CN115787007A - Acidic sulfate electronic copper electroplating additive composition and application thereof - Google Patents
Acidic sulfate electronic copper electroplating additive composition and application thereof Download PDFInfo
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- CN115787007A CN115787007A CN202211395327.4A CN202211395327A CN115787007A CN 115787007 A CN115787007 A CN 115787007A CN 202211395327 A CN202211395327 A CN 202211395327A CN 115787007 A CN115787007 A CN 115787007A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
- 239000010949 copper Substances 0.000 title claims abstract description 59
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 37
- 239000000654 additive Substances 0.000 title claims abstract description 34
- 230000000996 additive effect Effects 0.000 title claims abstract description 32
- 238000009713 electroplating Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 24
- 238000007747 plating Methods 0.000 claims abstract description 46
- 238000011049 filling Methods 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 8
- -1 polydithio-dipropyl Polymers 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims description 6
- CAULSPKRQNHKIT-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanol Chemical compound OCCOCCS CAULSPKRQNHKIT-UHFFFAOYSA-N 0.000 claims description 6
- VFAXPOVKNPTBTM-UHFFFAOYSA-N 2-[1-(sulfanylmethyl)cyclopropyl]acetic acid Chemical compound OC(=O)CC1(CS)CC1 VFAXPOVKNPTBTM-UHFFFAOYSA-N 0.000 claims description 6
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 6
- BLBDTBCGPHPIJK-UHFFFAOYSA-N 4-Amino-2-chloropyridine Chemical compound NC1=CC=NC(Cl)=C1 BLBDTBCGPHPIJK-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229940100242 glycol stearate Drugs 0.000 claims description 6
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 6
- 229940055577 oleyl alcohol Drugs 0.000 claims description 6
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- OBDVFOBWBHMJDG-UHFFFAOYSA-M 3-sulfanylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-M 0.000 claims description 3
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 3
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 claims description 2
- HNXGGWNCFXZSAI-UHFFFAOYSA-N 2-morpholin-2-ylethanesulfonic acid Chemical compound OS(=O)(=O)CCC1CNCCO1 HNXGGWNCFXZSAI-UHFFFAOYSA-N 0.000 claims description 2
- TUBRCQBRKJXJEA-UHFFFAOYSA-N 3-[hexadecyl(dimethyl)azaniumyl]propane-1-sulfonate Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O TUBRCQBRKJXJEA-UHFFFAOYSA-N 0.000 claims description 2
- NFHGWQLAJYTULJ-UHFFFAOYSA-N 3-methylsulfanyl-1,2,4-triazine Chemical compound CSC1=NC=CN=N1 NFHGWQLAJYTULJ-UHFFFAOYSA-N 0.000 claims description 2
- TZCYLJGNWDVJRA-UHFFFAOYSA-N 6-chloro-1-hydroxybenzotriazole Chemical group C1=C(Cl)C=C2N(O)N=NC2=C1 TZCYLJGNWDVJRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- LLYOXZQVOKALCD-UHFFFAOYSA-N chembl1400298 Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC1=CC=CC=N1 LLYOXZQVOKALCD-UHFFFAOYSA-N 0.000 claims description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- IZDROVVXIHRYMH-UHFFFAOYSA-N methanesulfonic anhydride Chemical compound CS(=O)(=O)OS(C)(=O)=O IZDROVVXIHRYMH-UHFFFAOYSA-N 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 claims description 2
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 26
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical class OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Abstract
The invention discloses an acidic sulfate electronic copper electroplating additive composition and application thereof, wherein the acidic sulfate electronic copper electroplating additive composition consists of a carrier inhibitor, a refiner and a plating leveler in a mass ratio of 100-800: 0.5-10: 0.5-20. Within the range of using conditions, the invention can effectively reduce the surface tension of the plating solution, refine copper layer particles, improve the efficiency of deposition current, realize the dense filling of PCB blind holes and thin surface copper thickness, realize the dense filling of blind holes with the aperture of 100 mu m and the hole depth of 50 mu m, have excellent surface smoothness and the thickness of the copper layer can be lower than 15 mu m.
Description
Technical Field
The invention belongs to the technical field of electronic electroplating, and particularly relates to an acidic sulfate electronic copper electroplating additive composition and application thereof.
Background
With the development of electronic products in terms of functionality, miniaturization, and weight reduction, the manufacturing technology of electronic component carriers (chips, package substrates, and printed circuit boards) has also been developed in terms of multilayering, thinning, and densification. High density interconnect printed circuit boards (HDI-PCBs) have been produced. In order to fully utilize the space of the whole board, the high-density printed circuit board not only adopts the design of a full-through hole, but also introduces an interconnection structure of a micro-blind buried hole, thereby improving the wiring density, reducing the layer number and reducing the cost.
The PCB blind hole causes uneven distribution of current in the hole and on the surface of the hole due to the special geometrical structure of the PCB blind hole; the transfer rates of metal ions and additives are also different, making it difficult to achieve dense copper fill, low surface flatness after fill, and thin copper coatings. The additive composition is added into the acidic electronic copper plating solution, so that the electronic plating of the PCB blind holes can realize compact filling, and the copper layer on the surfaces of the holes is thinner, uniform and flat. The PCB structure is beneficial to realizing electronic interconnection of different PCB layers, and can improve the fineness degree of a circuit, so that the reliability and the portability of an electronic product are improved. Therefore, the additive has high flatness and thin surface copper layer, and is suitable for PCB blind hole electronic copper electroplating, and has important industrial application value.
CN112899737A discloses an acidic copper plating additive, which comprises 0.002-0.02 g/L of disulfide, 0.1-0.3 g/L of polyalcohol compound, 0.01-0.1 g/L of quaternary ammonium compound and 0.002-0.02 g/L of stabilizer. The additive combination can realize the dense filling of blind holes (the hole depth: 75 microns, the pore diameter: 100 microns), but the additive combination is complex, and the additive also contains a stabilizer besides an inhibitor, an accelerator and a leveling agent, so that the additive is not beneficial to the maintenance of a plating solution. CN111364076A discloses an electronic copper electroplating solution for filling blind holes, in which the additives are respectively sodium polydithiodipropyl sulfonate (brightener), polyethylene glycol (carrier) and a mixture of isonicotinic acid compounds and oligomeric quaternary amine compounds (leveler). The additive combination can realize the compact filling of blind holes (the hole depth: 75 microns, the pore diameter: 100 microns), and the surface copper has good smoothness; but leveler composition is more complex.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an acidic sulfate electronic copper electroplating additive composition and application thereof.
The invention also aims to provide the acid sulfate electronic copper electroplating solution.
The invention further aims to provide an electronic electroplating method for densely filling the blind holes of the PCB.
The technical scheme of the invention is as follows:
an acidic sulfate electro-coppering additive composition, characterized in that: the concentration of the copper electroplating solution in the acidic sulfate electronic copper electroplating solution is 100-800mg/L, the copper electroplating solution consists of a carrier inhibitor, a refiner and a plating leveler in a mass ratio of 100-800: 0.5-10: 0.5-20, the acidic sulfate electronic copper electroplating solution takes water as a solvent and contains 180-240g/L of blue vitriol, 50-120g/L of concentrated sulfuric acid and 0.04-0.08g/L of chloride ions, wherein,
the carrier stopping agent is segmented polymer of ethylene oxide and propylene oxide, polyethylene glycol dodecyl ether, stearyl alcohol polyether, polyethylene glycol ether, oleyl alcohol polyoxyethylene ether, lauryl alcohol polyether, polyvinyl alcohol, polyoxyethylene sorbitan monopalmitate, polyethylene glycol stearate or fatty alcohol polyoxyethylene ether carboxylate;
the refiner is sodium polydithio-dipropyl sulfonate, 3-mercapto-1-propane sulfonate, 1-mercaptomethylcyclopropyl acetic acid, 2-mercaptoethoxy ethanol, methyl sulfonic anhydride or 2-morpholine ethanesulfonic acid;
the plating homogenizing agent is 6-chloro-1-hydroxybenzotriazole, 1, 3-dithioic acid-2-thionine, basic red, 1- (2-pyridylazo) -2-naphthol, 2-chloro-4-aminopyridine, 2-phenylthiocarbamic acid benzene, N-phenylthiourea, thiosemicarbazide, 3-sulfopropylhexadecyldimethylammonium, tetrabutylammonium hydrogen sulfate, dioctadecyldimethylammonium chloride or 3-methylthio-1, 2, 4-triazine.
In a preferred embodiment of the invention, the carrier blocker is a block polymer of ethylene oxide and propylene oxide, a polyethylene glycol ether, a polyethylene glycol stearate or an oleyl alcohol polyoxyethylene ether.
In a preferred embodiment of the invention, the refiner is sodium polydithiodipropanesulfonate, sodium 3-mercapto-1-propanesulfonate, 1-mercaptomethylcyclopropylacetic acid or 2-mercaptoethoxyethanol.
In a preferred embodiment of the invention, the leveler is 2-chloro-4-aminopyridine, 2-phenylthiocarbamic acid benzene, N-phenylthiourea or thiosemicarbazide.
In a preferred embodiment of the invention, the carrier stopping agent is a block polymer of ethylene oxide and propylene oxide, polyethylene glycol ether, polyethylene glycol stearate or oleyl alcohol polyoxyethylene ether, the refiner is sodium polydithiodipropionate, sodium 3-mercapto-1-propanesulfonate, 1-mercaptomethylcyclopropylacetic acid or 2-mercaptoethoxyethanol, and the plating homogenizing agent is 2-chloro-4-aminopyridine, 2-phenylthiocarbamate benzene, N-phenylthiourea or thiosemicarbazide.
In a preferred embodiment of the invention, the mass ratio of the carrier stopping agent, the refiner and the leveling agent is 300-700: 0.5-6: 1-8.
Further preferably, the concentration of the copper electroplating solution in the acidic sulfate electro-coppering solution is 200-700mg/L.
The concentration of the carrier stopping agent in the acid sulfate electronic copper electroplating solution is higher than 800mg/L, so that the deposition of copper ions at the bottom of a blind hole is strongly inhibited, and the blind hole cannot be densely filled; the concentration is lower than 100mg/L, the copper ion deposition inhibition effect at the top of the blind hole is weak, and the surface copper is thicker;
the concentration of the refiner in the acidic sulfate electronic copper electroplating solution is higher than 10mg/L, so that the copper deposition speed in the hole is too high, the coating is easy to be rough, the particles are large, and the coating is poor in smoothness; the concentration is lower than 0.5mg/L, so that the deposition rate of copper in the hole is lower, and the filling efficiency of the blind hole is reduced;
the concentration of the plating homogenizing agent in the acid sulfate electronic copper electroplating solution is higher than 20mg/L, so that the plating layer is mixed with the substances, and the physical properties of the plating layer such as conductivity are influenced; the concentration is lower than 0.5mg/L, so that the copper deposition rate in the holes cannot be regulated and controlled, and the flatness of the plating layer is poor.
The other technical scheme of the invention is as follows:
an acidic sulfate electro-coppering solution, which takes water as solvent and contains 180-240g/L of blue vitriol, 50-120g/L of concentrated sulfuric acid, 0.04-0.08g/L of chloride ions and the acidic sulfate electro-coppering additive composition.
The invention adopts another technical scheme as follows:
an electronic electroplating method for densely filling PCB blind holes uses the acid sulfate electronic copper electroplating solution.
In a preferred embodiment of the invention, a constant-current double-anode electronic plating mode is adopted, the distance between a cathode and an anode is 6-25cm, the cathode moves, and the current density of the cathode is 0.5-6A/dm 2 The temperature is 20-35 ℃, and the electronic electroplating time is 30-100min; the stirring mode is that the air is pumped at the two sides of the cathode and is respectively 2-5cm away from the cathode, and the air stirring speed is 1-5L/min; the anode is made of phosphor copper.
The condition of the electronic electroplating is not suitable, if the cathode air blowing distance is more than 5cm, the surface quality of copper ions facing the cathode is insufficient, the current efficiency is reduced, and the blind hole filling time is prolonged.
The beneficial effects of the invention are:
1. the invention adopts macromolecular polymer of polybasic ether, alcohol or ester as carrier stopping agent; the substances are used as main adsorbents in the plating solution, play a role in reducing surface tension and mainly inhibiting (orifice inhibition), are simultaneously co-adsorption carriers of the refiner and the uniform plating agent, and are beneficial to the functioning of the refiner and the uniform plating agent with low content.
2. The invention uses specific sulfur-containing compounds as refiners: effectively promotes the formation of copper crystal nucleus, refines the particle size of copper plating particles, and ensures that the particles are compact and the plating is bright. And meanwhile, the copper deposition accelerating function is mainly exerted at the bottom of the hole, so that the dense filling of the blind hole is facilitated.
3. The invention adopts special nitrogen heterocyclic ring, quaternary ammonium salt, sulfur-containing compound and other substances as the plating homogenizing agent: the substance cooperates with the carrier stopping agent and the refiner in a high current density area to strongly stop the reduction of copper ions, and cooperates with the carrier stopping agent and the refiner in a low current density area to weakly stop the reduction of the copper ions, so that the thickness of a plating layer in the high current density area is uniform.
4. Within the range of using conditions, the invention can effectively reduce the surface tension of the plating solution, refine copper layer particles, improve the efficiency of the deposition current, realize the compact filling of PCB blind holes, excellent smoothness of the surface and thin surface copper thickness.
5. The invention can realize dense filling of blind holes with the aperture of 100 mu m and the hole depth of 50 mu m, excellent surface smoothness and copper layer thickness of less than 15 mu m within the using condition range.
Drawings
FIG. 1 is a graph showing the results of the experiment of comparative example 1 of the present invention, in which it can be seen that the concentration of the leveler is not suitable, the blind via cannot be densely filled, and a large void occurs.
FIG. 2 is a graph showing the results of the experiment of comparative example 2 of the present invention, in which it can be seen that the concentration of the leveler was not appropriate, the surface recess of the filled blind via hole was more than 15 μm, and the surface copper thickness was more than 20 μm.
FIG. 3 is a graph showing the results of the experiment of comparative example 3 of the present invention, in which it can be seen that the concentration of the carrier inhibitor is not appropriate and the surface copper is too thick.
FIG. 4 is a graph showing the experimental results of comparative example 4 of the present invention, in which it can be seen that the electron plating conditions are not suitable, the blind via dense filling time is too long (60 min), and the current efficiency is low.
FIG. 5 is a metallographic microscope (magnified 1000 times) of a blind via electro-plated copper layer of a PCB prepared in example 1 of the present invention.
FIG. 6 is a metallographic microscopic photograph (magnified 1000 times) of a blind via electro-plated copper layer of a PCB prepared in example 2 of the present invention.
FIG. 7 is a metallographic microscope (magnified 1000 times) of a PCB blind hole electro-plated copper layer prepared in example 3 of the present invention.
FIG. 8 is a metallographic microscope (magnified 1000 times) of a PCB blind hole electro-plated copper layer prepared in example 4 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 4 and comparative examples 1 to 4
Taking preparation of 1L of concentrate as an example:
(1) accurately weighing 200g of carrier stopping agent, and mixing the carrier stopping agent, the refiner and the uniform plating agent according to the mass ratio of 100:1:3, weighing a refiner and a plating leveler, and fixing the volume to 1L to prepare an additive concentrated solution; according to different contents of the additive, additive compositions with different content ratios can be prepared.
(2) When in electronic plating, the solution is added into basic solution with high copper and low acid (namely acid sulfate electronic copper plating solution which takes water as solvent and contains 180-240g/L of blue vitriol, 50-120g/L of concentrated sulfuric acid and 0.04-0.08g/L of chloride ions) according to the dosage of 1mL/L of concentrated solution.
(3) Removing oil from the blind hole printed circuit board with alkali solution and 5-10% 2 SO 4 Washing with ultrapure water after aqueous solution pickling and activation pretreatment, then directly placing in a plating bath of the acidic sulfate electronic copper electroplating plating solution, and carrying out blind hole electronic copper electroplating according to electronic electroplating conditions; after the electronic plating is finished, taking out the cathode from the electronic plating solution, cleaning the surface with distilled water, and drying with cold air, wherein: the electrocoppering adopts constant current, double anode electrocoppering mode, the cathode moves, the distance between the cathode and the anode is 6-25cm, and the current density of the cathode is 0.5-6A/dm 2 The temperature is 20-35 ℃, and the electronic plating time is 30-100min; the stirring mode is that air is pumped from two sides of the cathode and is respectively 2-5cm away from the cathode, and the air stirring speed is 1-5L/min; the anode is made of phosphor copper.
By taking 1L of electronic electroplating solution, the aperture of a blind hole is 100 mu m and the depth of the blind hole is 50 mu m as an example, the initial surface copper thickness of the blind hole is 10 mu m, and ideal effects of blind hole dense electronic electroplating filling and thin surface copper thickness can be obtained by adopting the acid sulfate electronic electroplating copper additive composition. Examples and comparisons of specific acid sulfate electrocoppering additive compositions are shown in table 1 below:
TABLE 1 different acidic sulfate electrocoppering additive composition combinations
As shown in FIGS. 5 to 8, the thickness of the electro-coppering layer at the blind hole opening of the PCB is measured by a metallographic microscope, and it can be seen that the acid sulfate electro-coppering additive composition of the embodiment 1 of the present invention can successfully realize compact electro-coppering filling of the blind hole of the PCB, and the surface copper thickness is only 14.85 μm. The acid sulfate electronic plating copper additive composition of the embodiments 2 to 4 can also realize the dense electronic plating filling of PCB blind holes, the surface copper thickness is less than 20 μm, and the surface copper thickness is respectively 15.21, 16.10 and 19.32 μm. It is to be noted that: the results obtained are the same as or similar to those of the above-described embodiment when the PCB hole depth is in the range of 50-100 μm.
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, which is defined by the appended claims.
Claims (10)
1. An acidic sulfate electro-coppering additive composition, characterized in that: the concentration of the copper plating solution in the acidic sulfate electronic copper plating solution is 100-800mg/L, the copper plating solution consists of a carrier inhibitor, a refiner and a plating leveler in a mass ratio of 100-800: 0.5-10: 0.5-20, the acidic sulfate electronic copper plating solution takes water as a solvent and contains 180-240g/L of blue vitriol, 50-120g/L of concentrated sulfuric acid and 0.04-0.08g/L of chloride ions, wherein,
the carrier stopping agent is block polymer of ethylene oxide and propylene oxide, polyethylene glycol dodecyl ether, stearyl alcohol polyether, polyethylene glycol ether, oleyl alcohol polyoxyethylene ether, lauryl alcohol polyether, polyvinyl alcohol, polyoxyethylene sorbitan monopalmitate, polyethylene glycol stearate or fatty alcohol polyoxyethylene ether carboxylate;
the refiner is sodium polydithio-dipropyl sulfonate, 3-mercapto-1-propane sulfonate, 1-mercaptomethylcyclopropyl acetic acid, 2-mercaptoethoxy ethanol, methyl sulfonic anhydride or 2-morpholine ethanesulfonic acid;
the plating homogenizing agent is 6-chloro-1-hydroxybenzotriazole, 1, 3-dithioic acid-2-thionine, basic red, 1- (2-pyridylazo) -2-naphthol, 2-chloro-4-aminopyridine, 2-phenylthiocarbamic acid benzene, N-phenylthiourea, thiosemicarbazide, 3-sulfopropylhexadecyldimethylammonium, tetrabutylammonium hydrogen sulfate, dioctadecyldimethylammonium chloride or 3-methylthio-1, 2, 4-triazine.
2. The acid sulfate electro-coppering additive composition as claimed in claim 1, wherein: the carrier stopping agent is block polymer of ethylene oxide and propylene oxide, polyethylene glycol ether, polyethylene glycol stearate or oleyl alcohol polyoxyethylene ether.
3. The acid sulfate electrocoppering additive composition of claim 1, wherein: the refiner is sodium polydithio-dipropyl sulfonate, 3-mercapto-1-propane sulfonate, 1-mercaptomethylcyclopropyl acetic acid or 2-mercaptoethoxy ethanol.
4. The acid sulfate electro-coppering additive composition as claimed in claim 1, wherein: the plating homogenizing agent is 2-chloro-4-aminopyridine, 2-thiophenyl carbamic acid benzene, N-phenylthiourea or thiosemicarbazide.
5. The acid sulfate electrocoppering additive composition of claim 1, wherein: the carrier inhibitor is a block polymer of ethylene oxide and propylene oxide, polyethylene glycol ether, polyethylene glycol stearate or oleyl alcohol polyoxyethylene ether, the refiner is sodium polydithio-dipropyl sulfonate, 3-mercapto-1-propane sodium sulfonate, 1-mercaptomethylcyclopropyl acetic acid or 2-mercaptoethoxy ethanol, and the plating homogenizing agent is 2-chloro-4-aminopyridine, 2-thiophenyl carbamate benzene, N-phenylthiourea or thiosemicarbazide.
6. The acidic sulfate electro-coppering additive composition as claimed in any one of claims 1 to 5, wherein: the mass ratio of the carrier inhibitor, the refiner and the plating leveler is 300-700: 0.5-6: 1-8.
7. The acid sulfate electrocoppering additive composition of claim 6, wherein: the concentration of the acid sulfate electro-coppering solution is 200-700mg/L.
8. An acidic sulfate electro-coppering plating solution is characterized in that: an acidic sulfate electro-coppering additive composition as claimed in any one of claims 1 to 7, comprising 180-240g/L of copper sulfate pentahydrate, 50-120g/L of concentrated sulfuric acid, 0.04-0.08g/L of chloride ion, and water as a solvent.
9. An electronic electroplating method for densely filling a PCB blind hole is characterized by comprising the following steps: an acidic sulfate electro-coppering bath as claimed in claim 8.
10. The electronic plating method of claim 9, wherein: adopting a constant current double anode electronic electroplating mode, the distance between the cathode and the anode is 6-25cm, the cathode moves, and the current density of the cathode is 0.5-6A/dm 2 The temperature is 20-35 ℃, and the electronic plating time is 30-100min; the stirring mode is that air is pumped from two sides of the cathode and is respectively 2-5cm away from the cathode, and the air stirring speed is 1-5L/min; the anode is made of phosphor copper.
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| CN116230621A (en) * | 2023-05-08 | 2023-06-06 | 四川科尔威光电科技有限公司 | Preparation method of ferrite-based thin film circuit product |
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