EP2772566B1 - Zusammensetzung für die stromlose abscheidung von silber und entsprechendes verfahren - Google Patents

Zusammensetzung für die stromlose abscheidung von silber und entsprechendes verfahren Download PDF

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EP2772566B1
EP2772566B1 EP12843616.9A EP12843616A EP2772566B1 EP 2772566 B1 EP2772566 B1 EP 2772566B1 EP 12843616 A EP12843616 A EP 12843616A EP 2772566 B1 EP2772566 B1 EP 2772566B1
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Prior art keywords
silver
plating solution
plating
mol
reducing
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English (en)
French (fr)
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EP2772566A1 (de
EP2772566A4 (de
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Daisuke Hashimoto
Kota KITAJIMA
Akira Okada
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Uemera Kogyo Co Ltd
C Uyemura and Co Ltd
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Uemera Kogyo Co Ltd
C Uyemura and Co Ltd
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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
    • C23C18/44—Coating with noble metals using reducing agents
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the present invention relates to a reducing electroless silver plating solution and a reducing electroless silver plating method, more specifically, relates to a reducing electroless silver plating solution and a reducing electroless silver plating method using the silver plating solution, the reducing electroless silver plating solution being stable and being capable of forming a good plating film without excessive roughening of an underlying metal or the like.
  • Silver plating has been long used for ornamental purposes and the like, and in recent years, with making use of its electrical characteristics and high reflectivity, it has been frequently used in the field of electrical industry, and the field of optical industry, and also in other fields, such as the field of electromagnetic wave shield and the field of sterilization coating. Especially, electroless silver plating has been more frequently used since it allows film thickness to be controlled and a plating film having a necessary thickness to be easily formed.
  • Electroless silver plating is broadly divided into substituting electroless silver plating and reducing electroless silver plating.
  • Substituting electroless silver plating is relatively excellent in stability of a plating solution, and has been frequently employed in the market (for example, refer to Patent Literatures 1 and 2.).
  • substituting electroless silver plating is performed in such a manner that silver plating is precipitated by a substitution reaction with an underlying metal, there is a problem that a limited kind of underlying material is used for substituting electroless silver plating.
  • reducing electroless silver plating is performed in such a manner that silver plating is precipitated on an underlying metal by making a reducing agent to be contained in a plating solution and thereby reducing a water-soluble silver compound to metallic silver, and this reducing electroless silver plating is capable of forming a good silver plating film without roughening of an underlying material and also without limiting a kind of underlying material.
  • a reducing electroless silver plating solution is made to contain a silver cyanide compound, such as silver potassium cyanide, as a water-soluble silver salt.
  • a silver cyanide compound such as silver potassium cyanide
  • an amount of cyanogen contained in a plating solution is more than twice as that of silver at a molar ratio.
  • Patent Literature 3 a method for improving the stability of a reducing electroless silver plating solution by adding a cyanide, such as potassium cyanide, wherein many free cyanides are present in the plating solution.
  • a cyanide such as potassium cyanide
  • Patent Literatures 4 and 5 a cyanogen-free reducing electroless silver plating solution has been also proposed (For example, Patent Literatures 4 and 5.).
  • cyanogen-free electroless silver plating solution cyanogen is not present in the plating solution and therefore an underlying metal or the like is not dissolved, and accordingly, a surface thereof is not excessively roughened, however, with respect to the solution stability, the cyanogen-free electroless silver plating solution has been remarkably inferior to that of a plating solution containing cyanogen.
  • Patent Literatures 4 and 5 there has been proposed a technique to improve the stability of a cyanogen-free silver plating solution by adding an additive thereto, but the cyanogen-free silver plating solution has not yet had sufficient stability.
  • the thicker a silver film becomes the more the silver film becomes yellowish, and thus a problem arises also in view of appearance of a plating film.
  • Non PTL 1 " Mudenkai Mekki - Kiso to Ohyo” (Electroless Plating - Fundamentals and Applications) (edited by Electroplating Research Society Japan, published by Nikkan Kogyo Shimbun, Ltd., pp176-177 )
  • GB 1 058 915 A1 teaches an autocatalytic plating solution capable of depositing silver on catalytic surfaces.
  • Alkali cyanides in an amount of between 5 micrograms and 500 milligrams per liter can be added to the bath.
  • a reducing agent can be present in the bath.
  • DE 34 19 755 A1 discloses a chemical bath for depositing silver on the surface of a substrate, wherein the bath contains as complexing agent thiocyanate ions and as reducing agent hydroxylamine.
  • the present invention is proposed in view of such actual circumstances, and aims at providing a reducing electroless silver plating solution and a reducing electroless silver plating method using the silver plating solution, the reducing electroless silver plating solution being capable of preventing decomposition of silver in the plating solution thereby to maintain the stability of the solution and also being capable of preventing excessive roughening of metal or the like as an underlying plating material thereby to form a plating film having good film characteristics and a good appearance.
  • the present inventors earnestly studied to achieve the above-mentioned aim, and as a result, found that control of a cyanogen concentration in a plating solution allows the stability of the plating solution to be maintained and prevents an underlying metal or the like from being excessively roughened, whereby a plating film having good film characteristics and being excellent in appearance can be formed, and the present inventors completed the present invention.
  • a reducing electroless silver plating solution according to the present invention comprises a water-soluble silver salt and a reducing agent selected from hydroxylammonium sulfate and hydroxylammonium acetate, wherein cyanide ions in a concentration of 0.006 ⁇ 10 -3 mol/L to 12.5 ⁇ 10 -3 mol/L are contained.
  • the above-mentioned water-soluble silver salt is preferably a silver salt other than a cyanide, and the above-mentioned cyanide ions are preferably contained as an alkali metal cyanide.
  • the above-mentioned reducing agent is at least one kind or more selected from hydroxylammonium sulfate and hydroxylammonium acetate.
  • the reducing electroless silver plating solution according to the present invention preferably has a pH of 8 to 11.
  • a reducing electroless silver plating method is such that electroless silver plating is applied to a plated material, using a reducing electroless silver plating solution comprising a water-soluble silver salt and a reducing agent selected from hydroxylammonium sulfate and hydroxylammonium acetate, wherein cyanide ions in a concentration of 0.006 ⁇ 10 -3 mol/L to 12.5 ⁇ 10 -3 mol/L are contained.
  • the reducing electroless silver plating solution and the reducing electroless silver plating method according to the present invention are capable of preventing decomposition of silver in the plating solution thereby to make the stability of the solution good and also capable of preventing excessive roughening of metal or the like as an underlying plating material thereby to form a plating film having good film characteristics and a good appearance.
  • Figure 1 illustrates graphs showing relationships between film thickness of a plating film and plating time where different reducing agents are employed.
  • the present embodiment a specific embodiment of the reducing electroless silver plating solution according to the present invention (hereinafter, referred to as the present embodiment.) will be described in detail.
  • a reducing electroless silver plating solution according to the present embodiment comprises a water-soluble silver salt and a reducing agent, the silver plating solution being capable of reducing the water-soluble silver salt to metallic silver with the reducing agent and precipitating silver plating on a plated material, such as an underlying metal, thereby forming a silver plating film.
  • the reducing electroless silver plating solution according to the present embodiment is characterized in that, in the plating solution comprising a water-soluble silver salt and a reducing agent selected from hydroxylammonium sulfate and hydroxylammonium acetate, cyanide ions prepared to have a predetermined concentration range are contained. Specifically, cyanide ions in a concentration of 0.006 ⁇ 10 -3 mol/L to 12.5 ⁇ 10 -3 mol/L are contained.
  • a reducing electroless silver plating solution to which a water-soluble silver salt, such as silver potassium cyanide, and a cyanide, such as potassium cyanide, are added as additives is excellent in solution stability, but, excessively dissolves and roughens metal or the like as an underlying plating material composed of, for example, copper or nickel, whereby a plating film having good film characteristics has not been formed.
  • a water-soluble silver salt such as silver potassium cyanide
  • a cyanide such as potassium cyanide
  • a cyanogen-free plating solution has been also developed in order to avoid such excessive dissolution of an underlying metal or the like, but, where a silver plating solution having low stability of the solution, in particular, is made to be cyanogen-free, then such plating solution causes rapid decomposition of silver contained in the plating solution, whereby the stability of the plating solution has been remarkably decreased. Furthermore, such cyanogen-free plating solution causes a yellowish plating film to be formed, whereby formation of a plating film having a good appearance has not been realized. The application of such silver plating film having a poor appearance to a LED device, for example, has caused a lower reflectivity.
  • the reducing electroless silver plating solution according to the present embodiment is made to contain cyanide ions having a concentration of 0.006 ⁇ 10 -3 mol/L to 12.5 ⁇ 10 -3 mol/L in the plating solution.
  • Such reducing electroless silver plating solution can achieve only the advantages brought by both the prior electroless silver plating solution using a cyanide and the prior cyanogen-free electroless silver plating solution, that is, achieve higher solution stability, and can form a plating film having excellent film characteristics without excessive roughening of a plated material, such as a underlying metal. Furthermore, this reducing electroless silver plating solution allows a plating film to have a beautiful white silver color and thus to have a good appearance, and when the plating film is applied to, for example, a LED device, reflectance characteristics thereof can be improved.
  • a source of cyanide ions is not particularly limited, but, for example, alkali metal cyanide, such as potassium cyanide or sodium cyanide, may be used. Furthermore, a silver cyanide compound, such as silver potassium cyanide, may be used as a water-soluble silver salt and made to be contained as a part or a whole of a source of cyanide ions so as to have the above-mentioned cyanide ion content.
  • alkali metal cyanide is more preferably used.
  • the use of alkali metal cyanide allows the cyanide having a cyanide ion concentration within the above-mentioned range to be appropriately and easily prepared, and allows solution stability to be maintained and a plating film having good film characteristics to be formed more efficiently and more effectively. Furthermore, also when a plating solution is continuously used, it is not necessary to add alkali metal cyanide too often, and furthermore, unlike the case with adding a silver cyanide compound , due to an increase in amount of silver contained in the plating solution, the solution stability are not decreased.
  • the water-soluble silver salt is not particularly limited as long as it is soluble in the plating solution, and examples of the water-soluble silver salt which may be used include silver nitrate, silver oxide, silver sulfate, silver chloride, silver sulfite, silver carbonate, silver acetate, silver lactate, silver sulfosuccinate, silver sulfonate, silver sulfamate, and silver oxalate.
  • a silver cyanide compound such as silver potassium cyanide, may be used as a water-soluble silver salt. These water-soluble silver salts may be used alone or two or more kinds thereof may be used in combination.
  • the water-soluble silver salt is preferably contained in a silver concentration of 0.1 g/L to 10 g/L (0.9 ⁇ 10 -3 mol/L to 90 ⁇ 10 -3 mol/L), more preferably 0.1 g/L to 3.0 g/L (0.9 ⁇ 10 -3 mol/L to 30 ⁇ 10 -3 mol/L).
  • a water-soluble silver salt is contained in a silver concentration within a range of 0.1 g/L to 10 g/L, a precipitation rate of silver plating can be higher, and also a plating solution having higher stability can be achieved.
  • a silver cyanide compound to be added or a cyanide as an additive contained together with the silver cyanide compound are made to be contained in a cyanide ion concentration within the above-mentioned range, that is a concentration of 0.006 ⁇ 10 -3 mol/L to 12.5 ⁇ 10 -3 mol/L.
  • the reducing agent is a hydroxylammonium salt.
  • the reducing agent is selected from hydroxylammonium sulfate and hydroxylammonium acetate.
  • these reducing agents make it possible to easily change plating thickness by controlling plating time, and to form a plating film having a desired plating thickness and good film characteristics with a film-thickening treatment or the like.
  • cyanide ions are controlled to be in a predetermined concentration range.
  • a reducing agent having higher reducing power such as DMAB
  • hydroxylammonium salt such as hydroxylammonium sulfate or hydroxylammonium acetate, prevents decomposition of silver in a plating solution, and thus can lead to a stable reduction reaction.
  • a reducing agent having weaker reducing power such as hydrazine or formaldehyde
  • a silver precipitation rate is slower. Therefore, a portion of the surface of an underlying metal or the like on which silver is not precipitated is present for a long time, and thus cyanogen in a plating solution may act on the portion and excessively dissolve it.
  • hydroxylammonium salts such as hydroxylammonium sulfate or hydroxylammonium acetate allows silver plating to be certainly precipitated by a reduction reaction without dissolution of an underlying metal or the like, and therefore, by control of plating time, the underlying metal or the like can be coated with silver plating with a desired film thickness, and a plating film having good film characteristics can be formed.
  • hydroxylammonium sulfate or hydroxylammonium acetate allows a plating film with a desired film thickness to be easily formed and solution stability to be higher, and prevents excessive dissolution of an underlying metal or the like due to cyanogen, whereby a plating film having good film characteristics can be more effectively formed.
  • a reducing agent is preferably contained in a concentration of, for example, 0.006 mol/L to 0.12 mol/L, more preferably 0.006 mol/L to 0.03 mol/L.
  • a reducing agent is contained in a concentration of less than 0.006 mol/L, it is possible that a water-soluble silver salt in a plating solution cannot be reduced to metallic silver and sufficient silver plating cannot be precipitated.
  • a reducing agent is contained in a concentration of more than 0.12 mol/L, the stability of a plating solution is adversely affected and it is not economically preferable.
  • the reducing electroless silver plating solution according to the present embodiment may be used at a liquid temperature within a range of 0 to 80 degrees C, and, particularly, the use of the plating solution at a temperature of approximately 30 to 60 degrees C allows the stability of the plating solution to be higher.
  • the temperature of the plating solution is too low, silver is precipitated at a slow rate, and it takes a long time to obtain a predetermined amount of silver precipitate.
  • the temperature of the plating solution is too high, it is easily to cause the loss of a reducing agent due to its autolysis reaction and the decrease in the stability in plating solution..
  • the reducing electroless silver plating solution may be used when the solution has a pH of 2 to 14, but, since cyanide ions are contained in a predetermined concentration as mentioned above, in particular, the reducing electroless silver plating solution preferably has a pH of 8 to 11.
  • the plating solution has a pH of not less than 8
  • generation of cyanogen gas can be effectively controlled and the plating solution can be safely used without adverse effects on environment.
  • the stability of the plating solution can be higher.
  • the plating solution having a pH of not more than 11 allows the stability of the plating solution and the film characteristics of a plating film to be improved.
  • the pH adjustment for a plating solution is carried out in such a manner that, when pH is lowered, an acid is usually used which has the same kind of anion portion as an anion portion of a water-soluble silver salt, for example, sulfuric acid in the case of using silver sulfate as a water-soluble silver salt, or nitric acid in the case of using silver nitrate as a water-soluble silver salt.
  • an acid which has the same kind of anion portion as an anion portion of a water-soluble silver salt
  • sulfuric acid in the case of using silver sulfate as a water-soluble silver salt
  • nitric acid in the case of using silver nitrate as a water-soluble silver salt.
  • alkali metal hydroxide such as sodium hydroxide, ammonia, or the like is used.
  • a complexing agent may be added as needed.
  • the complexing agent is not particularly limited, and examples of the complexing agent include sulfite, succinimide, hydantoin derivatives, ethylenediamine, and ethylenediaminetetraacetic acid (EDTA). These complexing agents may be used alone or two or more kinds thereof may be used in combination.
  • An amount of additive of the complexing agent depends on its kind and is not particularly limited, but preferably approximately 1 g/L to 100 g/L.
  • the complexing agent having such concentration allows a good precipitation rate of silver plating to be achieved and the plating solution to have more excellent stability.
  • an additive such as a well-known surface active agent, a pH adjuster, a buffer, a lubricant, and a stress relaxation agent, may be mixed, as needed.
  • a plating method using the reducing electroless silver plating solution having the above-mentioned characteristics is, for example, such that a plated material is immersed in the reducing electroless silver plating solution having the liquid temperature and the pH value each adjusted as mentioned above, whereby silver-plating is applied to the material. Also, the reducing electroless silver plating solution is sprayed or applied to a plated material, whereby the plated material is brought into contact with the plating solution to undergo a plating treatment.
  • the electroless silver plating method operates in such a manner that, mainly, a water-soluble silver salt is reduced to metallic silver with the reducing agent contained in the plating solution, and silver plating is precipitated on a plated material, such as metal, as an underlying plating material, whereby a plating film is formed.
  • the plated material to form an electroless silver plating film is not particularly limited, and metallic materials, such as copper and nickel, various kinds of other conductive materials and non-conductive materials, and the like may be applied.
  • a pretreatment such as a degreasing treatment, is applied thereto in accordance with a usual method, and then the plated material is directly immersed in a plating solution.
  • a pretreatment such as a degreasing treatment
  • an activation treatment is applied thereto, followed by immersion thereof in the plating solution.
  • the activation treatment is performed using a palladium catalyst(catalyst-accelerator process, sensitizer-activator process, or the like), a silver catalyst, a copper catalyst, or the like, in accordance with well-known conditions.
  • the reducing electroless silver plating solution comprises a water-soluble silver salt and a reducing agent selected from hydroxylammonium sulfate and hydroxylammonium acetate, wherein cyanide ions are contained at a concentration of 0.006 ⁇ 10 -3 mol/L to 12.5 ⁇ 10 -3 mol/L.
  • a reducing agent selected from hydroxylammonium sulfate and hydroxylammonium acetate, wherein cyanide ions are contained at a concentration of 0.006 ⁇ 10 -3 mol/L to 12.5 ⁇ 10 -3 mol/L.
  • Such reducing electroless silver plating solution is capable of effectively preventing the decomposition of silver contained in the silver plating solution thereby to achieve good stability of the solution and also capable of preventing excessive roughening of a plated material, such as an underlying metal, thereby to form a plating film having good film characteristics and a good appearance.
  • a reducing electroless silver plating solution was prepared in the same manner as in Example 1, except that potassium cyanide in a concentration of 300 mg/L was added, thereby allowing the plating solution to have a cyanide ion concentration of 1.8 ⁇ 10 -3 mol/L.
  • a reducing electroless silver plating solution was prepared in the same manner as in Example 1, except that potassium cyanide in a concentration of 500 mg/L was added, thereby allowing the plating solution to have a cyanide ion concentration of 3.0 ⁇ 10 -3 mol/L.
  • a reducing electroless silver plating solution was prepared in the same manner as in Example 1, except that potassium cyanide in a concentration of 1000 mg/L was added, thereby allowing the plating solution to have a cyanide ion concentration of 6.5 ⁇ 10 -3 mol/L.
  • a reducing electroless silver plating solution was prepared in the same manner as in Example 1, except that potassium cyanide in a concentration of 2000 mg/L was added, thereby allowing the plating solution to have a cyanide ion concentration of 12.5 ⁇ 10 -3 mol/L.
  • a reducing electroless silver plating solution was prepared in the same manner as in Example 1, except that a silver potassium cyanide having a silver concentration of 9.0 ⁇ 10 -3 mol/L (1.0 g/L) was added in place of silver nitrate, and furthermore a potassium cyanide in a concentration of 300 mg/L was added, whereby the plating solution had a cyanide ion concentration of 19.8 ⁇ 10 -3 mol/L.
  • a reducing electroless silver plating solution was prepared in the same manner as in Example 1, except that a silver potassium cyanide having a silver concentration of 9.0 ⁇ 10 -3 mol/L (1.0 g/L) was added in place of silver nitrate, and potassium cyanide was not added, whereby the plating solution had a cyanide ion concentration of 18.0 ⁇ 10 -3 mol/L.
  • a reducing electroless silver plating solution was prepared in the same manner as in Example 1, except that potassium cyanide was not added. In other words, a cyanogen-free reducing electroless silver plating solution was prepared.
  • a reducing electroless silver plating solution was prepared in the same manner as in Example 1, except that a potassium cyanide in a concentration of 2100 mg/L was added, thereby allowing the plating solution to have a cyanide ion concentration of 13.0 ⁇ 10 -3 mol/L.
  • reducing electroless silver plating was applied to a BGA substrate (manufactured by C. Uyemura & Co., Ltd.) as a plated material.
  • each step shown in the following Table 1 was performed in order as a pretreatment.
  • a cleaner treatment degreasing
  • ACL-738 manufactured by C. Uyemura & Co., Ltd.
  • SPS sodium persulfate solution
  • etching residues were removed using a 10% sulfuric acid (H 2 SO 4 ) solution (acid pickling), and pre-dipping was performed using a 3% sulfuric acid solution, and then a Pd catalyst treatment was performed using MNK-4 (manufactured by C. Uyemura & Co., Ltd.) (catalyst treatment).
  • MNK-4 manufactured by C. Uyemura & Co., Ltd.
  • electroless palladium solution TPD-30 manufactured by C. Uyemura & Co., Ltd.
  • the electroless silver plating treatment was performed in such a manner that a plated material was immersed in the above-mentioned reducing electroless silver plating solution at 60 degrees C for 20 minutes. After performing the plating treatment, the plating solution was left for 100 hours with keeping the temperature at 60 degrees C. Then, the stability of the plating solution was evaluated by whether the plating solution was self-decomposed or not, and also the solder joint strength and the appearance of a plating film were evaluated.
  • Table 2 shows evaluation results.
  • solder joint strength of a plating film in order to evaluate the solder joint strength of a plating film, a reflow treatment was performed once at 240 degrees C, and the joint strength was evaluated in such a manner that, when a solder fracture mode was found in 16 or more among 20 solder joints, the joint strength was evaluated to be good ( ⁇ ), on the other hand, when a solder fracture mode was found in less than 16 solder joints, the joint strength was evaluated to be poor ( ⁇ ). Furthermore, the appearance of a silver plating film was evaluated by visually observing the appearance of the plating film having a thickness of 0.5 micrometer.
  • a reducing electroless silver plating solution having a cyanide ion concentration of 0.006 ⁇ 10 -3 mol/L was prepared in the same manner as in Example 2, except that hydrazine (hydrazine sulfate) in a concentration of 1.24 ⁇ 10 -3 mol/L was added as a reducing agent.
  • a reducing electroless silver plating solution having a cyanide ion concentration of 0.006 ⁇ 10 -3 mol/L was prepared in the same manner as in Example 2, except that formaldehyde in a concentration of 1.24 ⁇ 10 -3 mol/L was added as a reducing agent.
  • the use of a hydroxylammonium salt, such as hydroxylammonium sulfate or hydroxylammonium acetate as a reducing agent allows a reduction reaction to proceed more effectively and dissolution of an underlying metal by a substitution reaction not to be caused, whereby a plating film having good film characteristics can be formed.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Claims (4)

  1. Reduktionslösung zur stromlosen Abscheidung von Silber, umfassend: ein wasserlösliches Silbersalz und ein Reduktionsmittel,
    wobei Cyanid-Ionen in einer Konzentration von 0,006 x 10-3 Mol/L bis 12,5 x 10-3 Mol/L enthalten sind, und
    wobei das oben erwähnte Reduktionsmittel zumindest eine Art oder mehr ist, die aus Hydroxylammoniumsulfat und Hydroxylammoniumacetat ausgewählt wird.
  2. Reduktionslösung zur stromlosen Abscheidung von Silber nach Anspruch 1, wobei das oben erwähnte wasserlösliche Silbersalz ein anderes Silbersalz als ein Cyanid ist und die oben erwähnten Cyanid-Ionen als ein Alkalimetallcyanid enthalten sind.
  3. Reduktionslösung zur stromlosen Abscheidung von Silber nach Anspruch 1, mit einem pH von 8 bis 11.
  4. Reduktionsverfahren zur stromlosen Abscheidung von Silber, wobei unter Verwendung der Reduktionslösung zur stromlosen Abscheidung von Silber nach Anspruch 1 eine stromlose Abscheidung von Silber auf ein plattiertes Material angewendet wird.
EP12843616.9A 2011-10-27 2012-10-09 Zusammensetzung für die stromlose abscheidung von silber und entsprechendes verfahren Active EP2772566B1 (de)

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CH710579A1 (fr) * 2014-12-23 2016-06-30 Metalor Tech Int Sa Procédé de placage autocatalytique d'un métal précieux.
US20170051411A1 (en) * 2015-08-20 2017-02-23 Macdermid Acumen, Inc. Electroless Silver Plating Bath and Method of Using the Same
JP6650136B2 (ja) * 2015-09-02 2020-02-19 学校法人神奈川大学 フレキシブル熱電変換部材の作製方法
JP6645881B2 (ja) * 2016-03-18 2020-02-14 上村工業株式会社 銅めっき液及び銅めっき方法
KR102077426B1 (ko) * 2019-07-01 2020-04-08 최철수 박형 전도성 부직포 제조방법 및 이에 의해 제조된 박형 전도성 부직포
CN112159975A (zh) * 2020-10-12 2021-01-01 福建新大陆环保科技有限公司 在细长玻璃管内镀金属银制备高压电极的方法
CN114808052B (zh) * 2022-04-02 2024-03-15 中国机械总院集团武汉材料保护研究所有限公司 一种氰化物镀银溶液的无氰化转化方法
CN114959666A (zh) * 2022-05-12 2022-08-30 李正新 化学镀银液以及化学镀银新方法
CN114932218B (zh) * 2022-05-30 2023-08-04 暨南大学 一种通过化学镀银来降低3d打印锌粉蒸发形成锌银合金的方法

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