CN112210801A - Electroplating solution for electroplating through hole of circuit board with high aspect ratio and electroplating method thereof - Google Patents
Electroplating solution for electroplating through hole of circuit board with high aspect ratio and electroplating method thereof Download PDFInfo
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- CN112210801A CN112210801A CN201910612573.2A CN201910612573A CN112210801A CN 112210801 A CN112210801 A CN 112210801A CN 201910612573 A CN201910612573 A CN 201910612573A CN 112210801 A CN112210801 A CN 112210801A
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- 238000009713 electroplating Methods 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000654 additive Substances 0.000 claims abstract description 49
- 230000000996 additive effect Effects 0.000 claims abstract description 49
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 49
- 239000011572 manganese Substances 0.000 claims abstract description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 14
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 48
- -1 polydithio-dipropyl Polymers 0.000 claims description 23
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 23
- 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 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- DPWJHXHCEHPXGF-UHFFFAOYSA-N [amino(sulfanyl)methylidene]azanium;propane-1-sulfonate Chemical compound NC(S)=[NH2+].CCCS([O-])(=O)=O DPWJHXHCEHPXGF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- YPKOTWSAVCIFAM-UHFFFAOYSA-N [Na].CCC Chemical compound [Na].CCC YPKOTWSAVCIFAM-UHFFFAOYSA-N 0.000 claims description 5
- KHAZIIVSIJPRGF-UHFFFAOYSA-N [Na].CCCS Chemical compound [Na].CCCS KHAZIIVSIJPRGF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- 239000012224 working solution Substances 0.000 claims description 3
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000013589 supplement Substances 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000457 iridium oxide Inorganic materials 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 5
- 238000007747 plating Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
- H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to the technical field of copper electroplating, in particular to an electroplating solution for electroplating a through hole of a circuit board with a high aspect ratio and an electroplating method thereof, wherein the electroplating solution comprises 0.1-100 g/L of divalent manganese and 0.1-10 g/L of hexavalent manganese, 1-100 g/L of divalent manganese and 0.5-10 g/L of hexavalent manganese, 15-100 g/L of copper, 50-350 g/L of sulfuric acid and 5-200 mg/L of chloride, 0.2-10 ppm of additive A and 0.01-0.3% of additive B, a quasi-reversible oxidation reduction system can be formed by the added divalent manganese and hexavalent manganese, the hexavalent manganese in the oxidation reduction system is reduced by the divalent copper, compared with a divalent iron/trivalent iron system in the prior art, the situation that metal ions of high titanium oxide caused by concentration polarization are difficult to supplement in an electron transfer mode is avoided, therefore, a better electroplating effect can be obtained, the electroplating solution is suitable for an unnecessary anode (iridium oxide coating is coated on a titanium material), and the electroplating solution has higher efficiency for a circuit board with high aspect ratio when used with a pulse rectifier.
Description
Technical Field
The invention relates to the technical field of copper electroplating, in particular to electroplating solution for electroplating a through hole of a circuit board with a high aspect ratio and an electroplating method thereof.
Background
With the development of the 5G project, the base station construction continuously promotes the improvement of the circuit board manufacturing process; for the base station board, the demand for the high frequency board is increasing, the thickness of the circuit board is increasing, the via hole diameter is becoming smaller, and the so-called high aspect ratio appears. The circuit board has the advantages of large unit area, large plate thickness, small aperture, large hole density, small diameter of the bonding pad, small width of a part line, small line interval and more layers. This presents a significant challenge to the process of metallizing the holes to create vias between layers, where the drilling process, the filling material, and the subsequent processing steps of the printed wiring board all affect overall reliability and stability.
Patent CN101406569A describes an electrolytic process for filling holes and recesses with metals, which is characterized by adding a mixed system of fe (iii) ions and fe (ii) ions to a copper-ion-containing bath; by utilizing the property that Fe (III) ions can oxidize metallic copper, Fe (III) ions consumed in the hole or the recess are difficult to supplement, so that the deposition amount in the hole or the recess is larger; and a pulse current method is adopted, so that copper ions are preferentially deposited in the holes or the recesses. The method has the advantages of simple process and good filling effect. The method has the disadvantages that the concentration ratio of Fe (III) ions to Fe (II) ions in the plating solution must be well controlled, otherwise, the pore-filling quality is influenced, meanwhile, because the redox couple of the Fe (III) ions and the Fe (II) ions has good reversibility, under the action of concentration difference, the Fe (III) ions in the pores can be supplemented in a mode that the Fe (II) ions lose electrons, so that the pore-filling efficiency is influenced, in addition, the Fe (III) hydrated ions have smaller radius and can be diffused into the pores faster, so that the pore-filling efficiency is also reduced, and the method increases by using pulse current.
Disclosure of Invention
The invention aims to provide a plating solution for electroplating a through hole of a circuit board with a high aspect ratio and a plating method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
an electroplating solution for electroplating a through hole of a circuit board with a high aspect ratio comprises 0.1-100 g/L of divalent manganese and 0.1-10 g/L of hexavalent manganese, the electroplating solution comprises 1-100 g/L of divalent manganese and 0.5-10 g/L of hexavalent manganese, the electroplating solution comprises 15-100 g/L of copper, 50-350 g/L of sulfuric acid and 5-200 mg/L of chloride, and the electroplating solution comprises 0.2-10 ppm of additive A and 0.01-0.3% of additive B.
Preferably, divalent manganese ions and hexavalent manganese ions are present in the electroplating working solution.
Preferably, the divalent manganese is MnSo 4.
Preferably, the additive A is one or at least two of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-propane sulfonate, sodium N, N-dimethyl dithio-carbonyl-propane sulfonate, isothiourea propane sulfonate inner salt and 3- (benzothiazole-2-mercapto) -propane sulfonate.
Preferably, the additive B is a mixture of polyoxypropylene polyoxyethylene ether and polyethylene glycol monomethyl ether.
Preferably, the pH of the electroplating solution is less than 1.
Preferably, the method comprises the following steps:
s1: preparing and preparing 0.1-100 g/L divalent manganese and 0.1-10 g/L hexavalent manganese, 1-100 g/L divalent manganese and 0.5-10 g/L hexavalent manganese, 15-100 g/L copper, 50-350 g/L sulfuric acid and 5-200 mg/L chloride, 0.2-10 ppm additive A and 0.01-0.3% additive B contained in the electroplating solution;
s2: immersing a plate-shaped member with holes on the surface into an electroplating solution containing 0.1-100 g/L of divalent manganese and 0.1-10 g/L of hexavalent manganese, and electroplating under electrification by using the plate-shaped member as a cathode;
s3: adding 1-100 g/L of divalent manganese and 0.5-10 g/L of hexavalent manganese, 15-100 g/L of copper, 50-350 g/L of sulfuric acid and 5-200 mg/L of chloride, wherein the divalent manganese and the hexavalent manganese added into the electroplating solution can form a quasi-reversible redox system, and pentavalent vanadium in the redox system is prior to reduction of divalent copper;
s4: adding an additive, wherein 0.2-10 ppm of additive A with the mass concentration of 0.01-0.3% of additive B can be added, the additive A is one or at least two of sodium polydithio-dipropyl sulfonate, 3-mercapto-propane sodium sulfonate, N-dimethyl dithio-carbonyl propane sodium sulfonate, isothiourea propane sulfonic acid inner salt and 3- (benzothiazole-2-mercapto) -propane sodium sulfonate, and the additive B is a mixture of polyoxypropylene polyoxyethylene ether and polyethylene glycol monomethyl ether;
s5: and electrifying and electroplating, wherein the electrified current density is 1-20A/dm 2, and preferably 1-8A/dm 2.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, divalent manganese and hexavalent manganese added into the electroplating solution can form a quasi-reversible redox system, pentavalent vanadium in the redox system is prior to reduction of divalent copper, compared with a divalent iron/trivalent iron system in the prior art, the electroplating solution avoids that metal ions of high titanium oxide caused by concentration polarization are difficult to supplement in an electron transfer mode, so that a better hole filling effect can be obtained, the electroplating solution is suitable for an unnecessary anode (an iridium oxide coating is coated on a titanium material), and the electroplating solution is used under the cooperation of a pulse rectifier and has higher efficiency for a high-aspect-ratio circuit board.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The invention provides a technical scheme that:
an electroplating solution for electroplating through holes of a circuit board with a high aspect ratio and an electroplating method thereof comprise an electroplating solution, wherein the electroplating solution comprises 0.1-100 g/L of divalent manganese and 0.1-10 g/L of hexavalent manganese, the electroplating solution comprises 1-100 g/L of divalent manganese and 0.5-10 g/L of hexavalent manganese, the electroplating solution comprises 15-100 g/L of copper, 50-350 g/L of sulfuric acid and 5-200 mg/L of chloride, the electroplating solution comprises 0.2-10 ppm of additive A and 0.01-0.3% of additive B, a quasi-reversible oxidation-reduction system can be formed by the divalent manganese and the hexavalent manganese added into the electroplating solution, the pentavalent vanadium in the oxidation-reduction system is reduced in preference to the divalent copper, compared with a divalent iron/trivalent iron system in the prior art, the situation that metal ions of high titanium oxide caused by concentration polarization are difficult to supplement in an electron transfer mode is avoided, therefore, better hole filling effect can be obtained, the electroplating solution is suitable for the unnecessary anode (iridium oxide coating is coated on the titanium material), and the electroplating solution has higher efficiency for the high-aspect-ratio circuit board by being matched with the pulse rectifier.
Divalent manganese ions and hexavalent manganese ions exist in the electroplating working solution.
The divalent manganese is Mnso 4.
The additive A is one or at least two of sodium polydithio-dipropyl sulfonate, 3-mercapto-propane sulfonate, N-dimethyl dithio carbonyl propane sulfonate, isothiourea propane sulfonate inner salt and 3- (benzothiazole-2-mercapto) -propane sulfonate.
The additive B is a mixture of polyoxypropylene polyoxyethylene ether and polyethylene glycol monomethyl ether.
The pH of the plating solution is less than 1.
The method comprises the following steps:
s1: preparing and preparing 0.1-100 g/L divalent manganese and 0.1-10 g/L hexavalent manganese, 1-100 g/L divalent manganese and 0.5-10 g/L hexavalent manganese, 15-100 g/L copper, 50-350 g/L sulfuric acid and 5-200 mg/L chloride, 0.2-10 ppm additive A and 0.01-0.3% additive B contained in the electroplating solution;
s2: immersing a plate-shaped member with holes on the surface into an electroplating solution containing 0.1-100 g/L of divalent manganese and 0.1-10 g/L of hexavalent manganese, and electroplating under electrification by using the plate-shaped member as a cathode;
s3: adding 1-100 g/L of divalent manganese and 0.5-10 g/L of hexavalent manganese, 15-100 g/L of copper, 50-350 g/L of sulfuric acid and 5-200 mg/L of chloride, wherein the divalent manganese and the hexavalent manganese added into the electroplating solution can form a quasi-reversible redox system, and pentavalent vanadium in the redox system is prior to reduction of divalent copper;
s4: adding an additive, wherein 0.2-10 ppm of additive A with the mass concentration of 0.01-0.3% of additive B can be added, the additive A is one or at least two of sodium polydithio-dipropyl sulfonate, 3-mercapto-propane sodium sulfonate, N-dimethyl dithio-carbonyl propane sodium sulfonate, isothiourea propane sulfonic acid inner salt and 3- (benzothiazole-2-mercapto) -propane sodium sulfonate, and the additive B is a mixture of polyoxypropylene polyoxyethylene ether and polyethylene glycol monomethyl ether;
s5: and electrifying and electroplating, wherein the electrified current density is 1-20A/dm 2, and preferably 1-8A/dm 2.
Example 1: 0.1-100 g/L divalent manganese and 0.1-10 g/L hexavalent manganese contained in the electroplating solution, 1-100 g/L divalent manganese and 0.5-10 g/L hexavalent manganese, 15-100 g/L copper, 50-350 g/L sulfuric acid and 5-200 mg/L chloride, 0.2-10 ppm additive A and 0.01-0.3% additive B are prepared, a plate-shaped member with holes on the surface is immersed into the electroplating solution containing 0.1-100 g/L divalent manganese and 0.1-10 g/L hexavalent manganese, the plate-shaped member is used as a cathode for electroplating under electrification, 1-100 g/L divalent manganese and 0.5-10 g/L hexavalent manganese, 15-100 g/L copper, 50-350 g/L sulfuric acid and 5-200 mg/L chloride are added, the divalent manganese and the hexavalent manganese added in the electroplating solution can form a reversible redox system, in the redox system, pentavalent vanadium is reduced preferentially to divalent copper, an additive is added, 0.2-10 ppm of an additive A with the mass concentration of 0.01-0.3% of an additive B can be added, the additive A is one or at least two of sodium polydithio-dipropyl sulfonate, 3-mercapto propane sodium sulfonate, N-dimethyl dithio-carbonyl propane sodium sulfonate, isothiourea propane sulfonic acid inner salt and 3- (benzothiazole-2-mercapto) -propane sodium sulfonate, the additive B is a mixture of polyoxypropylene polyoxyethylene ether and polyethylene glycol monomethyl ether, the electrified current density is 1-10A/dm 2, and the electrified electroplating condition is observed.
Example 2: 0.1-100 g/L divalent manganese and 0.1-10 g/L hexavalent manganese contained in the electroplating solution, 1-100 g/L divalent manganese and 0.5-10 g/L hexavalent manganese, 15-100 g/L copper, 50-350 g/L sulfuric acid and 5-200 mg/L chloride, 0.2-10 ppm additive A and 0.01-0.3% additive B are prepared, a plate-shaped member with holes on the surface is immersed into the electroplating solution containing 0.1-100 g/L divalent manganese and 0.1-10 g/L hexavalent manganese, the plate-shaped member is used as a cathode for electroplating under electrification, 1-100 g/L divalent manganese and 0.5-10 g/L hexavalent manganese, 15-100 g/L copper, 50-350 g/L sulfuric acid and 5-200 mg/L chloride are added, the divalent manganese and the hexavalent manganese added in the electroplating solution can form a reversible redox system, in the redox system, pentavalent vanadium is reduced preferentially to divalent copper, an additive is added, 0.2-10 ppm of an additive A with the mass concentration of 0.01-0.3% of an additive B can be added, the additive A is one or at least two of sodium polydithio-dipropyl sulfonate, 3-mercapto propane sodium sulfonate, N-dimethyl dithio-carbonyl propane sodium sulfonate, isothiourea propane sulfonic acid inner salt and 3- (benzothiazole-2-mercapto) -propane sodium sulfonate, the additive B is a mixture of polyoxypropylene polyoxyethylene ether and polyethylene glycol monomethyl ether, the electrified current density is 10-20A/dm 2, and the electrified electroplating condition is observed.
In summary, the following steps: the observation of the electroplating condition with the current density of 1-10A/dm 2 shows that the hole filling effect is better when the current density is 1-8A/dm 2.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. The electroplating solution for electroplating the through hole of the circuit board with the high aspect ratio comprises 0.1-100 g/L of divalent manganese and 0.1-10 g/L of hexavalent manganese, comprises 1-100 g/L of divalent manganese and 0.5-10 g/L of hexavalent manganese, comprises 15-100 g/L of copper, 50-350 g/L of sulfuric acid and 5-200 mg/L of chloride, and comprises 0.2-10 ppm of additive A and 0.01-0.3% of additive B.
2. The electroplating solution and the electroplating method for electroplating the through hole of the high-aspect-ratio circuit board are characterized in that divalent manganese ions and hexavalent manganese ions are contained in the electroplating working solution.
3. The electroplating solution and the electroplating method for electroplating the through hole of the high-aspect-ratio circuit board according to claim 1, wherein the divalent manganese is Mnso 4.
4. The electroplating solution and the electroplating method for electroplating the through hole of the circuit board with the high aspect ratio as claimed in claim 1, wherein the additive A is one or at least two of sodium polydithio-dipropyl sulfonate, sodium 3-mercaptopropane sulfonate, sodium N, N-dimethyldithiocarbonyl propane sulfonate, isothiourea propane sulfonate inner salt and sodium 3- (benzothiazole-2-mercapto) -propane sulfonate.
5. The electroplating solution for electroplating through holes of high aspect ratio circuit boards and the electroplating method thereof as claimed in claim 1, wherein the additive B is a mixture of polyoxypropylene polyoxyethylene ether and polyethylene glycol monomethyl ether.
6. The electroplating solution for electroplating through holes of high aspect ratio circuit boards and the electroplating method thereof as claimed in claim 1, wherein the pH of the electroplating solution is less than 1.
7. The electroplating solution and the electroplating method thereof for electroplating the through hole of the high-aspect-ratio circuit board according to claim 1 are characterized by comprising the following method steps:
s1: preparing and preparing 0.1-100 g/L divalent manganese and 0.1-10 g/L hexavalent manganese, 1-100 g/L divalent manganese and 0.5-10 g/L hexavalent manganese, 15-100 g/L copper, 50-350 g/L sulfuric acid and 5-200 mg/L chloride, 0.2-10 ppm additive A and 0.01-0.3% additive B contained in the electroplating solution;
s2: immersing a plate-shaped member with holes on the surface into an electroplating solution containing 0.1-100 g/L of divalent manganese and 0.1-10 g/L of hexavalent manganese, and electroplating under electrification by using the plate-shaped member as a cathode;
s3: adding 1-100 g/L bivalent manganese and 0.5-10 g/L hexavalent manganese, 15-100 g/L copper, 50-350 g/L sulfuric acid and 5-200 mg/L chloride, wherein the bivalent manganese and the hexavalent manganese added into the electroplating solution can form a quasi-reversible oxidation-reduction system, and pentavalent vanadium in the oxidation-reduction system is prior to reduction of bivalent copper;
s4: adding an additive, wherein 0.2-10 ppm of additive A with the mass concentration of 0.01-0.3% of additive B can be added, the additive A is one or at least two of sodium polydithio-dipropyl sulfonate, 3-mercapto-propane sodium sulfonate, N-dimethyl dithio-carbonyl propane sodium sulfonate, isothiourea propane sulfonic acid inner salt and 3- (benzothiazole-2-mercapto) -propane sodium sulfonate, and the additive B is a mixture of polyoxypropylene polyoxyethylene ether and polyethylene glycol monomethyl ether;
s5: electrifying and electroplating, wherein the electrified current density is 1-20A/dm 2, and is selected to be 1-8A/dm 2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114351195A (en) * | 2022-03-19 | 2022-04-15 | 深圳市创智成功科技有限公司 | Electro-coppering formula for pulse through hole filling and electro-coppering process thereof |
| TWI816388B (en) * | 2021-05-17 | 2023-09-21 | 美商麥克達米德恩索龍股份有限公司 | Single step electrolytic method of filling through holes in printed circuit boards and other substrates |
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| US20140069805A1 (en) * | 2012-09-12 | 2014-03-13 | Samsung Electro-Mechanics Co., Ltd. | Electro-copper plating apparatus |
| CN107313081A (en) * | 2017-07-24 | 2017-11-03 | 苏州天承化工有限公司 | A kind of logical blind hole plates electroplate liquid and electro-plating method altogether |
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| US6099711A (en) * | 1995-11-21 | 2000-08-08 | Atotech Deutschland Gmbh | Process for the electrolytic deposition of metal layers |
| US20140069805A1 (en) * | 2012-09-12 | 2014-03-13 | Samsung Electro-Mechanics Co., Ltd. | Electro-copper plating apparatus |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI816388B (en) * | 2021-05-17 | 2023-09-21 | 美商麥克達米德恩索龍股份有限公司 | Single step electrolytic method of filling through holes in printed circuit boards and other substrates |
| CN114351195A (en) * | 2022-03-19 | 2022-04-15 | 深圳市创智成功科技有限公司 | Electro-coppering formula for pulse through hole filling and electro-coppering process thereof |
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