CN106987874B - Copper electrolyte is electroplated - Google Patents
Copper electrolyte is electroplated Download PDFInfo
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- CN106987874B CN106987874B CN201710357312.1A CN201710357312A CN106987874B CN 106987874 B CN106987874 B CN 106987874B CN 201710357312 A CN201710357312 A CN 201710357312A CN 106987874 B CN106987874 B CN 106987874B
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- 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
Abstract
The present invention relates to a kind of plating copper electrolytes, including following component: cupric sulfate pentahydrate 20g/L-240g/L, sulfuric acid 20g/L-300g/L, chloride ion 25mg/L-120mg/L, brightener 0.1mg/L-20mg/L, inhibitor 1mg/L-2000mg/L, transition metal salt 50mg/L-1000mg/L, deionized water surplus.In above-mentioned plating copper electrolyte, it is added and the transition metal salt of 50-1000mg/L (ppm), the transition metal salt can be adsorbed on copper anode surface very well, protect the Cu on anode3The black film of P is not easily to fall off, to delay falling off for copper anode mud.The transition metal salt is consumed extremely low in electro-coppering production process or is not consumed, and does not need additionally to supplement.
Description
Technical field
The present invention relates to printed wiring board chemicals technical fields, more particularly to a kind of plating copper electrolyte.
Background technique
Sour copper plating has important application in electronics industry especially in the manufacture of printed wiring board and semiconductor.Allusion quotation
The acid copper plating bath sulfur acid copper and sulfuric acid of type, effect are to provide copper source and electric conductivity for plating.Also contain in electroplate liquid
Cl-, brightener, inhibitor and leveling agent to go on smoothly plating can improve quality of coating and covering power.Cl-And light
Bright dose (also referred to as promotor) can promote copper in the deposition plated on plate and keep coating surface bright.Inhibitor plays wetting plating plate, suppression
The deposition velocity of copper processed.Leveling agent plays especially important effect in plating, it makes the rough smooth surface of substrate simultaneously
The covering power of plated hole can be improved, to obtain the plating piece of high quality.
In acid copper-plating technique, galvanic anode be typically all the copper for containing 99.9% or more using soluble copper ball,
0.03~0.06% or so phosphorus and other metals.During plating, copper and phosphorus in copper anode can be in anode surfaces
Form the Cu of one layer of black3P film prevents cuprous ion from entering directly into and generates copper powder or copper particle in tank liquor.It was producing
Cheng Zhong, since copper ball is gradually consumed, the earth of positive pole is gradually increased, in addition being influenced by washing away in tank liquor, the Cu of this black3P
It can gradually fall off, be deposited on the bottom of titanium basket, cause the earth of positive pole excessive, to influence electroplating evenness, cause in electroplating process
Copper thickness difference above and below plate is larger, and therefore, factory needs to propose titanium basket for general 2 to 3 months, carries out anode cleaning.
Therefore need to develop it is a kind of the earth of positive pole can be delayed to fall off, extend cleaning anodic cycle plating copper electrolyte.
Summary of the invention
Based on this, the earth of positive pole can be delayed to fall off the object of the present invention is to provide a kind of, extend the plating of cleaning anodic cycle
Copper electrolyte.
Specific technical solution is as follows:
A kind of plating copper electrolyte, including following component:
In wherein some embodiments, which includes following component:
In wherein some embodiments, the cation of the transition metal salt is selected from VO2+、Mn2+、Fe2+、Co2+Or ZrO2+
One or more of.
In wherein some embodiments, the anion of the transition metal salt is selected from S2O3 2-Or Cl-。
In wherein some embodiments, the brightener is selected from dithio-bis-propylene sulfonic acid sodium salt, the thio propane sulfonic acid of phenyl two
Sodium, N, N- dimethylthiocarbamoyl propane sulfonic acid sodium, the poly- dithiopropane sodium sulfonate of imidazolinyl, N, N- diethyl thiourea
Middle one or more.
In wherein some embodiments, the brightener is selected from dithio-bis-propylene sulfonic acid sodium salt, the thio propane sulfonic acid of phenyl two
It is one or two kinds of in sodium.
In wherein some embodiments, it is fine that the inhibitor is selected from polyalkylene glycol compounds, polyvinyl alcohol, carboxymethyl
Dimension element, polyethylene glycol, stearic acid macrogol ester, alkoxynaphthols, Polyethylene Glycol Oleate, poly- (ethylene glycol and 1,2-propylene glycol) nothing
Advise copolymer, poly- (polyethylene glycol propylene glycol-polyethylene glycol) block copolymer, poly- (polypropylene glycol-polyethylene glycol the third two
Alcohol) it is one or more of in block copolymer.
In wherein some embodiments, it is total that the inhibitor is selected from poly- (polypropylene glycol-polyethylene glycol propylene glycol) block
It is one or more of in polymers, poly- (ethylene glycol and 1,2-propylene glycol) random copolymer or polyethylene glycol.
In above-mentioned plating copper electrolyte, the transition metal salt with 50-1000mg/L (ppm) is added, which can be very
It is adsorbed on copper anode surface well, protects the Cu on anode3The black film of P is not easily to fall off, to delay falling off for copper anode mud.The mistake
It crosses metal salt to consume extremely low or do not consume in electro-coppering production process, does not need additionally to supplement.
Detailed description of the invention
Fig. 1 is the photo that the earth of positive pole after copper electrolyte normally produces three months is electroplated in embodiment 1；
Fig. 2 is the photo that the earth of positive pole after copper electrolyte normally produces three months is electroplated in comparative example 1.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
Embodiment 1
A kind of plating copper electrolyte, including following component:
Transition metal salt can be added by the following method: in the container of 50kg, the deionized water of 38.85kg is added,
It is slow added into 98% concentrated sulfuric acid of 1.9kg, is stirred evenly, adds the VOSO of 9.25kg under stiring4·4H2O is stirred to molten
Solution completely, allows solution to drop to room temperature, finally uses the filter element filtering in 5 aperture μ of aperture, obtains additive.
The trimestral copper anode of continuous production, after cleaning up outside line, is put back into electroplating bath.Analysis allotment plating medicine
After water concentration is in working range, additive is added by the amount of 3ml/L, can normally produce again.
Embodiment 2
A kind of plating copper electrolyte, including following component:
Transition metal salt can be added by the following method: in the container of 100kg, the deionized water of 68kg is added, then
98 concentrated sulfuric acids of 1.0kg and 37% formaldehyde of 1.0kg are slowly added to, are stirred evenly, add the MnSO of 5kg under stiring4·
7H2O, stirring allow solution to drop to room temperature, finally use the filter element filtering in 5 apertures μ, obtain additive to dissolving completely.
Copper ball pickling is completely placed in electroplating bath by the electroplating bath newly to burst at the seams, prepares new electroplating liquid medicine, including sulphur
Sour copper, sulfuric acid, chloride ion and suitable electroplating additive.After analysis allotment liquid medicine to working range, it is added with the amount of 1ml/L
Additive stirs evenly, and can newly be opened the normal production of cylinder.
Embodiment 3
A kind of plating copper electrolyte, including following component:
Transition metal salt can be added by the following method: in the container of 100kg, the deionized water of 86.7kg is added,
It is slow added into the concentrated sulfuric acid of 2.5kg and 37% formaldehyde of 0.8kg, is stirred evenly, adds the CoSO of 20kg under stiring4·
7H2O, stirring allow solution to drop to room temperature, finally use the filter element filtering in 5 aperture μ of aperture, obtain additive to dissolving completely.
Electroplating bath or the new electroplating bath of cylinder of opening after cleaning copper anode, can be according to just with the amount addition additive of 5ml/L
Often production.
Embodiment 4
A kind of plating copper electrolyte, including following component:
Transition metal salt can be added by the following method: in the container of 50kg, the deionized water of 32.5kg is added, then
It is slowly added to 98% concentrated sulfuric acid of 2.5kg, is stirred evenly, adds the FeSO of 8kg under stiring4·9H2O and 10kg are put into
VOSO4·4H2O, stirring allow solution to drop to room temperature, finally use the filter element filtering in 5 aperture μ of aperture, added to dissolving completely
Add agent.
Electroplating bath or the new electroplating bath of cylinder of opening after cleaning copper anode, can be according to just with the amount addition additive of 1ml/L
Often production.
Embodiment 5
A kind of plating copper electrolyte, including following component:
Transition metal salt can be added by the following method: in the container of 50kg, the deionized water of 24.8kg is added, then
It is slowly added to 98% concentrated sulfuric acid of 2.7kg and 37% formaldehyde of 0.5kg, is stirred evenly, adds the FeCl of 4kg under stiring3·
6H2O and 8kg are put into ZrOSO4·4H2O, stirring allow solution to drop to room temperature, finally use the filter in 5 aperture μ of aperture to dissolving completely
Core filtering, obtains additive.
Electroplating bath or the new electroplating bath of cylinder of opening after cleaning copper anode, can be according to just with the amount addition additive of 4ml/L
Often production.
Embodiment 6
A kind of plating copper electrolyte, including following component:
Transition metal salt can be added by the following method: electroplating bath or the new electroplating bath for opening cylinder after cleaning copper anode,
Add the MnSO of 1000ppm4·7H2O can be according to normal production after unlatching circulation stirring is uniform.
Embodiment 7
A kind of plating copper electrolyte, including following component:
Transition metal salt can be added by the following method: electroplating bath or the new electroplating bath for opening cylinder after cleaning copper anode,
Add the VOSO of 50ppm4·4H2The ZrOSO of O and 50ppm4·4H2O can be according to normal raw after unlatching circulation stirring is uniform
It produces.
Comparative example 1
A kind of plating copper electrolyte, including following component:
The plating copper electrolyte of embodiment 1 and comparative example 1 after normal production 3 months, the photo of the earth of positive pole respectively such as Fig. 1 and
Shown in Fig. 2.
Fig. 1 is the copper electroplating solution containing transition metal salt, and after 3 months, titanium basket bottom anode mud is seldom, redfree
Copper powder occur；Fig. 2 be the copper electroplating solution without transition metal salt, after 3 months, titanium basket bottom have a large amount of earth of positive pole and
Red copper powder occurs.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of plating copper electrolyte delay the acid copper-plating technique earth of positive pole fall off in application, the plating copper electrolyte is including such as
Lower component:
Cupric sulfate pentahydrate 20g/L-240g/L,
Sulfuric acid 20g/L-300g/L,
Chloride ion 25mg/L-120mg/L,
Brightener 0.1mg/L-20mg/L,
Inhibitor 100mg/L-2000mg/L,
50 mg/L -1000mg/L of transition metal salt,
Deionized water is added to 1L；
The cation of the transition metal salt is selected from VO2+、Mn2+、Fe2+、Co2+Or ZrO2+One or more of；
The brightener is selected from the thio propane sulfonic acid sodium of phenyl two, N, N- dimethylthiocarbamoyl propane sulfonic acid sodium, miaow
The poly- dithiopropane sodium sulfonate of oxazoline base, N, it is one or more of in N- diethyl thiourea；
The inhibitor be selected from polyalkylene glycol compounds, alkoxynaphthols, poly- (ethylene glycol and 1,2-propylene glycol) random copolymer,
Poly- (polyethylene glycol propylene glycol-polyethylene glycol) block copolymer, poly- (polypropylene glycol-polyethylene glycol propylene glycol) block are total
It is one or more of in polymers.
2. application according to claim 1, which is characterized in that the plating copper electrolyte includes following component:
Cupric sulfate pentahydrate 40g/L-100 g/L,
180/L-240g/L of sulfuric acid,
Chloride ion 40mg/L-90mg/L,
Brightener 2mg/L-8mg/L,
Inhibitor 200mg/L-1000 mg/L,
Transition metal salt 50mg/L -1000mg/L,
Deionized water is added to 1L.
3. application according to claim 1, which is characterized in that the anion of the transition metal salt is selected from SO4 2-Or Cl-。
4. application according to any one of claims 1 to 3, which is characterized in that the brightener is the thio propane of phenyl two
Sodium sulfonate.
5. application according to any one of claims 1 to 3, which is characterized in that the inhibitor is selected from poly- (polypropylene glycol-
Polyethylene glycol propylene glycol) it is block copolymer, one or more of in poly- (ethylene glycol and 1,2-propylene glycol) random copolymer.
6. a kind of method for delaying acid copper-plating technique Anodic mud to fall off, which is characterized in that in acid copper-plating technique, to electricity
Plating copper electrolyte is added in coating bath, the plating copper electrolyte includes following component:
Cupric sulfate pentahydrate 20g/L-240g/L,
Sulfuric acid 20g/L-300g/L,
Chloride ion 25mg/L-120mg/L,
Brightener 0.1mg/L-20mg/L,
Inhibitor 100mg/L-2000mg/L,
50 mg/L -1000mg/L of transition metal salt,
Deionized water is added to 1L；
The cation of the transition metal salt is selected from VO2+、Mn2+、Fe2+、Co2+Or ZrO2+One or more of；
The brightener is selected from the thio propane sulfonic acid sodium of phenyl two, N, N- dimethylthiocarbamoyl propane sulfonic acid sodium, miaow
The poly- dithiopropane sodium sulfonate of oxazoline base, N, it is one or more of in N- diethyl thiourea；
The inhibitor be selected from polyalkylene glycol compounds, alkoxynaphthols, poly- (ethylene glycol and 1,2-propylene glycol) random copolymer,
Poly- (polyethylene glycol propylene glycol-polyethylene glycol) block copolymer, poly- (polypropylene glycol-polyethylene glycol propylene glycol) block are total
It is one or more of in polymers.
7. according to claim 6 delay that the method that Anodic mud falls off is electroplated, which is characterized in that the plating copper electrolyte
Including following component:
Cupric sulfate pentahydrate 40g/L-100 g/L,
180/L-240g/L of sulfuric acid,
Chloride ion 40mg/L-90mg/L,
Brightener 2mg/L-8mg/L,
Inhibitor 200mg/L-1000 mg/L,
Transition metal salt 50mg/L -1000mg/L,
Deionized water is added to 1L.
8. according to claim 6 delay that the method that Anodic mud falls off is electroplated, which is characterized in that the transition metal salt
Anion be selected from SO4 2-Or Cl-。
9. according to the described in any item methods for delaying plating Anodic mud to fall off of claim 6 to 8, which is characterized in that described
Brightener is the thio propane sulfonic acid sodium of phenyl two.
10. according to the described in any item methods for delaying plating Anodic mud to fall off of claim 6 to 8, which is characterized in that described
Inhibitor is selected from poly- (polypropylene glycol-polyethylene glycol propylene glycol) block copolymer, poly- (ethylene glycol and 1,2-propylene glycol) random copolymerization
It is one or more of in object.
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| CN109989077A (en) * | 2017-12-29 | 2019-07-09 | 广东东硕科技有限公司 | A kind of copper electrolyte |
| CN110359051B (en) * | 2019-06-18 | 2020-09-22 | 龙建国 | Method for recycling waste etching liquid of circuit board |
| CN110424030B (en) * | 2019-08-30 | 2020-06-30 | 广州三孚新材料科技股份有限公司 | Cyanide-free alkaline copper electroplating solution, preparation thereof and application thereof in flexible printed circuit board |
| CN111155152B (en) * | 2019-12-26 | 2022-11-01 | 西安泰金工业电化学技术有限公司 | Method for reducing production cost in horizontal electroplating process of PCB |
| CN111058065A (en) * | 2020-01-17 | 2020-04-24 | 浙江金欣新材料科技股份有限公司 | Composite electroplating brightener and preparation method thereof |
| CN111962109A (en) * | 2020-08-20 | 2020-11-20 | 苏州大学 | Acid copper additive and preparation method thereof |
| CN112877739B (en) * | 2021-01-13 | 2022-08-23 | 上海天承化学有限公司 | Electroplating solution and electroplating method and application thereof |
| CN114277413A (en) * | 2021-12-29 | 2022-04-05 | 广东利尔化学有限公司 | Copper plating solution for circuit board |
| CN114318436A (en) * | 2022-03-09 | 2022-04-12 | 深圳市创智成功科技有限公司 | Preparation method of high-purity copper sulfate for wafer copper interconnection and copper electroplating process thereof |
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| US20120024713A1 (en) * | 2010-07-29 | 2012-02-02 | Preisser Robert F | Process for electrodeposition of copper chip to chip, chip to wafer and wafer to wafer interconnects in through-silicon vias (tsv) with heated substrate and cooled electrolyte |
| CN102212853B (en) * | 2011-04-30 | 2012-11-14 | 山东金宝电子股份有限公司 | Surface treatment coarsening process for improving peel strength of copper foil |
| CN104131319B (en) * | 2014-08-15 | 2017-06-23 | 苏州天承化工有限公司 | For the electroplate liquid and its electro-plating method of the filling perforation of plate-shaped members surface |
| CN105887144B (en) * | 2016-06-21 | 2018-09-21 | 广东光华科技股份有限公司 | Copper electrolyte and its copper plating process is electroplated |
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