CN115142100A - Acidic sulfate electronic copper electroplating combined additive for metal dense filling of PCB (printed circuit board) through hole - Google Patents
Acidic sulfate electronic copper electroplating combined additive for metal dense filling of PCB (printed circuit board) through hole Download PDFInfo
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- CN115142100A CN115142100A CN202210732452.3A CN202210732452A CN115142100A CN 115142100 A CN115142100 A CN 115142100A CN 202210732452 A CN202210732452 A CN 202210732452A CN 115142100 A CN115142100 A CN 115142100A
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- acid
- refiner
- agent
- electrocoppering
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- 238000009713 electroplating Methods 0.000 title claims abstract description 32
- 239000000654 additive Substances 0.000 title claims abstract description 29
- 238000011049 filling Methods 0.000 title claims abstract description 28
- 230000000996 additive effect Effects 0.000 title claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 20
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 7
- 239000002184 metal Substances 0.000 title claims abstract description 7
- 239000010949 copper Substances 0.000 title abstract description 38
- 229910052802 copper Inorganic materials 0.000 title abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 238000007747 plating Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- -1 halogen anion Chemical class 0.000 claims abstract description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 229920000570 polyether Polymers 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 7
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 6
- CMNQZZPAVNBESS-UHFFFAOYSA-N 6-sulfanylhexanoic acid Chemical compound OC(=O)CCCCCS CMNQZZPAVNBESS-UHFFFAOYSA-N 0.000 claims description 6
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims description 6
- 125000002917 halogen containing inorganic group Chemical group 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000136 polysorbate Polymers 0.000 claims description 6
- 229950008882 polysorbate Drugs 0.000 claims description 6
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical group CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 4
- QPUSANCBJDDXSA-UHFFFAOYSA-N ethanethiol;sodium Chemical compound [Na].CCS QPUSANCBJDDXSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 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 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000001082 (3R)-3-sulfanylpentan-2-one Substances 0.000 claims description 2
- BDNDQOCRJGGSJO-UHFFFAOYSA-N 1-amino-2-phenylpropan-2-ol Chemical compound NCC(O)(C)C1=CC=CC=C1 BDNDQOCRJGGSJO-UHFFFAOYSA-N 0.000 claims description 2
- LYFRUBQVZGVXPR-UHFFFAOYSA-N 1h-indole-3-thiol Chemical compound C1=CC=C2C(S)=CNC2=C1 LYFRUBQVZGVXPR-UHFFFAOYSA-N 0.000 claims description 2
- HKAVADYDPYUPRD-UHFFFAOYSA-N 1h-pyrazine-2-thione Chemical compound SC1=CN=CC=N1 HKAVADYDPYUPRD-UHFFFAOYSA-N 0.000 claims description 2
- UHTVFSCCUGCUPJ-UHFFFAOYSA-N 2,3-bis(sulfanyl)propane-1-sulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)CC(S)CS UHTVFSCCUGCUPJ-UHFFFAOYSA-N 0.000 claims description 2
- ADVPTQAUNPRNPO-UHFFFAOYSA-N 2-azaniumyl-3-sulfinopropanoate Chemical compound OC(=O)C(N)CS(O)=O ADVPTQAUNPRNPO-UHFFFAOYSA-N 0.000 claims description 2
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 claims description 2
- WYKHFQKONWMWQM-UHFFFAOYSA-N 2-sulfanylidene-1h-pyridine-3-carboxylic acid Chemical group OC(=O)C1=CC=CN=C1S WYKHFQKONWMWQM-UHFFFAOYSA-N 0.000 claims description 2
- SZECUQRKLXRGSJ-UHFFFAOYSA-N 3-Mercapto-2-pentanone Chemical compound CCC(S)C(C)=O SZECUQRKLXRGSJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940086681 4-aminobenzoate Drugs 0.000 claims description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002199 base oil Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- ZAASRHQPRFFWCS-UHFFFAOYSA-P diazanium;oxygen(2-);uranium Chemical compound [NH4+].[NH4+].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[U].[U] ZAASRHQPRFFWCS-UHFFFAOYSA-P 0.000 claims description 2
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical group NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 claims description 2
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 claims description 2
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 2
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 claims description 2
- 229960003966 nicotinamide Drugs 0.000 claims description 2
- 235000005152 nicotinamide Nutrition 0.000 claims description 2
- 239000011570 nicotinamide Substances 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000223 polyglycerol Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 claims description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical group CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000007664 blowing Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 2
- 150000003335 secondary amines Chemical class 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 150000003512 tertiary amines Chemical class 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 3
- XKPKIGSYCLTAJO-UHFFFAOYSA-N 1-butoxypropane-1,2-diol Chemical compound CCCCOC(O)C(C)O XKPKIGSYCLTAJO-UHFFFAOYSA-N 0.000 description 2
- XOGTZOOQQBDUSI-UHFFFAOYSA-M Mesna Chemical compound [Na+].[O-]S(=O)(=O)CCS XOGTZOOQQBDUSI-UHFFFAOYSA-M 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
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- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
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- 241001391944 Commicarpus scandens Species 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- 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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
Abstract
The invention discloses an acidic sulfate electronic copper electroplating combined additive for densely filling metal in through holes of PCBs (printed Circuit boards), which consists of a bridging agent, a carrying agent, a refiner and a leveling agent in a mass ratio of 10-100: 50-1500: 0.1-20: 0.1-100. The invention uses inorganic substance providing halogen anion as bridging agent, uses polyalcohol or polyether or polyester compound as carrier, uses sulfur-containing compound as refiner, uses primary/secondary/tertiary amine or quaternary ammonium salt as leveling agent, and combines specific current density conditions of high copper, low acid, temperature, plating solution stirring, air blowing, cathode moving and electroplating to realize dense filling of PCB through holes.
Description
Technical Field
The invention belongs to the technical field of electronic electroplating, and particularly relates to an acidic sulfate electronic copper electroplating combined additive for densely filling metal in a PCB (printed circuit board) through hole.
Background
With the rapid development in the fields of 5G communication, energy devices, wearable devices, and the like, printed Circuit Boards (PCBs) supporting various circuit components have received much attention. Through-hole interconnection is one of the core technologies to realize high-density interconnection of PCBs. Through-hole interconnection techniques include resin via filling and fill plating. Resin plugging, i.e. via hole wall, first deposits a layer of conductive copper of equal thickness, followed by filling the remaining space in the hole with a plugging ink. The method has low cost, but the copper layer is thin, so that the signal transmission area is small, and the heat can not be effectively dissipated. And filling electroplating, namely electroplating the through hole to densely fill the copper layer. The method can increase the conductive area of copper, improve the signal transmission capability and effectively dissipate heat. Therefore, the through hole electroplating filling can better meet the continuous development of high-density interconnection of the PCB.
Acid sulfate electrocoppering is the most common process to achieve dense via fill. The specific combined additive is added into the acidic sulfate electronic plating solution, so that the deposition rates of copper at the orifice and the hole middle part can be reversed, namely the deposition rate of copper at the orifice is lower than that of copper at the hole middle part, and the dense filling of the through hole is realized. Therefore, the acid sulfate electronic copper electroplating combined additive capable of realizing dense filling of the through holes has important industrial application value.
CN109972180A discloses a through hole electroplating additive using 2,2-dithiodipyridine as a leveling agent, which is combined with an inhibitor polyethylene glycol and an accelerator sodium polydithio propane sulfonate to realize dense filling of through holes, but disulfide bonds in 2,2-dithiodipyridine are easy to break. CN111424296A, CN112030203A and CN113802158A both disclose a methyl sulfonate electronic copper electroplating solution for through hole electroplating filling, which can realize through hole dense filling by combining with specific additives (inhibitor, accelerator and leveling agent), but the methyl sulfonic acid is stronger in acidity than sulfuric acid and is easier to corrode equipment. Therefore, the invention of the acidic sulfate electrocoppering combined additive suitable for through hole dense filling has great practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an acidic sulfate electronic copper electroplating combined additive for densely filling metal in through holes of PCBs (printed circuit boards).
The technical scheme of the invention is as follows:
an acidic sulfate electronic copper plating combination additive for densely filling through holes of PCBs (printed Circuit Board) consists of a bridging agent, a carrying agent, a refiner and a leveling agent in a mass ratio of 10-100: 50-1500: 0.1-20: 0.1-100, wherein,
the bridging agent is a halogen-containing inorganic compound, wherein the halogen is chlorine, bromine or iodine,
the carrier is polypropylene glycol, butoxy polypropylene glycol, polyvinyl acetate, polyoxyethylene stearic acid ether, glycolic acid ethoxy base oil ether, tetraethylene glycol monooctyl ether, polyether alcohol, polyglycerol, polyethylene oxide, polysorbate, poly-1,4-butanediol bis (4-aminobenzoate), fatty alcohol polyoxyethylene ether, polycaprolactone glycol, polyethylene glycol block copolymer or polypropylene glycol block copolymer,
the refiner is 2-mercaptonicotinic acid, 2-mercaptopyrazine, 3-mercapto-2-pentanone, 3-mercapto-1-propanol, 2-mercaptothiazoline, 3-mercaptoindole, 6-mercaptohexanoic acid, L-cysteine sulfinic acid, cysteine sulfone, 2,3-dimercaptopropanesulfonic acid sodium, alpha-alkenyl sodium sulfonate, 2-mercaptoethane sodium sulfonate or methyl propylene sodium sulfonate,
the leveling agent is furfuryl amine, beta-naphthylamine, dimethyl pyridine amine, tribenzylamine, propargyl amine, N-ethyl propyl amine, melamine, diallyl amine, ammonium succinate, acid red, alkaline red, neutral red, ammonium glycyrrhetate, ammonium diuranate or nicotinamide.
In a preferred embodiment of the present invention, the halogen-containing inorganic compound is sodium chloride, hydrochloric acid or potassium bromide.
In a preferred embodiment of the invention, the vehicle is a butoxypropylene glycol, a polysorbate or a fatty alcohol polyoxyethylene ether.
In a preferred embodiment of the present invention, the refiner is 2-mercaptothiazoline, sodium 2-mercaptoethanesulfonate or 6-mercaptohexanoic acid.
In a preferred embodiment of the invention, the leveler is lutidine amine, ammonium succinate or basic red.
In a preferred embodiment of the present invention, the halogen-containing inorganic compound is sodium chloride, hydrochloric acid or potassium bromide, the vehicle is butoxypropylene glycol, polysorbate or fatty alcohol-polyoxyethylene ether, the refiner is 2-mercaptothiazoline, sodium 2-mercaptoethanesulfonate or 6-mercaptohexanoic acid, and the leveler is lutidine, ammonium succinate or basic red.
In a preferred embodiment of the present invention, the mass ratio of the bridging agent, the carrier, the refiner and the leveler is 40-90: 500-1000: 0.2-16: 0.5-60.
In a preferred embodiment of the present invention, the electro-plating conditions to which it is applied are: the electroplating solution contains 180-250g/L CuSO 4 ·5H 2 O and 20-80g/L H 2 SO 4 The electroplating temperature is 20-35 ℃, and the electroplating current density is 0.5-4.0A/dm 2 。
Further preferably, the plating solution is added, wherein the final concentration of the bridging agent is 10-100mg/L, the final concentration of the carrier agent is 50-1500mg/L, the final concentration of the refiner is 0.1-20mg/L, and the final concentration of the leveler is 0.1-100mg/L.
Still more preferably, the final concentration of the bridging agent is 40-90mg/L, the final concentration of the carrier is 200-1000mg/L, the final concentration of the refiner is 0.2-16mg/L, and the final concentration of the leveler is 0.5-60mg/L.
The beneficial effects of the invention are:
1. the invention uses inorganic substance providing halogen anion as bridging agent, uses polyalcohol or polyether or polyester compound as carrier, uses sulfur-containing compound as refiner, uses primary/secondary/tertiary amine or quaternary ammonium salt as leveling agent, and combines specific current density conditions of high copper, low acid, temperature, plating solution stirring, air blowing, cathode moving and electroplating to realize dense filling of PCB through holes.
2. The bridging agent has the functions of connecting copper ions in the electronic electroplating solution and cooperatively transporting a carrier agent, a refiner or a leveler to form an electronic bridge; when the mass concentration of the bridging agent is lower than 10mg/L, an electronic bridge is difficult to form; when the mass concentration of the bridging agent is higher than 100mg/L, a cuprous barrier film layer is easily formed on the surface of the coating, which is not beneficial to reducing copper ions into metallic copper.
3. The carrying agent has the mixing characteristics of inhibiting the reduction of copper ions, promoting the uniform adsorption of a refiner and a leveling agent, reducing the surface tension of electronic electroplating liquid and improving the wettability of a plating layer; when the mass concentration of the carrier is lower than 50mg/L, the deposition rate of copper at the orifice of the through hole of the PCB is high, the orifice is quickly sealed, and a hole is formed in Kong Nadu layer; when the mass concentration of the carrier is higher than 1500mg/L, a carrier-cuprous-bridging agent composite barrier film layer is easily formed on the surface of the plating layer, copper ions are not favorably reduced into metal copper, and a large amount of foam is generated in the electronic plating process.
4. The refiner of the invention has the mixing characteristic of promoting the reduction of copper ions and reducing the overpotential of copper nucleation. When the mass concentration of the refiner is lower than 0.1mg/L, the refiner cannot be combined with a bridging agent, and copper deposition in the middle of a PCB through hole is accelerated; when the mass concentration of the refiner is higher than 20mg/L, copper deposition in the middle of the PCB hole is strongly inhibited, resulting in pore formation.
5. The leveling agent of the invention has the mixed characteristics of inhibiting the reduction of copper ions and controlling the consumption in the electronic plating process by diffusion. When the mass concentration of the leveling agent is lower than 0.1mg/L, the relative rates of copper deposition in the middle of the hole and the copper deposition in the hole opening cannot be regulated; when the mass concentration of the leveling agent is higher than 100mg/L, the leveling agent is easily mixed in a deposited copper layer due to the strong adsorption capacity, and the physical properties of the copper layer, such as heat conductivity, electric conductivity, ductility and the like, are influenced.
Drawings
FIG. 1 is a microscopic image of PCB through hole copper-electroplating filling metallographic due to unreasonable additive collocation in comparative example 1 of the present invention.
FIG. 2 is a microscopic view of PCB blind via copper-electroplating filling in the PCB of embodiment 1 of the present invention.
FIG. 3 is a microscopic view of PCB blind via copper-electroplating filling in the PCB of embodiment 2 of the present invention.
FIG. 4 is a microscopic view of PCB blind via copper-electroplating filling in the PCB in embodiment 3 of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Examples 1 to 3
The specific preparation and use processes of the combined additive for PCB through hole copper dense filling are as follows (taking preparation of 1000mL of concentrated solution as an example):
(1) Accurately weighing 10-100g of bridging agent, weighing the bridging agent, the transportation agent, the refiner and the leveler according to the mass ratio of 10-100: 50-1500: 0.1-20: 0.1-100, metering the transportation agent, the refiner and the leveler to 1000mL, and preparing into an additive concentrated solution; when the combined additive is prepared, the components can be independently prepared according to the mass proportion of the combined additive;
(2) When in electronic plating, 1mL/L of concentrated solution is added into high-copper low-acid base solution (80-250 g/L CuSO) 4 ·5H 2 O and 20-80g/L H 2 SO 4 )；
The electroplating process flow for the PCB through hole copper dense filling is as follows (taking a through hole with the aperture of 125 μm and the hole depth of 250 μm as an example):
oil removal (50-70 ℃,5 min) → deionized water washing → 5% dilute sulfuric acid activation, ultrasound (30 s) → deionized water washing → pre-immersion in plating solution (3 min) → electro-coppering (120 min) → passivation (1 min).
Using 1000mL of an electronic plating solution, a through-hole having an aperture of 125 μm and a depth of 250 μm, a pure copper plate, a phosphorus-containing copper plate, and an insoluble iridium-coated titanium mesh were used as an anode, and a PCB plate subjected to electroless copper plating conductive treatment was used as a cathode. The combined additive is combined with high copper and low acid (180-250 g/L CuSO) 4 ·5H 2 O and 20-80g/L H 2 SO 4 ) At 20-35 deg.C, stirring the plating solution, blowing air, moving cathode, and electroplating at current density of 0.5-4.0A/dm 2 The conditions, which can realize the dense filling of the via hole copper, are as shown in the following table 1 and fig. 1 to 4, and the specific composition of the electronic plating solution, the implementation conditions and the obtained filling effect are as follows: when the additive in the electronic electroplating solution is not reasonably matched, the deposition rate of copper at the orifice is higher than that of copper at the middle part of the hole, so that the through hole is filled with a hole;when the additives in the electronic electroplating solution are reasonably matched, the deposition rate of copper at the orifice is lower than that at the middle part of the hole, and the dense filling of the through hole is realized.
TABLE 1 formulation of 1000mL plating solutions and corresponding effects in examples 1 to 3 and comparative example 1
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, and all equivalent variations and modifications made within the scope of the present invention and the content of the description should be included in the scope of the present invention.
Claims (10)
1. An acidic sulfate electro-coppering combined additive for metal dense filling of PCB through holes is characterized in that: consists of bridging agent, carrier agent, refiner and leveler in the mass ratio of 10-100 to 50-1500 to 0.1-20 to 0.1-100, wherein,
the bridging agent is a halogen-containing inorganic compound, wherein the halogen is chlorine, bromine or iodine,
the carrier is polypropylene glycol, butoxy polypropylene glycol, polyvinyl acetate, polyoxyethylene stearic acid ether, glycolic acid ethoxy base oil ether, tetraethylene glycol monooctyl ether, polyether alcohol, polyglycerol, polyethylene oxide, polysorbate, poly-1,4-butanediol bis (4-aminobenzoate), fatty alcohol polyoxyethylene ether, polycaprolactone glycol, polyethylene glycol block copolymer or polypropylene glycol block copolymer,
the refiner is 2-mercaptonicotinic acid, 2-mercaptopyrazine, 3-mercapto-2-pentanone, 3-mercapto-1-propanol, 2-mercaptothiazoline, 3-mercaptoindole, 6-mercaptohexanoic acid, L-cysteine sulfinic acid, cysteine sulfone, 2,3-dimercaptopropanesulfonic acid sodium, alpha-alkenyl sodium sulfonate, 2-mercaptoethane sodium sulfonate or methyl propylene sodium sulfonate,
the leveling agent is furfuryl amine, beta-naphthylamine, dimethyl pyridine amine, tribenzylamine, propargyl amine, N-ethyl propyl amine, melamine, diallyl amine, ammonium succinate, acid red, alkaline red, neutral red, ammonium glycyrrhetate, ammonium diuranate or nicotinamide.
2. The acid sulfate electrocoppering composition additive as claimed in claim 1, wherein: the halogen-containing inorganic compound is sodium chloride, hydrochloric acid or potassium bromide.
3. The acid sulfate electrocoppering composition additive as claimed in claim 1, wherein: the carrier is butoxy polypropylene glycol, polysorbate or fatty alcohol polyoxyethylene ether.
4. The acid sulfate electrocoppering composition additive as claimed in claim 1, wherein: the refiner is 2-mercaptothiazoline, 2-mercaptoethane sodium sulfonate or 6-mercaptohexanoic acid.
5. The acid sulfate electrocoppering composition additive as claimed in claim 1, wherein: the leveling agent is dimethyl pyridylamine, ammonium succinate or basic red.
6. The acid sulfate electrocoppering composition additive as claimed in claim 1, wherein: the halogen-containing inorganic compound is sodium chloride, hydrochloric acid or potassium bromide, the carrier is butoxy polypropylene glycol, polysorbate or fatty alcohol polyoxyethylene ether, the refiner is 2-mercaptothiazoline, 2-mercaptoethane sodium sulfonate or 6-mercaptohexanoic acid, and the leveler is lutidine, ammonium succinate or basic red.
7. The acid sulfate electrocoppering composition additive as claimed in claim 1, wherein: the mass ratio of the bridging agent, the carrier, the refiner and the leveling agent is 40-90: 500-1000: 0.2-16: 0.5-60.
8. The acid sulfate electrocoppering composition additive as claimed in any one of claims 1 to 7, wherein: the applicable electronic plating conditions are as follows: the electroplating solution contains 180-250g/L CuSO 4 ·5H 2 O and 20-80g/L H 2 SO 4 The electroplating temperature is 20-35 ℃, and the electroplating current density is 0.5-4.0A/dm 2 。
9. The acid sulfate electrocoppering composition additive as claimed in claim 8, wherein: the final concentration of the bridging agent is 10-100mg/L, the final concentration of the carrier agent is 50-1500mg/L, the final concentration of the refiner is 0.1-20mg/L, and the final concentration of the leveler is 0.1-100mg/L.
10. The acid sulfate electrocoppering composition additive as claimed in claim 9, wherein: the final concentration of the bridging agent reaches 40-90mg/L, the final concentration of the carrier reaches 200-1000mg/L, the final concentration of the refiner reaches 0.2-16mg/L, and the final concentration of the leveler reaches 0.5-60mg/L.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210732452.3A CN115142100A (en) | 2022-06-24 | 2022-06-24 | Acidic sulfate electronic copper electroplating combined additive for metal dense filling of PCB (printed circuit board) through hole |
| PCT/CN2023/101793 WO2023246889A1 (en) | 2022-06-24 | 2023-06-21 | Acid sulfate electroplating copper combination additive for dense filling of pcb through hole metal |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210732452.3A CN115142100A (en) | 2022-06-24 | 2022-06-24 | Acidic sulfate electronic copper electroplating combined additive for metal dense filling of PCB (printed circuit board) through hole |
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| CN115142100A true CN115142100A (en) | 2022-10-04 |
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| WO (1) | WO2023246889A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115787007A (en) * | 2022-11-03 | 2023-03-14 | 厦门大学 | Acidic sulfate electronic copper electroplating additive composition and application thereof |
| WO2023246889A1 (en) * | 2022-06-24 | 2023-12-28 | 厦门大学 | Acid sulfate electroplating copper combination additive for dense filling of pcb through hole metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115142100A (en) * | 2022-06-24 | 2022-10-04 | 厦门大学 | Acidic sulfate electronic copper electroplating combined additive for metal dense filling of PCB (printed circuit board) through hole |
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2022
- 2022-06-24 CN CN202210732452.3A patent/CN115142100A/en active Pending
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- 2023-06-21 WO PCT/CN2023/101793 patent/WO2023246889A1/en unknown
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| JP2013053336A (en) * | 2011-09-02 | 2013-03-21 | Ishihara Chem Co Ltd | Electrolytic copper plating bath and electronic part having electrodeposited film formed by the bath |
| CN109972180A (en) * | 2019-04-12 | 2019-07-05 | 博敏电子股份有限公司 | The new application of 2,2 '-dithiodipyridine and the electro-plating method that filling perforation additive is electroplated and uses the additive for using it |
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| CN113337857A (en) * | 2021-04-29 | 2021-09-03 | 厦门大学 | Acidic sulfate copper electroplating combined additive for thickening PCB through hole metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023246889A1 (en) * | 2022-06-24 | 2023-12-28 | 厦门大学 | Acid sulfate electroplating copper combination additive for dense filling of pcb through hole metal |
| CN115787007A (en) * | 2022-11-03 | 2023-03-14 | 厦门大学 | Acidic sulfate electronic copper electroplating additive composition and application thereof |
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| WO2023246889A1 (en) | 2023-12-28 |
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