CN114990654B - Electrolytic copper foil surface treatment process, HVLP copper foil product and application thereof - Google Patents
Electrolytic copper foil surface treatment process, HVLP copper foil product and application thereof Download PDFInfo
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- CN114990654B CN114990654B CN202210627146.3A CN202210627146A CN114990654B CN 114990654 B CN114990654 B CN 114990654B CN 202210627146 A CN202210627146 A CN 202210627146A CN 114990654 B CN114990654 B CN 114990654B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000011889 copper foil Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 100
- 230000008569 process Effects 0.000 title claims abstract description 94
- 238000004381 surface treatment Methods 0.000 title claims abstract description 36
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 36
- 238000003618 dip coating Methods 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000005275 alloying Methods 0.000 claims abstract description 17
- 238000007747 plating Methods 0.000 claims abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 16
- 239000011651 chromium Substances 0.000 claims abstract description 16
- 230000008054 signal transmission Effects 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000004070 electrodeposition Methods 0.000 claims description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000005554 pickling Methods 0.000 claims description 15
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 13
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 12
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 12
- 229930182817 methionine Natural products 0.000 claims description 12
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 11
- 241000080590 Niso Species 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 11
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 11
- 239000011684 sodium molybdate Substances 0.000 claims description 11
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 11
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 11
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 11
- 239000011686 zinc sulphate Substances 0.000 claims description 11
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 8
- 235000018417 cysteine Nutrition 0.000 claims description 8
- 229910020881 PMo12O40 Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 239000010949 copper Substances 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 67
- 230000000052 comparative effect Effects 0.000 description 21
- 239000011888 foil Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 5
- 238000007788 roughening Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses an electrolytic copper foil surface treatment process, which takes double-sided photoelectric copper foil as a base material, and sequentially carries out acid washing, coarsening, curing, alloying, chromium plating and dip-coating silane coupling agent treatment processes to prepare an HVLP (ultra low profile) copper foil product. The invention also provides an HVLP copper foil product prepared by the electrolytic copper foil surface treatment process and application thereof in high-speed signal transmission. The invention can prepare copper nodule shapes with low roughness, high specific surface area and even distribution on the surface of the smooth copper foil, the prepared copper nodule sizes can reach submicron and nanometer levels, the bonding reliability of the electrolytic copper foil and resin can be ensured, good bonding force is formed, and the prepared copper foil product can meet the high-speed transmission of signals under high frequency.
Description
Technical Field
The invention relates to the technical field of electrolytic copper foil processing, in particular to an electrolytic copper foil surface treatment process, an HVLP copper foil product and application thereof.
Background
With the rapid development of global information technology to digitization and networking, the number of 5G base station construction will be greatly increased, and the updating of 5G mobile phones will be accelerated. The functions of high frequency, high speed and the like put higher requirements on the base material of the printed circuit board, and the functions are mainly represented by low loss, high frequency and high reliability.
According to the relation between the skin depth and the frequency, when the signal transmission frequency exceeds 1GHz, the signal transmission is only carried out within the order of magnitude range of the surface roughness, wherein the skin depth of 1GHz is 2 mu m, and the skin depth of 10GHz is only 0.66 mu m. According to the theory of signal transmission, the fluctuation of the surface roughness can lead to signal standing waves and reflection, influence signal transmission, increase signal loss and further influence the integrity of signal transmission under the high-frequency and high-speed conditions. Therefore, the copper foil performs a signal transmission process in the circuit board, and the surface roughness thereof is an important factor affecting the transmission of high-frequency signals.
In order to ensure high-frequency and high-speed transmission of signals and reduce transmission loss, the surface roughness of the copper foil is required to be as low as possible, even the copper foil tends to be profile-free, and meanwhile, the copper foil also has a larger specific surface area, so that good bonding force between the copper foil and a base material is kept, and the roughening treatment technology of the surface of the copper foil is very high in challenge. Therefore, it is important to develop a surface roughening treatment process for an electrolytic copper foil for high-speed signal transmission.
Disclosure of Invention
The present invention aims to solve the above technical problems existing in the prior art. The invention provides an electrolytic copper foil surface treatment process, an HVLP copper foil product and application thereof, which can prepare copper nodule morphology with low roughness, high specific surface area and uniform distribution on the surface of a smooth copper foil, the size of the prepared copper nodule can reach submicron and nanometer levels, the bonding reliability of the electrolytic copper foil and resin can be ensured, good bonding force is formed, and the performance requirements of high transmission frequency, high speed and low loss under 5G signals are met.
In order to solve the technical problems, the embodiment of the invention discloses an electrolytic copper foil surface treatment process, which takes a double-sided photoelectric copper foil as a base material, and sequentially carries out acid washing, roughening, curing, alloying, chromium plating and silane coupling agent dip coating treatment processes to prepare an HVLP copper foil product.
Further, the method specifically comprises the following process steps:
(1) Acid washing: soaking the substrate in pickling solution for a certain time;
(2) Coarsening: placing the substrate subjected to acid washing treatment in roughening liquid for electrodeposition;
(3) Curing: placing the coarsened base material into a curing solution for electrodeposition;
(4) Alloying: immersing the base material subjected to the solidification treatment in an alloy water solution for electrodeposition, wherein the alloy water solution contains 0.4-2g/L of NiSO 4 1-3g/L,ZnSO4 1.5-3g/L,Na2MoO4, 50-80g/L of sodium citrate, the pH of the solution is 3-6, the working temperature is 30-50 ℃, the current density is 0.5-6A/dm 2, and the electrodeposition time is 4-10s;
(5) Plating chromium: immersing the base material subjected to alloying treatment in an aqueous solution of CrO 3 to 5g/L for electrodeposition, wherein the pH of the solution is 10 to 13, the working temperature is 20 to 36 ℃, the current density is 2 to 8A/dm 2, and the electrodeposition time is 2 to 8s;
(6) Dip coating of silane coupling agent: preparing 1-10g/L of coating liquid, and dip-coating the chromed double-sided photoelectric copper foil at 20-35 ℃ for 2-5s.
Further, in the step (1), the pickling solution is an aqueous solution of sulfuric acid of 80-180g/L, and the substrate is immersed in the pickling solution for 4-8s at 20-35 ℃.
Further, in the step (2), the roughening solution is an aqueous solution containing CuSO 4 17.5-62.5g/L,CoSO4 1.5-5g/L,H2SO4 and 220g/L, the working temperature is 10-35 ℃, the current density is 25-50A/dm 2, and the electrodeposition time is 3-8s.
Further, the coarsening liquid also contains 0.05-5g/L of additive A and 20-80ppm of Cl -;
The structural formula of the additive A is Y nXM12O40·nH2 O or Y nX2M18O62·nH2 O, wherein Y is any one of H +、Na+、Cu2+, X is any one of P, si, ge, as, and M is any one of Mo, W, V, cr, nb.
Further, in the step (3), the curing liquid is an aqueous solution containing CuSO 4 62.5-112.5g/L,H2SO4 and 220g/L, the working temperature is 35-55 ℃, the current density is 10-25A/dm 2, and the electrodeposition time is 2-6s.
Further, the curing liquid also comprises 0.02-0.2g/L of additive B and 20-80ppm of Cl -;
the additive B is any one or two of cysteine and methionine.
Further, the silane coupling agent is any one or more of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyldiethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltriethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldiethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3- (methacryloyloxy) propyltriethoxysilane, vinyltrimethylsilane, vinyltriethoxysilane.
The embodiment of the invention also discloses an HVLP copper foil product prepared by the electrolytic copper foil surface treatment process.
The embodiment of the invention also discloses application of the HVLP copper foil product in high-speed signal transmission.
Compared with the prior art, the invention has the following technical effects:
The invention develops an electrolytic copper foil surface treatment process for high-speed signal transmission, by adopting the treatment process, the shape of copper nodules can be regulated and controlled, the shape of copper nodules with low roughness, high specific surface area and uniform distribution is prepared on the surface of the smooth copper foil, the particle size of the copper nodules can reach 30-200nm, the reliability of the combination of the electrolytic copper foil and resin can be ensured, good binding force is formed, and the performance requirements of high transmission frequency, high speed and low loss under 5G signals are met.
Drawings
FIG. 1 shows an SEM image of the surface of a copper foil prior to surface treatment according to the present invention;
fig. 2 shows SEM images of the surface of the copper foil after the surface treatment according to the present invention.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present specification, by describing the embodiments of the present invention with specific examples. While the description of the invention will be described in connection with the preferred embodiments, it is not intended to limit the inventive features to the implementation. Rather, the purpose of the invention described in connection with the embodiments is to cover other alternatives or modifications, which may be extended by the claims based on the invention. The following description contains many specific details for the purpose of providing a thorough understanding of the present invention. The invention may be practiced without these specific details. Furthermore, some specific details are omitted from the description in order to avoid obscuring the invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Example 1
The electrolytic copper foil surface treatment process of the embodiment comprises the following process flows: pickling-coarsening-curing-alloying-chromeplating-dip-coating of a silane coupling agent;
The surface treatment is carried out by taking 18 mu m double-sided light copper foil as a raw foil, and the specific process is as follows:
(1) Acid washing: immersing the copper foil in the pickling solution for 4s at 30 ℃ in a pure water solution of H 2SO4 and 160 g/L;
(2) Coarsening: the pure water solution contains CuSO4 55g/L,CoSO4 2g/L,H2SO4 200g/L,H4PMo11VO40·30H2O 4g/L,Cl-40ppm, and the electrodeposition process comprises the following steps: the temperature is 30 ℃, the current density is 45A/dm 2, and the electrodeposition time is 5s;
(3) Curing: the pure water solution contains CuSO 4 65g/L,H2SO4 g/L, cysteine 0.08g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 46 ℃, the current density is 16A/dm 2, and the electrodeposition time is 4s;
(4) Alloying: the pure water solution contains NiSO 4 1.6g/L,ZnSO4 2.6g/L,Na2MoO4 g/L, sodium citrate 80g/L and PH 5.0, and the electrodeposition process is as follows: the temperature is 38 ℃, the current density is 2.5A/dm 2, and the electrodeposition time is 6s;
(5) Plating chromium: crO 3 g/L, PH 12.6 in pure water solution, electrodeposition technique is: the temperature is 26 ℃, the current density is 2A/dm 2, and the electrodeposition time is 6s;
(6) Dip coating of silane coupling agent: 3 g/L3- (2, 3-glycidoxy) propyl triethoxysilane is contained in the pure water solution, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 3s at 32 ℃.
Example 2
The electrolytic copper foil surface treatment process of the embodiment comprises the following process flows: pickling-coarsening-curing-alloying-chromeplating-dip-coating of a silane coupling agent;
The surface treatment is carried out by taking 18 mu m double-sided light copper foil as a raw foil, and the specific process is as follows:
(1) Acid washing: immersing the copper foil in the pickling solution for 8s at 35 ℃ in a pure water solution of H 2SO4 and 80 g/L;
(2) Coarsening: the pure water solution contains CuSO4 22.5g/L,CoSO4 5g/L,H2SO4 150g/L,H4PMo11VO40·30H2O 0.1g/L,Cl-20ppm, and the electrodeposition process comprises the following steps: the temperature is 15 ℃, the current density is 26A/dm 2, and the electrodeposition time is 8s;
(3) Curing: the pure water solution contains CuSO 4 100g/L,H2SO4 g/L, methionine 0.18g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 50 ℃, the current density is 25A/dm 2, and the electrodeposition time is 2s;
(4) Alloying: the pure water solution contains 0.4g/L of NiSO 4 3g/L,ZnSO4 1.6g/L,Na2MoO4, 60g/L of sodium citrate and pH 3.5, the electrodeposition process is that the temperature is 48 ℃, the current density is 5A/dm 2, and the electrodeposition time is 4s;
(5) Plating chromium: crO 3 g/L, PH 12.0, electrodeposition process at 32 deg.C, current density 6A/dm 2, electrodeposition time 4s;
(6) Dip coating of silane coupling agent: the pure water solution contains 1.6g/L of 3- (methacryloyloxy) propyl trimethoxy silane, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 5s at 20 ℃.
Example 3
The electrolytic copper foil surface treatment process of the embodiment comprises the following process flows: pickling-coarsening-curing-alloying-chromeplating-dip-coating of a silane coupling agent;
The surface treatment is carried out by taking 18 mu m double-sided light copper foil as a raw foil, and the specific process is as follows:
(1) Acid washing: immersing the copper foil in a pure water solution of H 2SO4 to 120g/L at 23 ℃ for 8s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 42.5g/L,CoSO4 3g/L,H2SO4 120g/L,Na3PMo12O40·6H2O 0.5g/L,Cl-80ppm, and the electrodeposition process comprises the following steps: the temperature is 20 ℃, the current density is 35A/dm 2, and the electrodeposition time is 4s;
(3) Curing: the pure water solution contains CuSO 4 87.5g/L,H2SO4 g/L, cysteine 0.08g/L, methionine 0.08g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 36 ℃, the current density is 14A/dm 2, and the electrodeposition time is 6s;
(4) Alloying: the pure water solution contains 1.6g/L of NiSO 4 1g/L,ZnSO4 3g/L,Na2MoO4, 60g/L of sodium citrate and pH 6.0, the electrodeposition process is that the temperature is 32 ℃, the current density is 0.5A/dm 2, and the electrodeposition time is 10s;
(5) Plating chromium: crO 3 1.6.6 g/L, PH 10.5, electrodeposition process at 30 ℃ and current density 3A/dm 2, electrodeposition time 8s;
(6) Dip coating of silane coupling agent: the pure water solution contains 10g/L of 3- (2, 3-glycidoxy) propyl triethoxysilane, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 3s at 32 ℃.
Example 4
The electrolytic copper foil surface treatment process of the embodiment comprises the following process flows: pickling-coarsening-curing-alloying-chromeplating-dip-coating of a silane coupling agent;
The surface treatment was performed using an 18 μm double-sided bare copper foil as a raw foil. The specific process is as follows:
(1) Acid washing: soaking the copper foil in a pure water solution of H 2SO4 g/L at 32 ℃ for 5s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 32.5g/L,CoSO4 4g/L,H2SO4 160g/L,H6P2W9Mo9O62·30H2O 3.5g/L,Cl-30ppm, and the electrodeposition process comprises the following steps: the temperature is 32 ℃, the current density is 32A/dm 2, and the electrodeposition time is 3s;
(3) Curing: the pure water solution contains CuSO 4 75g/L,H2SO4 g/L, methionine 0.1g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 40 ℃, the current density is 20A/dm 2, and the electrodeposition time is 3s;
(4) Alloying: the pure water solution contains 1.2g/L of NiSO 4 2.8g/L,ZnSO4 2g/L,Na2MoO4, 60g/L of sodium citrate and pH 4.2, the electrodeposition process is that the temperature is 46 ℃, the current density is 1A/dm 2, and the electrodeposition time is 8s;
(5) Plating chromium: crO 3 g/L, PH 12.6, electrodeposition process at 26 ℃ and current density 3A/dm 2, electrodeposition time 6s;
(6) Dip coating of silane coupling agent: the pure water solution contains 5g/L of vinyl triethoxysilane, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 2s at 25 ℃.
Example 5
The electrolytic copper foil surface treatment process of the embodiment comprises the following process flows: pickling-roughening-curing-alloying-chromeplating-dip-coating the silane coupling agent;
The surface treatment is carried out by taking 18 mu m double-sided light copper foil as a raw foil, and the specific process is as follows:
(1) Acid washing: soaking the copper foil in a pure water solution of H 2SO4 g/L at 32 ℃ for 5s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 32.5g/L,CoSO4 4g/L,H2SO4 160g/L,H6P2W9Mo9O62·30H2O 3.5g/L,Cl-30ppm, and the electrodeposition process comprises the following steps: the temperature is 32 ℃, the current density is 32A/dm 2, and the electrodeposition time is 3s;
(3) Curing: the pure water solution contains CuSO 4 75g/L,H2SO4 g/L, methionine 0.1g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 40 ℃, the current density is 20A/dm 2, and the electrodeposition time is 3s;
(4) Alloying: the pure water solution contains 1.2g/L of NiSO 4 2.8g/L,ZnSO4 2g/L,Na2MoO4, 60g/L of sodium citrate and pH 4.2, the electrodeposition process is that the temperature is 46 ℃, the current density is 1A/dm 2, and the electrodeposition time is 8s;
(5) Plating chromium: crO 3 g/L, PH 12.6, electrodeposition process at 26 ℃ and current density 3A/dm 2, electrodeposition time 6s;
(6) Dip coating of silane coupling agent: the pure water solution contains 5g/L of vinyl triethoxysilane, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 2s at 25 ℃.
Example 6
The electrolytic copper foil surface treatment process of the embodiment comprises the following process flows: pickling-roughening-curing-alloying-chromeplating-dip-coating the silane coupling agent;
The surface treatment is carried out by taking 18 mu m double-sided light copper foil as a raw foil, and the specific process is as follows:
(1) Acid washing: soaking the copper foil in a pure water solution of H 2SO4 g/L at 32 ℃ for 5s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 32.5g/L,CoSO4 4g/L,H2SO4 160g/L,H6P2W9Mo9O62·30H2O 3.5g/L,Cl-30ppm, and the electrodeposition process comprises the following steps: the temperature is 32 ℃, the current density is 32A/dm 2, and the electrodeposition time is 3s;
(3) Curing: the pure water solution contains CuSO 4 75g/L,H2SO4 g/L, methionine 0.1g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 40 ℃, the current density is 20A/dm 2, and the electrodeposition time is 3s;
(4) Alloying: the pure water solution contains 1.2g/L of NiSO 4 2.8g/L,ZnSO4 2g/L,Na2MoO4, 60g/L of sodium citrate and pH 4.2, the electrodeposition process is carried out at 46 ℃ with the current density of 1A/dm 2 and the electrodeposition time of 8s.
(5) Plating chromium: crO 3 g/L, PH 12.6, electrodeposition process at 26 ℃ and current density 3A/dm 2, electrodeposition time 6s;
(6) Dip coating of silane coupling agent: the pure water solution contains 5g/L of vinyl triethoxysilane, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 2s at 25 ℃.
Comparative example 1
The electrolytic copper foil surface treatment process of comparative example 1 comprises the following process flows: acid washing-coarsening-curing-chromium plating-dip coating of a silane coupling agent;
The surface treatment is carried out by taking 18 mu m double-sided light copper foil as a raw foil, and the specific process is as follows:
(1) Acid washing: immersing the copper foil in a pure water solution of H 2SO4 to 120g/L at 23 ℃ for 8s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 42.5g/L,CoSO4 3g/L,H2SO4 120g/L,Na3PMo12O40·6H2O 0.5g/L,Cl-80ppm, and the electrodeposition process comprises the following steps: the temperature is 20 ℃, the current density is 35A/dm 2, and the electrodeposition time is 4s;
(3) Curing: the pure water solution contains CuSO 4 87.5g/L,H2SO4 g/L, cysteine 0.08g/L, methionine 0.08g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 36 ℃, the current density is 14A/dm 2, and the electrodeposition time is 6s;
(4) Plating chromium: crO 3 1.6.6 g/L, PH 10.5, electrodeposition process at 30 ℃ and current density 3A/dm 2, electrodeposition time 8s;
(5) Dip coating of silane coupling agent: the pure water solution contains 10g/L of 3- (2, 3-glycidoxy) propyl triethoxysilane, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 3s at 32 ℃.
Comparative example 2
The electrolytic copper foil surface treatment process of comparative example 2 comprises the following process flows: pickling-coarsening-curing-alloying-dip-coating a silane coupling agent;
The surface treatment is carried out by taking 18 mu m double-sided light copper foil as a raw foil, and the specific process is as follows:
(1) Acid washing: immersing the copper foil in a pure water solution of H 2SO4 to 120g/L at 23 ℃ for 8s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 42.5g/L,CoSO4 3g/L,H2SO4 120g/L,Na3PMo12O40·6H2O 0.5g/L,Cl-80ppm, and the electrodeposition process comprises the following steps: the temperature is 20 ℃, the current density is 35A/dm 2, and the electrodeposition time is 4s;
(3) Curing: the pure water solution contains CuSO 4 87.5g/L,H2SO4 g/L, cysteine 0.08g/L, methionine 0.08g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 36 ℃, the current density is 14A/dm 2, and the electrodeposition time is 6s;
(4) Alloying: the pure water solution contains 1.6g/L of NiSO 4 1g/L,ZnSO4 3g/L,Na2MoO4, 60g/L of sodium citrate and pH 6.0, the electrodeposition process is that the temperature is 32 ℃, the current density is 0.5A/dm 2, and the electrodeposition time is 10s;
(5) Dip coating of silane coupling agent: the pure water solution contains 10g/L of 3- (2, 3-glycidoxy) propyl triethoxysilane, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 3s at 32 ℃.
Comparative example 3
The electrolytic copper foil surface treatment process of comparative example 3 comprises the following process flows: pickling-coarsening-curing-alloying-chromeplating;
The surface treatment is carried out by taking 18 mu m double-sided light copper foil as a raw foil, and the specific process is as follows:
(1) Acid washing: immersing the copper foil in a pure water solution of H 2SO4 to 120g/L at 23 ℃ for 8s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 42.5g/L,CoSO4 3g/L,H2SO4 120g/L,Na3PMo12O40·6H2O 0.5g/L,Cl-80ppm, and the electrodeposition process comprises the following steps: the temperature is 20 ℃, the current density is 35A/dm 2, and the electrodeposition time is 4s;
(3) Curing: the pure water solution contains CuSO 4 87.5g/L,H2SO4 g/L, cysteine 0.08g/L, methionine 0.08g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 36 ℃, the current density is 14A/dm 2, and the electrodeposition time is 6s;
(4) Alloying: the pure water solution contains 1.6g/L of NiSO 4 1g/L,ZnSO4 3g/L,Na2MoO4, 60g/L of sodium citrate and pH 6.0, the electrodeposition process is that the temperature is 32 ℃, the current density is 0.5A/dm 2, and the electrodeposition time is 10s;
(5) Plating chromium: crO 3 1.6.6 g/L, PH 10.5 in pure water solution, the electrodeposition process is at 30 ℃ and the current density is 3A/dm 2, and the electrodeposition time is 8s.
Comparative example 4
The electrolytic copper foil surface treatment process of comparative example 4 comprises the following process flows: acid washing, coarsening and curing;
The surface treatment is carried out by taking 18 mu m double-sided light copper foil as a raw foil, and the specific process is as follows:
(1) Acid washing: immersing the copper foil in a pure water solution of H 2SO4 to 120g/L at 23 ℃ for 8s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 42.5g/L,CoSO4 3g/L,H2SO4 120g/L,Na3PMo12O40·6H2O 0.5g/L,Cl-80ppm, and the electrodeposition process comprises the following steps: the temperature is 20 ℃, the current density is 35A/dm 2, and the electrodeposition time is 4s;
(3) Curing: the pure water solution contains CuSO 4 87.5g/L,H2SO4 g/L, cysteine 0.08g/L, methionine 0.08g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature was 36℃and the current density was 14A/dm 2, the electrodeposition time was 6s.
The roughened surfaces of the copper foils were tested for line roughness and surface area ratio using a non-contact laser confocal microscope OLS5000 from the copper foil samples of examples 1-6 and comparative examples 1-4, and the data are detailed in Table 1.
TABLE 1
| Numbering device | Line roughness Rz | Surface area ratio |
| Example 1 sample | 0.71μm | 1.092 |
| Example 2 sample | 0.92μm | 1.165 |
| Example 3 sample | 1.34μm | 1.367 |
| Example 4 sample | 0.83μm | 1.106 |
| Example 5 sample | 1.426μm | 1.307 |
| Example 6 sample | 1.874μm | 1.521 |
| Comparative example 1 sample | 1.32μm | 1.362 |
| Comparative example 2 sample | 1.38μm | 1.372 |
| Comparative example 3 sample | 1.36μm | 1.365 |
| Comparative example 4 sample | 1.35μm | 1.370 |
The copper foil samples of examples 1-6 and comparative examples 1-4 were tested for peel strength with FR-4 prepreg laminates and the data are detailed in Table 2.
TABLE 2
| Numbering device | Peel strength of |
| Example 1 sample | 0.76N/mm |
| Example 2 sample | 1.03N/mm |
| Example 3 sample | 1.26N/mm |
| Example 4 sample | 0.78N/mm |
| Example 5 sample | 1.23N/mm |
| Example 6 sample | 1.42N/mm |
| Comparative example 1 sample | 0.74N/mm |
| Comparative example 2 sample | 0.92N/mm |
| Comparative example 3 sample | 0.89N/mm |
| Comparative example 4 sample | 0.53N/mm |
As can be seen from Table 1, the copper foil for high-speed signal transmission having low roughness and high specific surface area can be prepared by surface treatment using double-wool copper foil. The data in Table 2 show that when the surface roughness Rz of the copper foil sample prepared by the processing process flow of the patent is reduced to below 2.0 mu m or even below 1.0 mu m, the copper foil sample still has quite good binding force with the FR-4 pressing plate by virtue of excellent copper nodule distribution and surface area ratio. Compared with the example 3, the comparative examples 1-4 lack the process steps of alloying, plating chrome, dip-coating the silane coupling agent and alloying-plating chrome-silane coupling agent, respectively, so that the binding force between the copper foil samples of the comparative examples 1-4 and the FR-4 pressing plate is obviously reduced under the condition that the roughness and the surface area ratio are basically consistent with those of the copper foil sample of the example 3, and the binding force between the copper foil sample of the comparative example 4 and the plate is even reduced to 0.53N/mm, and the reduction degree is 58%.
In conclusion, the copper foil surface treatment process to be protected by the patent can meet the requirement of high-speed signal transmission, and has stable and reliable plate binding force.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a further detailed description of the invention with reference to specific embodiments, and it is not intended to limit the practice of the invention to those descriptions. Various changes in form and detail may be made therein by those skilled in the art, including a few simple inferences or alternatives, without departing from the spirit and scope of the present invention.
Claims (4)
1. The surface treatment process of the electrolytic copper foil is characterized in that an 18 mu m double-sided photoelectric copper foil is taken as a base material, and acid washing, coarsening, curing, alloying, chromium plating and dip-coating of a silane coupling agent treatment process are sequentially carried out, so that an HVLP copper foil product is prepared;
The method specifically comprises the following steps:
(1) Acid washing: immersing the copper foil in a pure water solution of H 2SO4 to 120g/L at 23 ℃ for 8s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 42.5g/L,CoSO4 3g/L,H2SO4 120g/L,Na3PMo12O40·6H2O 0.5g/L,Cl- 80ppm, and the electrodeposition process comprises the following steps: the temperature is 20 ℃, the current density is 35A/dm 2, and the electrodeposition time is 4s;
(3) Curing: the pure water solution contains CuSO 4 87.5g/L,H2SO4 g/L, cysteine 0.08g/L, methionine 0.08g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 36 ℃, the current density is 14A/dm 2, and the electrodeposition time is 6s;
(4) Alloying: the pure water solution contains 1.6g/L of NiSO 4 1g/L, ZnSO4 3g/L, Na2MoO4, 60g/L of sodium citrate and pH 6.0, the electrodeposition process is that the temperature is 32 ℃, the current density is 0.5A/dm 2, and the electrodeposition time is 10s;
(5) Plating chromium: crO 3 1.6.6 g/L, PH 10.5, electrodeposition process at 30 ℃ and current density 3A/dm 2, electrodeposition time 8s;
(6) Dip coating of silane coupling agent: the pure water solution contains 10g/L of 3- (2, 3-glycidoxy) propyl triethoxysilane, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 3s at 32 ℃.
2. The surface treatment process of the electrolytic copper foil is characterized in that an 18 mu m double-sided photoelectric copper foil is taken as a base material, and acid washing, coarsening, curing, alloying, chromium plating and dip-coating of a silane coupling agent treatment process are sequentially carried out, so that an HVLP copper foil product is prepared;
The method specifically comprises the following steps:
(1) Acid washing: soaking the copper foil in a pure water solution of H 2SO4 g/L at 32 ℃ for 5s in a pickling solution;
(2) Coarsening: the pure water solution contains CuSO4 32.5g/L,CoSO4 4g/L,H2SO4 160g/L,H6P2W9Mo9O62·30H2O 3.5g/L,Cl- 30ppm, and the electrodeposition process comprises the following steps: the temperature is 32 ℃, the current density is 32A/dm 2, and the electrodeposition time is 3s;
(3) Curing: the pure water solution contains CuSO 4 75g/L,H2SO4 g/L, methionine 0.1g/L and Cl - ppm, and the electrodeposition process is as follows: the temperature is 40 ℃, the current density is 20A/dm 2, and the electrodeposition time is 3s;
(4) Alloying: the pure water solution contains 1.2g/L of NiSO 4 2.8g/L, ZnSO4 2g/L, Na2MoO4, 60g/L of sodium citrate and pH 4.2, the electrodeposition process is that the temperature is 46 ℃, the current density is 1A/dm 2, and the electrodeposition time is 8s;
(5) Plating chromium: crO 3 g/L, PH 12.6, electrodeposition process at 26 ℃ and current density 3A/dm 2, electrodeposition time 6s;
(6) Dip coating of silane coupling agent: the pure water solution contains 5g/L of vinyl triethoxysilane, and after the silane coupling agent is hydrolyzed uniformly, the roughened surface of the copper foil is dip-coated for 2s at 25 ℃.
3. An HVLP copper foil product prepared by the electrolytic copper foil surface treatment process of any one of claims 1-2.
4. A use of the HVLP-copper foil product of claim 3 for high-speed signal transmission.
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