CN106917078A - Palladium method is plated in a kind of displacement for copper surface - Google Patents
Palladium method is plated in a kind of displacement for copper surface Download PDFInfo
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- CN106917078A CN106917078A CN201710224635.3A CN201710224635A CN106917078A CN 106917078 A CN106917078 A CN 106917078A CN 201710224635 A CN201710224635 A CN 201710224635A CN 106917078 A CN106917078 A CN 106917078A
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- palladium
- plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
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Abstract
Palladium method is plated the invention discloses a kind of displacement for copper surface, is concretely comprised the following steps：1）Oil removing is carried out to copper specimen surface and except oxide clean；2）The copper sample that will be cleaned is directly immersed in displacement plating aqueous palladium and carries out plating, and it is 20 70 DEG C that plating aqueous palladium temperature is replaced during plating, and plating time is 0.1 5 minutes；3）After the completion of plating, it is cleaned and dried；The composition of displacement plating aqueous palladium and the content of each component are：The 15g/L of palladium salt 1, the 120g/L of complexing agent 15, the 50g/L of organic acid 0.1, the 10g/L of additive 0.Displacement plating aqueous palladium disclosed by the invention is free of reducing agent, with low cost, stability it is high, can the advantage such as long-term use；It is disclosed by the invention using displacement plating aqueous palladium the method for copper surface replacement plating palladium have process is simple, be easy to operation, can the advantage such as scale application；Preparation-obtained palladium coating has good adhesion, the outstanding performance such as anti-oxidant and anticorrosive.
Description
Technical field
Palladium method is plated the present invention relates to a kind of displacement for copper surface, belongs to field of metal surface treatment technology.
Background technology
The features such as due to outstanding chemical stability, electric conductivity and solderability, palladium coating has been widely used for copper
Bonding wire and printed circuit board (PCB)（Printed circuit boards, PCBs）Copper circuit surface, with improve copper bonding wire and
The inoxidizability and corrosion resistance of PCB copper circuits, prevent the oxidation and corrosion of copper from being produced to performances such as its electric conductivity and solderabilities
Influence.The method of current copper plated surface palladium mainly has：Plating and electronation coating technology.Palladium plating is that unplated piece is born with power supply
Extremely it is connected, the palladium ion in solution obtains the method that electronics is separated out and form coating on unplated piece surface.But due to the copper on PCB
Circuit is in dispersed distribution, it is difficult to every circuit is connected with power cathode, and palladium electroplating solution complicated component, environmental pollution
It is more serious.Chemical deoxidizing plating palladium be according to principle of oxidation and reduction, using the reducing agent in chemical deoxidizing plating palladium liquid by palladium from
Son is reduced into Metal Palladium and is deposited on the method that unplated piece surface forms palladium coating.But it is harmful that chemical deoxidizing plating palladium is used
Reducing agent（Usually hypophosphite, boron hydride, formaldehyde, hydrazine etc.）Can largely influence plating palladium liquid stability and
Plating speed, and plating time is long, and production cost is high, in addition with that may form plating of overflowing outside PCB copper circuits, causes circuit short
Road etc..
Patent document CN 105296974A give a kind of plating palladium liquid without reducing agent and using it in copper plated surface palladium
Method, but its plating palladium process is not directly, using the palladium in copper displacement plating palladium liquid, but to need to contact aluminium flake with copper.By
Contacted with aluminium flake in every PCB copper circuit for being difficult to arrange dispersion, therefore the method is obviously not suitable for PCB copper circuits surface
Plating palladium.Patent document CN 103726037A give a kind of chemical palladium immersing solution, but the palladium immersing solution is only applicable to the nickel on copper surface
Palladium coating is prepared on coating.
The content of the invention
The technical problem to be solved in the present invention is to overcome the shortcomings of existing copper plated surface palladium process, there is provided one kind can
Simple and effective can industrial scale application for copper surface displacement plate palladium method.
The present invention is lower than palladium using the standard electrode potential of copper, and it is anti-that displacement directly occurs by the palladium ion in copper and plating solution
Answer and the purpose of copper surface direct plating palladium of the realization including including copper bonding wire and PCB copper circuits etc..Given displacement plating
Aqueous palladium is free of reducing agent, with low cost, sedimentation rate is fast, stability is high, can the advantage, prepared palladium such as long-term use
Thickness of coating is uniform, free from flaw, with good adhesion, outstanding inoxidizability, solderability, electric conductivity and corrosion resistance；
It is given using displacement plating aqueous palladium the method for copper surface replacement plating palladium have process is simple, be easy to operation, can scale
Change the advantages such as application.
Palladium method is plated in a kind of displacement for copper surface, is concretely comprised the following steps：
1）Oil removing is carried out to copper specimen surface and except oxide clean；
2）The copper sample that will be cleaned is directly immersed in displacement plating aqueous palladium and carries out plating, and plating aqueous palladium temperature is replaced during plating
It it is 20-70 DEG C, plating time is 0.1-5 minutes；
3）After the completion of plating, it is cleaned and dried；
It is characterized in that the content of the composition of the displacement plating aqueous palladium and each component is：Palladium salt 1-15g/L, complexing agent 15-
120g/L, organic acid 0.1-50g/L, additive 0-10g/L.
The palladium salt is one or more in palladium bichloride, the ammonia palladium of dichloro four, dichloro diamino palladium, palladium, palladium sulfate.
The complexing agent is the compound of edetate and ammonium salt.
The organic acid is the one kind or many in citric acid, tartaric acid, malic acid, formic acid, oxalic acid, hexanedioic acid, maleic acid
Kind.
The additive is one or more in lauryl sodium sulfate, neopelex and saccharin.
Beneficial effects of the present invention：The present invention has the standard electrode potential lower than palladium using copper, directly by displacement
Plating palladium method, aqueous palladium is plated using the displacement without traditional reducing agent, you can realization has in copper specimen surface stably depositing
Good combination power, outstanding anti-oxidant and corrosion resistance palladium coating.The displacement plating aqueous palladium that the present invention is given has cost
Low, stability is high, can the advantage such as long-term use；Displacement that the present invention is given plating palladium method have process is simple, be easy to operation, can
The advantages such as scale application.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of pure copper sheet surface replacement plating palladium layers in the embodiment of the present invention 1.
Fig. 2 is the pure copper sheet front and rear potentiodynamic polarization song in 3.5%NaCl solution of displacement plating palladium in the embodiment of the present invention 1
Line.
Specific embodiment
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
One kind displacement plating aqueous palladium, consisting of：Palladium bichloride 2g/L, disodium ethylene diamine tetraacetate 15g/L, ammonium sulfate 40g/L,
Citric acid 10g/L, neopelex 1g/L.
A kind of to plate method of the aqueous palladium in pure copper sheet plated surface palladium using above-mentioned displacement, it includes following steps：
（1）Ultrasonic cleaning is carried out using acetone to pure copper sheet to degrease, carrying out pure copper sheet pickling using watery hydrochloric acid removes surface
Oxide etc., then uses water and alcohol rinse and dries successively；
（2）Pure copper sheet after cleaning is immersed in above-mentioned displacement plating aqueous palladium in time, under conditions of being 30 DEG C in temperature, plating
2 minutes.
（3）After the completion of plating, sample is taken out, it is totally and dry with water and alcohol rinse successively.
The palladium with good appearance can be obtained using above-mentioned displacement plating aqueous palladium and plating palladium method on pure copper sheet surface to plate
Layer, palladium coating is good with the adhesion of pure copper sheet.The stereoscan photograph of palladium coating is shown in Fig. 1；3.5% before and after pure copper sheet plating palladium
Dynamic potential polarization curve in NaCl solution is shown in Fig. 2, relative to pure copper sheet, after displacement plating palladium under the corrosion electric current density of pure copper sheet
Drop 90%.
Embodiment 2
One kind displacement plating aqueous palladium, consisting of：Palladium bichloride 4g/L, disodium ethylene diamine tetraacetate 10g/L, ammonium chloride 50g/L,
Citric acid 12g/L, neopelex 1.5g/L, saccharin 0.2g/L.
A kind of to plate method of the aqueous palladium in pure copper sheet plated surface palladium using above-mentioned displacement, it includes following steps：
（1）Ultrasonic cleaning is carried out to pure copper sheet to degrease, pickling removing is carried out to pure copper sheet using watery hydrochloric acid using hot concentrated alkali liquid
Oxide on surface etc., then uses water and alcohol rinse and dries successively；
（2）Pure copper sheet part after cleaning is immersed in above-mentioned displacement plating aqueous palladium, under conditions of being 35 DEG C in temperature, plating
1 minute.
（3）After the completion of plating, sample is taken out, it is totally and dry with water and alcohol rinse successively.
Can be on part pure copper sheet surface using above-mentioned displacement plating aqueous palladium and plating palladium method（Immersion displacement plating aqueous palladium
Part）The palladium coating with good appearance is obtained, palladium coating is good with the adhesion of pure copper sheet.Aliquot replacement plating palladium pure copper sheet exists
200 DEG C are heated in air after 10 minutes, pure copper sheet surface is not replaced plating palladium region and significantly oxidation has occurred, and replaces plating
Palladium region remains unchanged presentation silvery white, aoxidizes.
Embodiment 3
One kind displacement plating aqueous palladium, consisting of：Dichloro four ammonia palladium 5g/L, disodium ethylene diamine tetraacetate 20g/L, ammonium chloride
40g/L, tartaric acid 20g/L, neopelex 2g/L.
A kind of to plate method of the aqueous palladium in copper bonding wire plated surface palladium using above-mentioned displacement, it includes following steps：
（1）Pickling is carried out to copper bonding wire using watery hydrochloric acid and removes oxide on surface etc., then use water and alcohol rinse simultaneously successively
Dry；
（2）Copper bonding wire after cleaning is immersed in above-mentioned displacement plating aqueous palladium in time, under conditions of being 45 DEG C in temperature, is applied
Plating 0.2 minute.
（3）After the completion of plating, sample is taken out, it is totally and dry with water and alcohol rinse successively.
Palladium with good appearance can be obtained on copper bonding wire surface using above-mentioned displacement plating aqueous palladium and plating palladium method
Coating, palladium coating is good with the adhesion of copper bonding wire.Temperature be 25 DEG C, relative humidity be 50% in the environment of, copper bonding wire
The displacement plating palladium layers on surface can for a long time keep good appearance.
Embodiment 4
One kind displacement plating aqueous palladium, consisting of：Palladium 5g/L, disodium ethylene diamine tetraacetate 20g/L, ammonium sulfate 50g/L,
Formic acid 15g/L, lauryl sodium sulfate 1.5g/L.
A kind of to plate method of the aqueous palladium in PCB copper circuit plated surface palladiums using above-mentioned displacement, it includes following steps：
（1）Pickling is carried out to PCB copper circuits using watery hydrochloric acid and removes oxide on surface etc., then use water and alcohol rinse simultaneously successively
Dry；
（2）PCB copper circuits after cleaning are immersed in above-mentioned displacement plating aqueous palladium in time, under conditions of being 25 DEG C in temperature,
Plating 1 minute.
（3）After the completion of plating, sample is taken out, it is totally and dry with water and alcohol rinse successively.
Palladium with good appearance can be obtained on PCB copper circuits surface using above-mentioned displacement plating aqueous palladium and plating palladium method
Coating, palladium coating is good with the adhesion of PCB copper circuits.Temperature be 25 DEG C, relative humidity be 50% in the environment of, PCB copper electricity
The displacement plating palladium layers of road surfaces can for a long time keep good appearance.
Embodiment 5
One kind displacement plating aqueous palladium, consisting of：Palladium sulfate 4g/L, disodium ethylene diamine tetraacetate 25g/L, ammonium fluoride 25g/L,
Citric acid 15g/L, oxalic acid 15g/L.
A kind of to plate method of the aqueous palladium in pure copper sheet plated surface palladium using above-mentioned displacement, it includes following steps：
（1）Pure copper sheet is carried out into ultrasonic cleaning using acetone to degrease, carrying out pure copper sheet pickling using watery hydrochloric acid removes surface
Oxide etc., then uses water and alcohol rinse and dries successively；
（2）Pure copper sheet after cleaning is immersed in above-mentioned displacement plating aqueous palladium in time, under conditions of being 50 DEG C in temperature, plating
1.5 minutes.
（3）After the completion of plating, sample is taken out, it is totally and dry with water and alcohol rinse successively.
The palladium with good appearance can be obtained using above-mentioned displacement plating aqueous palladium and plating palladium method on pure copper sheet surface to plate
Layer, palladium coating is good with the adhesion of pure copper sheet.Relative to pure copper sheet, pure copper sheet is in 3.5%NaCl solution after displacement plating palladium
Corrosion electric current density have dropped 73%.
Embodiment 6
One kind displacement plating aqueous palladium, consisting of：Palladium bichloride 8g/L, disodium ethylene diamine tetraacetate 30g/L, ammonium sulfate 40g/L,
Tartaric acid 15g/L, hexanedioic acid 10g/L, lauryl sodium sulfate 1g/L, saccharin 0.3g/L.
A kind of to plate method of the aqueous palladium in latten(-tin) plated surface palladium using above-mentioned displacement, it includes following steps：
（1）Latten(-tin) is carried out into ultrasound using acetone to degrease, carrying out latten(-tin) pickling using watery hydrochloric acid removes surface oxidation
Thing etc., then uses water and alcohol rinse and dries successively；
（2）Latten(-tin) after cleaning is immersed in above-mentioned displacement plating aqueous palladium in time, under conditions of being 40 DEG C in temperature, plating
3 minutes.
（3）After the completion of plating, sample is taken out, it is totally and dry with water and alcohol rinse successively.
The palladium with good appearance can be obtained using above-mentioned displacement plating aqueous palladium and plating palladium method on latten(-tin) surface to plate
Layer, palladium coating is good with the adhesion of latten(-tin).Relative to latten(-tin), pure copper sheet is in 3.5%NaCl solution after displacement plating palladium
Corrosion electric current density have dropped 81%.
Embodiment 7
One kind displacement plating aqueous palladium, consisting of：Palladium bichloride 2g/L, palladium sulfate 2g/L, disodium ethylene diamine tetraacetate 15g/L,
Ammonium sulfate 40g/L, citric acid 10g/L, malic acid 15g/L, lauryl sodium sulfate 2g/L.
A kind of to plate method of the aqueous palladium in red copper bar plated surface palladium using above-mentioned displacement, it includes following steps：
（1）Red copper bar is carried out into ultrasonic cleaning using acetone to degrease, carrying out red copper bar pickling using watery hydrochloric acid removes surface
Oxide etc., then uses water and alcohol rinse and dries successively；
（2）Red copper bar after cleaning is immersed in above-mentioned displacement plating aqueous palladium in time, under conditions of being 45 DEG C in temperature, plating
2 minutes.
（3）After the completion of plating, sample is taken out, it is totally and dry with water and alcohol rinse successively.
The palladium with good appearance can be obtained using above-mentioned displacement plating aqueous palladium and plating palladium method on red copper bar surface to plate
Layer, palladium coating is good with the adhesion of red copper bar.Temperature be 25 DEG C, relative humidity be 50% in the environment of, red copper bar surface
Displacement plating palladium layers can for a long time keep good appearance.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it still may be used
Modified with to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic.
All any modification, equivalent substitution and improvements within the spirit and principles in the present invention, made etc., should be included in of the invention
Within protection domain.
Claims (5)
1. palladium method is plated in a kind of displacement for copper surface, is concretely comprised the following steps：
1）Oil removing is carried out to copper specimen surface and except oxide clean；
2）The copper sample that will be cleaned is directly immersed in displacement plating aqueous palladium and carries out plating, and plating aqueous palladium temperature is replaced during plating
It it is 20-70 DEG C, plating time is 0.1-5 minutes；
3）After the completion of plating, it is cleaned and dried；
It is characterized in that the content of the composition of the displacement plating aqueous palladium and each component is：Palladium salt 1-15g/L, complexing agent 15-
120g/L, organic acid 0.1-50g/L, additive 0-10g/L.
2. the method for claim 1, it is characterised in that the palladium salt be palladium bichloride, the ammonia palladium of dichloro four, dichloro diamino palladium,
One or more in palladium, palladium sulfate.
3. the method for claim 1, it is characterised in that the complexing agent is the compound of edetate and ammonium salt
Thing.
4. the method for claim 1, it is characterised in that the organic acid be citric acid, tartaric acid, malic acid, formic acid,
One or more in oxalic acid, hexanedioic acid, maleic acid.
5. the method for claim 1, it is characterised in that the additive is lauryl sodium sulfate, detergent alkylate sulphur
One or more in sour sodium and saccharin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710224635.3A CN106917078B (en) | 2017-04-07 | 2017-04-07 | A kind of displacement plating palladium method for copper surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710224635.3A CN106917078B (en) | 2017-04-07 | 2017-04-07 | A kind of displacement plating palladium method for copper surface |
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| Publication Number | Publication Date |
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| CN106917078A true CN106917078A (en) | 2017-07-04 |
| CN106917078B CN106917078B (en) | 2019-03-29 |
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| CN201710224635.3A Active CN106917078B (en) | 2017-04-07 | 2017-04-07 | A kind of displacement plating palladium method for copper surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959665A (en) * | 2022-04-25 | 2022-08-30 | 金川集团股份有限公司 | Preparation method of colloidal palladium activation solution for electroless copper plating of printed circuit board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6472023B1 (en) * | 2001-07-10 | 2002-10-29 | Chang Chun Petrochemical Co., Ltd. | Seed layer of copper interconnection via displacement |
| CN105296974A (en) * | 2015-08-27 | 2016-02-03 | 中国科学院兰州化学物理研究所 | Palladium plating liquid and method for plating palladium on copper surface by using same |
-
2017
- 2017-04-07 CN CN201710224635.3A patent/CN106917078B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6472023B1 (en) * | 2001-07-10 | 2002-10-29 | Chang Chun Petrochemical Co., Ltd. | Seed layer of copper interconnection via displacement |
| CN105296974A (en) * | 2015-08-27 | 2016-02-03 | 中国科学院兰州化学物理研究所 | Palladium plating liquid and method for plating palladium on copper surface by using same |
Non-Patent Citations (2)
| Title |
|---|
| 张甜甜等: "铜表面化学镀钯工艺研究", 《电镀与涂饰》 * |
| 肖忠良等: "化学置换镀钯的研究", 《长沙理工大学学报（自然科学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959665A (en) * | 2022-04-25 | 2022-08-30 | 金川集团股份有限公司 | Preparation method of colloidal palladium activation solution for electroless copper plating of printed circuit board |
| CN114959665B (en) * | 2022-04-25 | 2024-03-01 | 金川集团股份有限公司 | Preparation method of colloid palladium activating solution for electroless copper plating of printed circuit board |
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| Publication number | Publication date |
|---|---|
| CN106917078B (en) | 2019-03-29 |
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