CN107988622A - A kind of unleaded copper plating bath production method - Google Patents
A kind of unleaded copper plating bath production method Download PDFInfo
- Publication number
- CN107988622A CN107988622A CN201711344056.9A CN201711344056A CN107988622A CN 107988622 A CN107988622 A CN 107988622A CN 201711344056 A CN201711344056 A CN 201711344056A CN 107988622 A CN107988622 A CN 107988622A
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- CN
- China
- Prior art keywords
- copper
- stress
- plating
- phenylurea
- deposition stress
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- 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.)
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Classifications
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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 copper electroplating liquid for the plating stress for being used to remove electroplating copper film.According to the present invention, in the copper electroplating liquid, glycerol propoxylate ethoxylate is used as to be used for the carrier for removing plating stress, and adds phenylurea as the additive for removing plating stress.The copper electroplating liquid of the present invention includes the phenylurea of 0.02g/l~about 0.08g/l.
Description
Technical field
Invention disclosed herein is related to a kind of copper plating bath, more specifically, is related to a kind of deposition for mitigating electroplating copper film
The copper electroplating liquid of stress.
Background technology
Using electrolysis principle, by using plating, the material requested to be plated is deposited on the body surface at cathode.
The primary element of plating includes anode, cathode and electrolyte.In addition, electrolyte includes the plan metallization of ionic species.
In electroplating process, deposition stress can be produced at plated film.Deposition stress includes compression stress and tensile stress.These
Stress causes various limitations.These limitation include electroplating film and base material adhesion, caused by substrate deformation phenomenon of rupture,
Carry out assembling difficulty during plating base material assembling procedure, the deterioration of product reliability, reduction of life of product etc..Particularly,
Compared with the product for being plated on its bilateral, the limitation that can be significantly more produced in its unilateral product caused by deposition stress is only plated on.
For example, when it is using the touch-screen electrode increased with the explosive increase of intelligent apparatus recently for manufacture,
It is usually only unilateral plated if replacing silk screen print method or sputtering method using galvanoplastic.It is in addition, normal when being replaced by galvanoplastic
It is usually only unilateral to be plated when the silk screen print method manufacture seen is used for as electrode in the solar cell of one of clean energy resource.
One side plating causes the substrate deformation of the product by electroplating manufacture, or such as silicon wafer, strengthened glass or plastic resin base material
Deteriorated with the adhesive strength of plated film because of above-mentioned deposition stress.
If the electrode of solar cell or the electrode of touch panel are manufactured by using galvanoplastic, with other electricity
Plating method is compared, and price competitiveness is higher.However, despite the presence of price competitiveness, but because galvanoplastic can caused by skill as described above
Art shortcoming, so galvanoplastic are not yet actually used.
Therefore, if the deposition stress produced in electroplating copper film can be mitigated, electrocoppering is can be utilized,
Thus production cost can significantly reduce.Particularly, cause when in view of the price increase of the silver paste because being currently used as electrode etc.
During production cost sharp increase, economic feasibility is more notable.
This technology described in this patent document is inventor's research work as a result, can be used for solving above-mentioned limitation.
The content of the invention
Technical problem
It is an object of the invention to provide a kind of new coating solution for being used to mitigate the deposition stress produced in electroplating copper film.
At the same time, it is believed that other benefits for not illustrating are can be easily by embodiment and this paper in the present invention
In the zone of reasonableness that effect hereinafter obtains.
Technical solution
In order to realize the purpose, embodiments of the present invention provide a kind of copper electroplating liquid, and the copper electroplating liquid includes phenylurea
As deposition stress palliative.In some embodiments, the additive amount of phenylurea can be about 0.02g/l~about 0.08g/
l。
Beneficial effect
By the copper electroplating liquid for preparing of the present invention even if also having low-down deposition stress under high current densities.Separately
Outside, when the electrode of solar cell or touch-screen is formed by using copper electroplating liquid, deformation of products is not produced.In addition, meeting
Realize the remarkable result for improving the adhesive strength between base material and electroplating copper film.
The reliability of product and the service life of product also can improve and extend at the same time.In addition, because of product in process for making
The fracture defect for deforming and producing can be reduced.As described above, caused deposition stress can be with during carrying out electro-coppering
It is reduced.In addition, the technology disclosed in this patent document can be widely applied to various applications.
Potential effect that is desired by the technical characteristic of the present invention but not specifically noted in specification will be construed to specification
In pointed effect.
Brief description of the drawings
Fig. 1 illustrates to work as by using the solution comprising phenylurea according to the embodiment of the present invention to solar cell
Carry out the plating object with minimum deformation of acquisition during electro-coppering；With
Fig. 2 illustrates by using the solution (comparative example 1) not comprising phenylurea according to conventional methods to solar-electricity
Pond carries out the plating object with deformation of acquisition during electro-coppering.
Including attached drawing to provide further understanding for invention thinking, but the scope not limited to this of the right of the present invention.
Embodiment
Hereinafter, when known function is apparent to those skilled in the art, for related known function
Be described in detail in the explanation present invention during will be omitted, it is believed to unnecessarily to obscure the purport of the present invention.
In the present invention, carry out electro-coppering after phenylurea is added and obtain plated film.When measuring the deposition stress of plated film,
Confirm that phenylurea alleviates the deposition stress of copper plating film.
That is, in the present invention, stress palliative of the addition for removing deposition stress during electro-coppering.Stress palliative
It can include phenylurea.The substrate bath (basic bath) added includes metal ion and such as copper sulphate electrolyte, sulphur
Acid and chlorion.In addition, the carrier as copper plating solution, can include glycerol propoxylate ethoxylate
One or both of (glycerinpropoxylate ethoxylate) derivative component.
Amount as the carrier glycerol propoxylate ethoxy substratess of additive is preferably from about 0.05g/l~2.0g/l.Most close
Suitable concentration is about 1.0g/l.In addition, as deposition stress palliative, the phenylurea of addition is about 0.02g/l~about 0.08g/l
Phenylurea, and most preferably concentration be about 0.06g/l.
The preferable working current density of the present invention is about 1.0A/dm 2~about 5.0A/dm 2.
[embodiment 1]
First, the condition of electro-coppering of the invention is as follows.Anode is used as using phosphorous copper electrode.At cathode, installation measurement is heavy
Product stress sample.Copper electroplating liquid include as substrate (base) acid solution (it includes 120g/l copper sulphate,
160g/l sulfuric acid and 70mg/l chlorions), and (it is the third oxygen of glycerine to the GEP2800 of 1.0g/l as carrier
Base ethoxylate derivatives).In addition, 0.02g/l phenylureas (PU) are added into coating solution.
Then, in 28 DEG C of operating temperature, using the working current density of 4.5A/dm 2, the coating solution plating is used
The sample 40 minutes at cathode with 2 plating areas of 7.6cm.As a result, obtain the plating with about 40 μm of thickness
Film.
[embodiment 2]
0.04g/l phenylureas are added into coating solution.Remaining condition is identical with embodiment 1.
[embodiment 3]
0.06g/l phenylureas are added into coating solution.Remaining condition is identical with embodiment 1.
[embodiment 4]
0.08g/l phenylureas are added into coating solution.Remaining condition is identical with embodiment 1.
[comparative example 1]
Different from above-described embodiment, conventional coating solution is used.That is, it is used as anode using phosphorous copper electrode.At cathode, installation
Measure deposition stress sample.Copper electroplating liquid include as substrate acid solution (it includes 120g/l copper sulphate,
160g/l sulfuric acid and 70mg/l chlorions) carrier (it includes 1.0g/l GEP2800 (glycerol propoxylate ethoxylate)).
In addition, the sodium salt (MPS) of 0.04g/l3- sulfydryl -1- propane sulfonic acid is added into coating solution.Then, in 28 DEG C of work
Make temperature, using the working current density of 4.5A/dm 2, there is 2 plating areas of 7.6cm using the coating solution plating
The sample 40 minutes at cathode.As a result, obtain the plated film with about 40 μm of thickness.
[comparative example 2]
Add levelling agent, i.e. 0.5mg/l PVP.Remaining condition is identical with comparative example 1.
[experimental example]
Measure the deposition stress of each sample of embodiment 1~4 and comparative example 1 and 2., will to compare deposition stress
1~4 and it is compared, and is measured using the sample of the comparative example 1 of common copper electroplating liquid according to an embodiment of the invention
Change of the deposition stress on the concentration of deposition stress palliative, and change of the deposition stress on the time after electro-coppering.Will
The deposition stress measuring method of calibration tape is used as measuring method, and 683EC deposition stress analyzer is used as measuring device, and will
Be-Cu alloy products are used as measurement sample.The measurement result of embodiment and the deposition stress of comparative example is shown in table 1 below.Table 1
In, it is shown that just carried out the deposition stress of the initial electroplating copper film after plating, and after a period of time is stored at room temperature it is heavy
The change of product stress.
[table 1]
When by embodiment 1~4 compared with the deposition stress of the electroplating copper film of comparative example 1 and 2, it may be found that real
The deposition stress for applying example 1~4 is very low.In addition, when the result of comparative example 1 and comparative example 2 is compared, will
It was found that deposition stress higher of the addition as the comparative example 2 of the levelling agent PVP of additive wherein into coating solution.That is,
Levelling agent class organic material is included not contributing to mitigate deposition stress；On the contrary, deposition stress is raising.
Based on experimental result, plating is carried out to solar cell, and first measures deformation extent to check actual product
The mitigation effect of deposition stress.The primary condition of copper electroplating liquid is arranged to the condition phase with embodiment 3 and comparative example 1
Together, and copper plating is carried out.Fig. 1 shows the deformation extent of product after progress copper plating.The measurement of deformation extent is by making
Carried out with feeler gauge.According to the deformation extent of the solar cell of 3 plating of embodiment less than or equal to about 0.15mm, and
Deformation extent according to the solar cell of 1 plating of comparative example is about 1.2mm.
Secondly, sample is prepared as follows, to examine influence of the deposition stress of electroplating copper film for adhesive strength.It is being coated with
On the glass substrate of ITO, the kind layer for being electroplated is used as by vacuum deposition chromium and copper.In 28 DEG C of work temperature
Degree, using the working current density of 1.5A/dm 2, the solution composition plated specimens 5 by using embodiment 3 or comparative example 1 divide
Clock, to form the copper plating film with about 2.5 μm of thickness.Then, to test the adhesive strength of electroplating copper film, with about 1mm's
Spacing carries out copper plating film crosscutting.By using 3M#610 adhesive tapes, repeat to adhere on plated film cross section and be desorbed 3
It is secondary, and compare adhesive strength.It turns out that the situation on adding phenylurea according to embodiment 3, adhesive strength improve very
It is more.
Thus experimental result, finds to substantially reduce for the situation using the copper electroplating liquid comprising phenylurea, deposition stress,
Therefore, the few generation of solar energy deformation caused by electroplating, and compared with using the situation of the copper electroplating liquid not comprising phenylurea,
Plating adhesive strength on the resins such as such as touch panel is improved.
In addition, protection scope of the present invention is not limited to the description and expression of the embodiment clearly stated for more than.In addition,
It should be appreciated that protection scope of the present invention is not limited by significantly changing or substituting in technical field.
Claims (2)
1. a kind of copper electroplating liquid, the copper electroplating liquid includes phenylurea as the additive for mitigating deposition stress.
2. the copper electroplating liquid as described in claim 1, wherein the amount of the phenylurea is about 0.02g/l~about 0.08g/
l。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711344056.9A CN107988622A (en) | 2017-12-15 | 2017-12-15 | A kind of unleaded copper plating bath production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711344056.9A CN107988622A (en) | 2017-12-15 | 2017-12-15 | A kind of unleaded copper plating bath production method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107988622A true CN107988622A (en) | 2018-05-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711344056.9A Pending CN107988622A (en) | 2017-12-15 | 2017-12-15 | A kind of unleaded copper plating bath production method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107988622A (en) |
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2017
- 2017-12-15 CN CN201711344056.9A patent/CN107988622A/en active Pending
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| PB01 | Publication | ||
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Application publication date: 20180504 |