CN106987874A - Electroplate copper electrolyte - Google Patents
Electroplate copper electrolyte Download PDFInfo
- Publication number
- CN106987874A CN106987874A CN201710357312.1A CN201710357312A CN106987874A CN 106987874 A CN106987874 A CN 106987874A CN 201710357312 A CN201710357312 A CN 201710357312A CN 106987874 A CN106987874 A CN 106987874A
- Authority
- CN
- China
- Prior art keywords
- poly
- copper electrolyte
- glycol
- plating copper
- metal salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Copper electrolyte, including following component are electroplated the present invention relates to one kind：Cupric sulfate pentahydrate 20g/L 240g/L, sulfuric acid 20g/L 300g/L, chlorion 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, the transition metal salt with 50 1000mg/L (ppm) is added, the transition metal salt can be adsorbed on copper anode surface very well, the Cu on protection anode3P black film is difficult for drop-off, so as to delay coming off for copper anode mud.The transition metal salt is consumed extremely low in electro-coppering production process or not consumed, it is not necessary to extra supplement.
Description
Technical field
The present invention relates to printed wiring board chemicals technical field, more particularly to a kind of plating copper electrolyte.
Background technology
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, it is to provide copper source and electric conductivity for plating that it, which is acted on,.Also contain in electroplate liquid
Cl-, brightener, inhibitor and leveling agent, to enable plating to be smoothed out, improve quality of coating and covering power.Cl-And light
Bright dose (also referred to as accelerator) can promote deposition of the copper on plating plate and make coating surface light.Inhibitor plays wetting plating plate, suppression
The deposition velocity of copper processed.Leveling agent plays especially important effect in plating, and it makes the rough surface of base material smooth simultaneously
The covering power of plated hole can be improved, to obtain high-quality plating piece.
In acid copper-plating technique, galvanic anode be typically all using soluble copper ball, its contain more than 99.9% copper,
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 films, prevent cuprous ion is entered directly into from generating copper powder or copper particle in tank liquor.Producing
Cheng Zhong, because copper ball is gradually consumed, the earth of positive pole gradually increases, and adding is influenceed by being washed away in tank liquor, the Cu of this black3P
It can gradually come off, be deposited on the bottom of titanium basket, cause the earth of positive pole excessive, so as 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 exploitation one kind is needed the earth of positive pole to be delayed to come off, the plating copper electrolyte of extension cleaning anodic cycle.
The content of the invention
Based on this, the earth of positive pole can be delayed to come off it is an object of the invention to provide one kind, the plating of extension cleaning anodic cycle
Copper electrolyte.
Specific technical scheme is as follows：
One kind plating copper electrolyte, including following component：
In wherein some embodiments, the plating copper electrolyte includes following component：
In wherein some embodiments, the cation of the transition metal salt is selected from VO2+、Mn2+、Fe2+、Co2+Or ZrO2+
In one or more.
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 acids sodium, the poly- dithiopropane sodium sulfonate of imidazolinyl, N, N- diethyl thioureas
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 propane diols-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 common that the inhibitor is selected from poly- (polypropylene glycol-polyethylene glycol propane diols) 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, the transition metal salt can be very
Cu of the good absorption on copper anode surface, protection anode3P black film is difficult for drop-off, so as to delay coming off for copper anode mud.The mistake
Cross metal salt to consume extremely low or do not consume in electro-coppering production process, it is not necessary to extra supplement.
Brief description of the drawings
Fig. 1 is the photo that embodiment 1 electroplates the earth of positive pole after copper electrolyte is normally produced three months；
Fig. 2 is the photo that comparative example 1 electroplates the earth of positive pole after copper electrolyte is normally produced three months.
Embodiment
For the ease of understanding the present invention, the present invention will be described more fully below.But, the present invention can be with perhaps
More different form is realized, however it is not limited to embodiment described herein.On the contrary, the purpose for providing these embodiments is to make
Understanding to the disclosure is more thorough comprehensive.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein 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
The arbitrary and all combination of the Listed Items of pass.
Embodiment 1
One kind plating copper electrolyte, including following component：
Transition metal salt can be added by the following method：In 50kg container, 38.85kg deionized water is added,
1.9kg 98% concentrated sulfuric acid is slow added into, is stirred, 9.25kg VOSO is added under agitation4·4H2O, is stirred to molten
Solution is complete, allows solution to drop to room temperature, finally using the filter element filtering in the μ apertures of aperture 5, obtains additive.
Trimestral copper anode is continuously produced, after being cleaned up outside line, is put back into electroplating bath.Analysis allotment plating medicine
After water concentration is in working range, additive is added by 3ml/L amount, you can normal production again.
Embodiment 2
One kind plating copper electrolyte, including following component：
Transition metal salt can be added by the following method：In 100kg container, 68kg deionized water is added, then
1.0kg 98 concentrated sulfuric acids and 1.0kg 37% formaldehyde are slowly added to, are stirred, 5kg MnSO is added under agitation4·
7H2O, stirring is complete to dissolving, and allows solution to drop to room temperature, finally using the filter element filtering in 5 μ apertures, obtains additive.
The electroplating bath newly burst at the seams, by copper ball pickling it is clean after be placed in electroplating bath, prepare new electroplating liquid medicine, including sulphur
Sour copper, sulfuric acid, chlorion and appropriate electroplating additive.Analysis allotment liquid medicine is added to after working range with 1ml/L amount
Additive, stirs, you can carry out the new normal production for opening cylinder.
Embodiment 3
One kind plating copper electrolyte, including following component：
Transition metal salt can be added by the following method：In 100kg container, 86.7kg deionized water is added,
The 2.5kg concentrated sulfuric acid and 0.8kg 37% formaldehyde are slow added into, is stirred, 20kg CoSO is added under agitation4·
7H2O, stirring is complete to dissolving, and allows solution to drop to room temperature, finally using the filter element filtering in the μ apertures of aperture 5, obtains additive.
Electroplating bath or the new electroplating bath for opening cylinder after cleaning copper anode add additive with 5ml/L amount, you can according to just
Often production.
Embodiment 4
One kind plating copper electrolyte, including following component：
Transition metal salt can be added by the following method：In 50kg container, 32.5kg deionized water is added, then
2.5kg 98% concentrated sulfuric acid is slowly added to, is stirred, 8kg FeSO is added under agitation4·9H2O and 10kg are put into
VOSO4·4H2O, stirring is complete to dissolving, and allows solution to drop to room temperature, finally using the filter element filtering in the μ apertures of aperture 5, is added
Plus agent.
Electroplating bath or the new electroplating bath for opening cylinder after cleaning copper anode add additive with 1ml/L amount, you can according to just
Often production.
Embodiment 5
One kind plating copper electrolyte, including following component：
Transition metal salt can be added by the following method：In 50kg container, 24.8kg deionized water is added, then
2.7kg 98% concentrated sulfuric acid and 0.5kg 37% formaldehyde are slowly added to, is stirred, 4kg FeCl is added under agitation3·
6H2O and 8kg are put into ZrOSO4·4H2O, stirring is complete to dissolving, and allows solution to drop to room temperature, finally using the filter in the μ apertures of aperture 5
Core is filtered, and obtains additive.
Electroplating bath or the new electroplating bath for opening cylinder after cleaning copper anode add additive with 4ml/L amount, you can according to just
Often production.
Embodiment 6
One kind 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 1000ppm MnSO4·7H2O, after ON cycle stirs, you can according to normal production.
Embodiment 7
One kind 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 50ppm VOSO4·4H2O and 50ppm ZrOSO4·4H2O, after ON cycle stirs, you can according to normal raw
Production.
Comparative example 1
One kind 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, after 3 months, and 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, to make description succinct, not to above-mentioned reality
Apply 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, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (8)
1. one kind plating copper electrolyte, it is characterised in that including following component：
2. plating copper electrolyte according to claim 1, it is characterised in that including following component：
3. plating copper electrolyte according to claim 1, it is characterised in that the cation of the transition metal salt is selected from VO2+、
Mn2+、Fe2+、Co2+Or ZrO2+In one or more.
4. plating copper electrolyte according to claim 1, it is characterised in that the anion of the transition metal salt is selected from SO4 2-
Or Cl-。
5. the plating copper electrolyte according to claim any one of 1-4, it is characterised in that the brightener is selected from poly- two sulphur two
The thio propane sulfonic acid sodium of propanesulfonate, phenyl two, N, N- dimethylthiocarbamoyl propane sulfonic acids sodium, imidazolinyl poly- two
It is one or more of in sulphur propane sulfonic acid sodium, N, N- diethyl thioureas.
6. plating copper electrolyte according to claim 5, it is characterised in that the brightener is selected from the poly- propane sulfonic acid of two sulphur two
It is one or two kinds of in the thio propane sulfonic acid sodium of sodium, phenyl two.
7. the plating copper electrolyte according to claim any one of 1-4, it is characterised in that the inhibitor is selected from polyalkylene
Diol compound, polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol, stearic acid macrogol ester, alkoxynaphthols, oleic acid gather
Glycol ester, poly- (ethylene glycol and 1,2-propylene glycol) random copolymer, poly- (polyethylene glycol propane diols-polyethylene glycol) block copolymerization
It is one or more of in thing, poly- (polypropylene glycol-polyethylene glycol propane diols) block copolymer.
8. plating copper electrolyte according to claim 7, it is characterised in that the inhibitor is selected from poly- (polypropylene glycol-poly- second
Glycol-polypropylene glycol) it is one or more of in block copolymer, poly- (ethylene glycol and 1,2-propylene glycol) random copolymer or polyethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710357312.1A CN106987874B (en) | 2017-05-19 | 2017-05-19 | Copper electrolyte is electroplated |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710357312.1A CN106987874B (en) | 2017-05-19 | 2017-05-19 | Copper electrolyte is electroplated |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106987874A true CN106987874A (en) | 2017-07-28 |
| CN106987874B CN106987874B (en) | 2019-07-02 |
Family
ID=59420632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710357312.1A Active CN106987874B (en) | 2017-05-19 | 2017-05-19 | Copper electrolyte is electroplated |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106987874B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109989077A (en) * | 2017-12-29 | 2019-07-09 | 广东东硕科技有限公司 | A kind of copper electrolyte |
| CN110359051A (en) * | 2019-06-18 | 2019-10-22 | 龙建国 | The method of circuitboard etching waste liquid cycling and reutilization |
| CN110424030A (en) * | 2019-08-30 | 2019-11-08 | 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 |
| 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 |
| CN111155152A (en) * | 2019-12-26 | 2020-05-15 | 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 |
| CN111962109A (en) * | 2020-08-20 | 2020-11-20 | 苏州大学 | Acid copper additive and preparation method thereof |
| CN112877739A (en) * | 2021-01-13 | 2021-06-01 | 苏州天承化工有限公司 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212853A (en) * | 2011-04-30 | 2011-10-12 | 山东金宝电子股份有限公司 | Surface treatment coarsening process for improving peel strength of copper foil |
| CN103038397A (en) * | 2010-07-29 | 2013-04-10 | 埃托特克德国有限公司 | 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 |
| CN104131319A (en) * | 2014-08-15 | 2014-11-05 | 苏州天承化工有限公司 | Electroplating solution for surface pore filling of plate parts and electroplating method thereof |
| CN105887144A (en) * | 2016-06-21 | 2016-08-24 | 广东光华科技股份有限公司 | Electric copper plating liquid and electric copper plating process thereof |
-
2017
- 2017-05-19 CN CN201710357312.1A patent/CN106987874B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103038397A (en) * | 2010-07-29 | 2013-04-10 | 埃托特克德国有限公司 | 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 |
| CN102212853A (en) * | 2011-04-30 | 2011-10-12 | 山东金宝电子股份有限公司 | Surface treatment coarsening process for improving peel strength of copper foil |
| CN104131319A (en) * | 2014-08-15 | 2014-11-05 | 苏州天承化工有限公司 | Electroplating solution for surface pore filling of plate parts and electroplating method thereof |
| CN105887144A (en) * | 2016-06-21 | 2016-08-24 | 广东光华科技股份有限公司 | Electric copper plating liquid and electric copper plating process thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109989077A (en) * | 2017-12-29 | 2019-07-09 | 广东东硕科技有限公司 | A kind of copper electrolyte |
| CN110359051A (en) * | 2019-06-18 | 2019-10-22 | 龙建国 | The method of circuitboard etching waste liquid cycling and reutilization |
| CN110424030A (en) * | 2019-08-30 | 2019-11-08 | 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 |
| CN111155152A (en) * | 2019-12-26 | 2020-05-15 | 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 |
| 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 |
| CN112877739A (en) * | 2021-01-13 | 2021-06-01 | 苏州天承化工有限公司 | 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 |
| CN114277413B (en) * | 2021-12-29 | 2024-05-17 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106987874B (en) | 2019-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106987874A (en) | Electroplate copper electrolyte | |
| CN105887144B (en) | Copper electrolyte and its copper plating process is electroplated | |
| CN106011965B (en) | A kind of fine roughening treatment technique of electrolytic copper foil surface | |
| CN105813378A (en) | copper foil provided with carrier, laminate, printed wiring board, electronic device, and method for fabricating printed wiring board | |
| CN107245742B (en) | A kind of aluminium alloy with no cyanogen sinks zinc agent and aluminium alloy sinks zinc method | |
| JP2009041097A (en) | Copper plating method | |
| JP2006210689A (en) | Copper foil for high frequency printed wiring board and its production method | |
| CN103857833A (en) | Copper foil excellent in adhesion with resin, method for manufacturing same, and printed wiring board or battery negative electrode material using electrolytic copper foil | |
| CN103343367A (en) | Nickel-plated steel strip and preparation method thereof | |
| CN103014787B (en) | A kind of copper electroplating liquid and electroplating technology thereof | |
| CN105603480A (en) | Black surface treatment method for rolled copper foil | |
| CN109972180B (en) | New use of 2, 2' -dithiodipyridine, electroplating hole-filling additive using the same and electroplating method using the additive | |
| CN106460217A (en) | Multilayer plating film and article having multilayer plating film | |
| CN102492968A (en) | Copper plating method on brass base material | |
| CN105002496A (en) | Black surface treatment method for electrolytic copper foil | |
| CN113802158B (en) | Electroplating solution and application thereof, copper plating process and plated part | |
| CN108130564A (en) | Vertical continuous is electroplated（VCP）High TP values acid copper-plating gloss agent and preparation method and application | |
| CN107099824A (en) | A kind of black chromium plating bath, composite deposite and preparation method thereof | |
| JP2003328179A (en) | Additive for acidic copper plating bath, acidic copper plating bath containing the additive and plating method using the plating bath | |
| JPH0319308B2 (en) | ||
| JPH01309997A (en) | Method for obtaining copper-nickel-chromium bright electroplating having excellent corrosion resistance and plating film obtained thereby | |
| CN114574911A (en) | Electroplating process for through hole of circuit board with high thickness-diameter ratio | |
| US20040074775A1 (en) | Pulse reverse electrolysis of acidic copper electroplating solutions | |
| CN110923757B (en) | Cyanide-free alkali copper electroplating solution and use method thereof | |
| CN102233699B (en) | Extremely thin copper foil using ultralow ridge copper foil as carrier and manufacturing method of extremely thin copper foil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |