH concentration is 0.5M, KHCO) 3 The concentration is 2M, and the volume ratio of ethanol to water is 2: 1) Immersing the carrier copper foil into the solution, and treating for 5min; and taking out the carrier copper foil, and cleaning the carrier copper foil by ethanol and water in sequence.
2. Preparing an organic coating:
(1) Dissolving 10g of chitosan (deacetylation degree 90%) in 90mL of acetic acid solution with concentration of 3wt%, adding 10mL of absolute ethyl alcohol, heating to 50 ℃, and stirring for 1h to carry out complete acidolysis on the chitosan; adding 8.33g of glutaraldehyde crosslinking agent (the mass ratio of chitosan to glutaraldehyde is 60:1) with the weight percentage of 2.0 percent, and continuously stirring for 2 hours to obtain chitosan pretreatment liquid;
(2) Mixing 50mL of aniline (0.5M) and 50mL of phosphoric acid (0.5M) to obtain a mixed solution;
(3) Adding the chitosan pretreatment solution in the step (1) into the mixed solution in the step (2) to obtain an electrodeposition solution (wherein the concentration of chitosan is 5% (w/v));
(4) Adopting constant current deposition method to set current density at 0.05mA/cm 2 Electrodepositing for 30min to obtain a carrier copper foil loaded with the organic coating;
(5) The carrier copper foil loaded with the organic coating is respectively washed by absolute ethyl alcohol and deionized water, and dried at the temperature of 100 ℃.
3. Preparing a metal coating:
(1) Adding chromium sulfate, boric acid, ammonium acetate and sodium dodecyl sulfate into 100mL of water according to the mass ratio of 20:80:40:0.1, and stirring for dissolution to obtain metal plating solution;
(2) Heating the metal plating solution to 50 ℃, and immersing the material dried in the second step into the metal plating solution; the current density was set to 0.5mA/cm 2 The electroplating time is 30s, and the plating solution is obtained.
4. Preparing an ultrathin copper foil layer:
(1) 8.73g of copper sulfate pentahydrate, 0.0005mg of collagen, 0.0005mg of hydroxyethyl cellulose and 0.0015mg of sodium chloride are added into 100mL of water to obtain a copper plating solution;
(2) Raising the temperature of the plating solution to 50 ℃, immersing the cleaned material obtained in the step three into copper plating solution, and setting the current density to 400mA/cm 2 The electroplating time is 20s, and the plating solution is obtained.
5. And (3) oxidation prevention treatment:
immersing the material obtained in the step four into an anti-oxidation liquid (mixed liquid of 1g/L benzotriazole and 1g/L benzoic acid), immersing for 5s, squeezing the liquid by a water accumulating roller, drying by hot air at 100 ℃, and winding.
6. And (3) pressing:
and pressing the composite copper foil subjected to the oxidation prevention treatment with a PCB (printed circuit board) for 1h at 180 ℃, solidifying, and then stripping and removing the carrier copper foil by a mechanical method to obtain the ultrathin copper foil.
Example 4
A carrier ultra-thin copper foil having the same structure as in example 1;
the preparation process comprises the following steps:
the preparation process comprises the following steps:
1. pretreatment of a carrier copper foil:
preparing NaOH and NaHCO 3 In the ethanol aqueous solution (wherein, the concentration of NaOH is 2M, naHCO) 3 The concentration is 0.5M, and the volume ratio of ethanol to water is 2: 1) Immersing the carrier copper foil into the solution, and treating for 5min; and taking out the carrier copper foil, and cleaning the carrier copper foil by ethanol and water in sequence.
2. Preparing an organic coating:
(1) Dissolving 40g of chitosan (deacetylation degree is 85%) in 90mL of acetic acid solution with concentration of 5wt%, adding 10mL of absolute ethyl alcohol, heating to 50 ℃, and stirring for 1h to carry out complete acidolysis on the chitosan; adding 12.5g of glutaraldehyde crosslinking agent with the weight ratio of 4.0 percent (80:1) and continuously stirring for 2 hours to obtain chitosan pretreatment liquid;
(2) Mixing 50mL of aniline (0.2M) and 50mL of phosphoric acid (0.5M) to obtain a mixed solution;
(3) Adding the chitosan pretreatment solution in the step (1) into the mixed solution in the step (2) to obtain an electrodeposition solution (wherein the concentration of chitosan is 20% (w/v));
(4) Adopting constant current deposition method to set current density at 0.05mA/cm 2 Electrodepositing for 30min to obtain a carrier copper foil loaded with the organic coating;
(5) The carrier copper foil loaded with the organic coating is respectively washed by absolute ethyl alcohol and deionized water, and dried at the temperature of 100 ℃.
3. Preparing a metal coating:
(1) Adding chromium sulfate, boric acid, ammonium acetate and sodium dodecyl sulfate into 100mL of water according to the mass ratio of 50:70:40:0.01, and stirring for dissolution to obtain metal plating solution;
(2) Heating the metal plating solution to 50 ℃, and immersing the material dried in the second step into the metal plating solution; the current density was set to 0.5mA/cm 2 The electroplating time is 30s, and the plating solution is obtained.
4. Preparing an ultrathin copper foil layer:
(1) 8.73g of copper sulfate pentahydrate, 0.0005mg of collagen, 0.0005mg of hydroxyethyl cellulose and 0.0015mg of sodium chloride are added into 100mL of water to obtain a copper plating solution;
(2) Raising the temperature of the plating solution to 50 ℃, and thenImmersing the cleaned material obtained in the third step into copper plating solution, and setting the current density to be 400mA/cm 2 The electroplating time is 20s, and the plating solution is obtained.
5. And (3) oxidation prevention treatment:
immersing the material obtained in the step four into an anti-oxidation liquid (mixed liquid of 1g/L benzotriazole and 1g/L benzoic acid), immersing for 5s, squeezing the liquid by a water accumulating roller, drying by hot air at 100 ℃, and winding.
6. And (3) pressing:
and pressing the composite copper foil subjected to the oxidation prevention treatment with a PCB (printed circuit board) for 1h at 180 ℃, solidifying, and then stripping and removing the carrier copper foil by a mechanical method to obtain the ultrathin copper foil.
Example 5
A carrier ultra-thin copper foil having the same structure as in example 1;
the preparation process comprises the following steps:
the preparation process comprises the following steps:
1. pretreatment of a carrier copper foil:
preparing KOH and KHCO 3 In an aqueous ethanol solution (wherein, the KOH concentration is 2M, naHCO) 3 The concentration is 0.5M, and the volume ratio of ethanol to water is 1: 1) Immersing the carrier copper foil into the solution, and treating for 5min; and taking out the carrier copper foil, and cleaning the carrier copper foil by ethanol and water in sequence.
2. Preparing an organic coating:
(1) Dissolving 40g of chitosan (deacetylation degree 80%) in 90mL of acetic acid solution with concentration of 5wt%, adding 10mL of absolute ethyl alcohol, heating to 50 ℃, and stirring for 1h to carry out complete acidolysis on the chitosan; adding 13.33g of 6.0% dopamine crosslinking agent (the mass ratio of chitosan to dopamine is 50:1), and continuously stirring for 2 hours to obtain chitosan pretreatment liquid;
(2) Mixing 50mL of aniline (0.5M) and 50mL of phosphoric acid (0.2M) to obtain a mixed solution;
(3) Adding the chitosan pretreatment solution in the step (1) into the mixed solution in the step (2) to obtain an electrodeposition solution (wherein the concentration of chitosan is 20% (w/v));
(4) Adopting constant current deposition method to set current density at 0.05mA/cm 2 Electrodepositing for 30min to obtain the loaded organic coatingIs a carrier copper foil of (a);
(5) The carrier copper foil loaded with the organic coating is respectively washed by absolute ethyl alcohol and deionized water, and dried at the temperature of 100 ℃.
3. Preparing a metal coating:
(1) Adding chromium sulfate, boric acid, ammonium acetate and sodium dodecyl sulfate into 100mL of water according to the mass ratio of 50:70:10:0.1, and stirring for dissolution to obtain metal plating solution;
(2) Heating the metal plating solution to 50 ℃, and immersing the material dried in the second step into the metal plating solution; the current density was set to 0.5mA/cm 2 The electroplating time is 30s, and the plating solution is obtained.
4. Preparing an ultrathin copper foil layer:
(1) 8.73g of copper sulfate pentahydrate, 0.0005mg of collagen, 0.0005mg of hydroxyethyl cellulose and 0.0015mg of sodium chloride are added into 100mL of water to obtain a copper plating solution;
(2) Raising the temperature of the plating solution to 50 ℃, immersing the cleaned material obtained in the step three into copper plating solution, and setting the current density to 400mA/cm 2 The electroplating time is 20s, and the plating solution is obtained.
5. And (3) oxidation prevention treatment:
immersing the material obtained in the step four into an anti-oxidation liquid (mixed liquid of 1g/L benzotriazole and 1g/L benzoic acid), immersing for 5s, squeezing the liquid by a water accumulating roller, drying by hot air at 100 ℃, and winding.
6. And (3) pressing:
and pressing the composite copper foil subjected to the oxidation prevention treatment with a PCB (printed circuit board) for 1h at 180 ℃, solidifying, and then stripping and removing the carrier copper foil by a mechanical method to obtain the ultrathin copper foil.
Comparative example 1
The only difference from example 1 is that chitosan is replaced with an equivalent amount of chitin.
Comparative example 2
The only difference from example 1 is that the chitosan was deacetylated to 50%.
Comparative example 3
The only difference from example 1 is that chitosan was replaced with glucosamine.
Comparative example 4
The only difference from example 1 is that in step (1), the chitosan was used in an amount of 5g.
Comparative example 5
The only difference from example 1 is that in step (1), the chitosan was used in an amount of 50g.
Comparative example 6
The only difference from example 1 is that the organic coating is not added with chitosan, and only the aniline solution is electrodeposited, resulting in a polyaniline layer.
Comparative example 7
The only difference from example 1 is that the release layer is only an organic coating, and no metal plating is prepared.
Comparative example 8
The only difference from example 1 is that the release layer is only a metal plating layer, and the organic coating layer is not prepared.
The characterization results of the relevant properties of the ultrasonic copper foil prepared by the comparative example of the invention are shown in table 1.
Table 1 results of characterization of composite copper foil properties
As can be seen from comparison of comparative examples 1 to 2 with example 1, in the case of insufficient deacetylation degree using chitin or chitosan which is not deacetylated, peeling is difficult, which may be related to its solubility, which is lowered, resulting in poor film forming property, affecting uniformity of subsequent copper plating, and thinner copper foil partial area, resulting in uneven peeling; comparative example 6 compared with example 1, the adsorption capacity of polyaniline to Cr in the organic coating was insufficient without using chitosan, and the organic layer portion adhered to the copper layer resulted in incomplete peeling, resulting in inability to perform peeling; in comparative example 3, the chitosan of the present invention was replaced with an equivalent amount of substances having amino groups and hydroxyl groups, and the peel strength was also somewhat lowered, and the cost was high, which was not suitable for industrial production. The Cr metal layer can be completely peeled off by using the Cr metal layer alone, but the Cr layer is more compact and uniform by adding the chitosan and the polyaniline layer, and the Cr metal layer is an organic-inorganic composite peeling layer, so that the effect is theoretically better than that of a pure metal Cr layer.
Compared with the embodiment 1, the comparative examples 4 and 5 have certain influence on the stripping performance of the ultrathin copper foil due to the use amount of chitosan, and the use amount of chitosan is too low, so that the thickness of the formed organic coating is small, and the adsorption capacity to Cr is insufficient; and the chitosan is excessively high in dosage, the formed organic coating is excessively large in thickness, copper plating is uneven, and the like, and the stripping of the ultrathin copper foil is also not facilitated.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A composite release layer for a carrier ultra-thin copper foil, characterized in that the composite release layer comprises an organic coating and a metal plating layer; the organic coating is prepared from chitosan and polyaniline; the metal coating is a metal chromium coating.
2. The composite release layer according to claim 1, wherein the organic coating layer is prepared by the following method:
s11: dissolving chitosan in an organic acid solution, adding ethanol, heating, stirring, dissolving, adding a cross-linking agent, and stirring to obtain chitosan pretreatment liquid;
s12: dissolving aniline in a phosphoric acid solution to obtain an aniline solution;
s13: adding chitosan pretreatment liquid into aniline solution to obtain electrodeposition liquid;
s14: immersing the carrier copper foil into electrodeposition liquid, and performing electrodeposition to obtain the copper foil.
3. The composite release layer according to claim 2, wherein the chitosan has a degree of deacetylation of 80-95%; the concentration in the electrodeposition liquid is 5-20% (w/v); the cross-linking agent is any one of glutaraldehyde, dopamine, ethylene glycol diacid and glucuronic acid, and the concentration is 1-6wt%.
4. The composite release layer according to claim 2, wherein the mass ratio of chitosan to cross-linking agent is 40-100:1.
5. the composite release layer according to claim 2, wherein the aniline concentration is 0.2 to 0.5mol/L; the concentration of the organic acid solution is 1-5wt%; the concentration of the phosphoric acid is 0.2-0.5mol/L.
6. The composite release layer according to claim 2, wherein the electrodeposition is a constant current method having a current density of 0.03 to 0.08mA/cm 2 The electrodeposition time is 6min-3h.
7. The composite release layer according to claim 1, wherein the metallic chromium plating is prepared by the following method:
s21: adding chromium sulfate, boric acid, ammonium acetate and sodium dodecyl sulfate into water, stirring and dissolving to obtain metal electroplating solution;
s22: immersing the carrier copper foil of the electrodeposited organic coating into metal electroplating liquid, and carrying out electroplating treatment to obtain the copper foil.
8. The composite release layer according to claim 7, wherein the mass ratio of chromium sulfate, boric acid, ammonium acetate, and sodium dodecyl sulfate is 20-100:60-80:10-40:0.01-0.1.
9. The composite release layer of claim 7, wherein the electroplating temperature is 20-50 ℃; the current density is 0.5-1mA/cm 2 The electroplating time is 5-30s.
10. Use of the composite release layer according to any one of claims 1-9 in the preparation of ultra-thin copper foil.
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