CN105274584A - Film-forming metal soution and metal film-forming method - Google Patents
Film-forming metal soution and metal film-forming method Download PDFInfo
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- CN105274584A CN105274584A CN201510426952.4A CN201510426952A CN105274584A CN 105274584 A CN105274584 A CN 105274584A CN 201510426952 A CN201510426952 A CN 201510426952A CN 105274584 A CN105274584 A CN 105274584A
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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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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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
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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
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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- Electroplating Methods And Accessories (AREA)
- Electrodes Of Semiconductors (AREA)
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Abstract
A film-forming metal solution for supplying metal ions to a solid electrolyte membrane in film formation is provided. In the film formation, the solid electrolyte membrane is disposed between an anode and a substrate as a cathode, and the solid electrolyte membrane is brought into contact with the substrate and a voltage is placed between the anode and the substrate to precipitate a metal on a surface of the substrate from the metal ions contained in the solid electrolyte membrane, so that a metal film of the metal is formed on the surface of the substrate. The film-forming metal solution contains a solvent, and the metal dissolved in the solvent in an ionic state. A hydrogen ion concentration of the film-forming metal solution is within a range of 0 to 10 -7.85 mol/L at 25 DEG C.
Description
Technical field
The present invention relates to the film forming metallic solution for the formation of nickel film, and use this film forming metallic solution to form the metal film formation method of metallic membrane.More specifically, the present invention relates to be adapted to pass through and solid electrolyte film is contacted with base material on the surface of base material, form the film forming metallic solution of metallic membrane, and use this film forming metallic solution to form the metal film formation method of metallic membrane.
Background technology
In the process manufacturing electronic circuit base material etc., on the surface of base material, be usually formed with nickel film to form nickel circuit pattern.The technology of this metal film of formation proposed comprises the technology (such as, see Japanese Patent Application No.2010-037622 (JP2010-037622A)) being formed metallic membrane by the plating of such as electroless plating and so on the surface of the semiconductor substrate be made up of silicon (Si) etc. and the technology being formed metallic membrane by the physical vapor deposition (PVD) of such as sputter and so on.
But the plating of such as electroless plating and so on defines to the demand of washing base material after plating with to the demand of washing the waste liquid that brings and processing.When the PVD by such as sputter and so on forms film on the surface of base material, in formed metallic membrane, produce internal stress.This is applied with restriction to the increase of thickness.Especially, when adopting sputter, film only can be formed under a high vacuum.
In view of this point, such as, propose film deposition system (such as, see WO2013/125643) as shown in Figure 4, this film deposition system at least comprises anode 11, solid electrolyte film 13 and power supply unit (not shown).Anode 11 is made of porous materials.Solid electrolyte film 13 is configured between anode 11 and the base material B being used as negative electrode, and the anode 11 side part of the aqueous solution and solid electrolyte film 13 comprising metal ion is contacted.Power supply unit applies voltage between anode 11 and base material B.
The outer cover 15 of this film deposition system has reservoir 19, and the aqueous solution comprising metal ion is stored in this reservoir.Anode 11 and solid electrolyte film 13 are arranged so that the aqueous solution comprising metal ion be stored in reservoir 19 can be fed into solid electrolyte film 13 via anode 11.
For above-mentioned film deposition system, the metallic membrane F be made of metal is formed on the surface of base material B.Particularly, when power supply unit applies voltage between anode 11 and base material B, metallic membrane F is formed on the surface of base material B, and the metal ion that metal is comprised from solid electrolyte film 13 is separated out on the surface of base material B.
But, when adopting the technology recorded in WO2013/125643, between solid electrolyte film 13 and base material B, may hydrogen be produced, and the hydrogen produced like this may be accumulated between solid electrolyte film 13 and base material B.The hydrogen of accumulation is present between solid electrolyte film 13 with the base material B contacted with solid electrolyte film 13 under stress in bubble form as shown in Figure 4.Thus, metal can be hindered to separate out in the position being formed with hydrogen gas bubbles.As a result, in metallic membrane F, define that metal is undecomposed does not separate out portion (space), and these spaces make metallic membrane F uneven.
Summary of the invention
The invention provides a kind of in order to suppress be positioned to the film forming metallic solution producing hydrogen between solid electrolyte film contacting one another and base material, and use this film forming metallic solution to form the metal film formation method of metallic membrane.
As the result conscientiously studied, the present inventor's presumption is when the metal solvent be dissolved under ionic condition is wherein water, the hydrogen ion (free hydrogen) existed due to the self-ionized of water is reduced when metal is separated out on the surface of base material being used as negative electrode, thus produces hydrogen.Based on this presumption, the present inventor obtained use the hydrogen ion concentration solvent lower than water to make can than when using water as the new discovery of generation suppressing hydrogen when solvent more reliably.
The present invention is this new discovery obtained based on the present inventor.A first aspect of the present invention relate to a kind of for when film forming to the film forming metallic solution of solid electrolyte film supply metal ion, when film forming, described solid electrolyte film is configured between anode and the base material as negative electrode, and described solid electrolyte film contacts with described base material and voltage is applied in the metal ion comprised from described solid electrolyte film precipitating metal on the surface of described base material between described anode and described base material, thus forms the metallic membrane of described metal on the surface of described base material.Described film forming metallic solution comprises solvent and under ionic condition, is dissolved in the metal in described solvent.The hydrogen ion concentration of described film forming metallic solution is in 0 to 10 at 25 DEG C
-7.85in the scope of mol/L.
According to a first aspect of the invention, by the hydrogen ion concentration of film forming metallic solution being maintained in above-mentioned scope the total amount reducing the hydrogen ion (proton) moving to cathode side from the anode side of solid electrolyte film.Therefore, can suppress to produce hydrogen being positioned between solid electrolyte film contacting one another and base material.
The hydrogen ion concentration of 0mol/L means that film forming metallic solution does not comprise hydrogen ion, and the higher limit 10 of hydrogen ion concentration
-7.85mol/L (at 25 DEG C) is lower than obtain when water self-ionized 10
-7the hydrogen ion concentration of mol/L.As the result of the experiment that the present inventor carries out, find when hydrogen ion concentration is more than 10
-7.85time mol/L (at 25 DEG C), do not form uniform metallic membrane due to the generation of hydrogen.
In the present invention, when the metal-salt being used as solute does not comprise hydrogen, the hydrogen ion concentration of film forming metallic solution equals the hydrogen ion concentration of solvent.The metal-salt of metal being used for being formed film due to major part does not comprise hydrogen, so the hydrogen ion concentration of film forming metallic solution equals the hydrogen ion concentration of solvent.
This solvent preferably has the hydrogen ion concentration lower than the hydrogen ion concentration of water when self-ionized, and the example of this solvent comprises protophobic solvent and alcoholic solvent.In these solvents, metal exists under ionic condition (that is, metal can be dissolved in these solvents under ionic condition).
Described solvent can be the alcoholic solvent comprising at least one being selected from methyl alcohol, ethanol and propyl alcohol (1-propyl alcohol or 2-propyl alcohol) or the solvent comprising described alcoholic solvent and water.
According to this aspect, the hydrogen ion concentration of methyl alcohol, ethanol or propyl alcohol is respectively 10
-8.35mol/L, 10
-8.55mol/L and 10
-8.25mol/L, these hydrogen ion concentrations are all lower than above-mentioned 10
-7.85the upper concentration of mol/L (at 25 DEG C), and the possibility therefore producing hydrogen between solid electrolyte film and base material is low.When using methyl alcohol, ethanol or propyl alcohol, the metal of such as nickel, tin or copper and so on can dissolve in a solvent under ionic condition.As long as hydrogen ion concentration is 10
-7.85below mol/L (at 25 DEG C), alcoholic solvent can comprise water.
The described metal dissolved in a solvent can have the ionization tendency higher than the ionization tendency of hydrogen.When use has the metal of the ionization tendency higher than the ionization tendency of hydrogen, during the precipitation of metal, easily produce hydrogen.Thus, as in this aspect of the invention, hydrogen ion concentration is limited effective especially.Thus, the possibility producing hydrogen during metal is separated out is low, and therefore forms uniform metallic membrane.
Among the metal species that will separate out, the metal (such as copper or silver) with the redox potential higher than the redox potential of hydrogen has the ionization tendency lower than the ionization tendency of hydrogen, and therefore easily separates out during separating out.But, even if when using this metal, also may hydrogen be produced during separating out under some filming condition.Thus, even if when using this metal, above-mentioned aspect of the present invention has also played the effect suppressing hydrogen to produce.
The described metal with the ionization tendency higher than the ionization tendency of hydrogen is nickel.Experiment as carried out from the present inventor is obvious, comprising nickel ion and the solution with the hydrogen ion concentration be in above-mentioned scope, obtaining uniform nickel film by using.
A second aspect of the present invention relates to a kind of metal film formation method for using above-mentioned film forming metallic solution to form metallic membrane.According to this metal film formation method, solid electrolyte film is configured with between anode and the base material as negative electrode, and solid electrolyte film contacted with base material and between anode and base material, applies voltage with the metal ion comprised from solid electrolyte film precipitating metal on the surface of base material, thus on the surface of base material, forming the metallic membrane of metal.
In the case, when by making film forming metallic solution contact to supply metal ion to solid electrolyte film with solid electrolyte film, between anode and base material, voltage is applied to form metallic membrane on the surface of base material.
According to this aspect, can suppress when by be positioned at solid electrolyte film and base material form metallic membrane from metal ion precipitating metal under state contacting one another time contingent hydrogen produce while formation metallic membrane.
According to each aspect of the present invention, can suppress to produce hydrogen being positioned between solid electrolyte film contacting one another and base material.
Accompanying drawing explanation
The feature of illustrative embodiments of the present invention, advantage and technology and industrial significance are described below with reference to accompanying drawings, and Reference numeral similar in the accompanying drawings represents similar key element, and wherein:
Fig. 1 is the schematic conceptualization figure of metallic membrane forming apparatus according to an embodiment of the invention;
Fig. 2 is the schematic sectional view of the metal film formation method that the metallic membrane forming apparatus for describing as shown in Figure 1 performs;
Fig. 3 A is the photo of the nickel film obtained in example 2;
Fig. 3 B is the photo of the nickel film obtained in comparative example 2; And
Fig. 4 is the figure for describing problem when using the conventional film deposition system comprising solid electrolyte film to form film.
Embodiment
Hereinafter, the metallic membrane forming apparatus that suitably can perform metal film formation method according to an embodiment of the invention will be described.
Fig. 1 is the schematic concept map of metallic membrane forming apparatus 1A (hereinafter, simply referred to as " film deposition system 1A ") according to this embodiment of the invention.Fig. 2 is the schematic sectional view for illustration of being performed the metal film formation method to form the metallic membrane F shown in Fig. 1 by film deposition system 1A.
As shown in Figure 1, film deposition system 1A according to the present invention from metal ion precipitating metal, to form the metallic membrane be made up of the metal of separating out on the surface of base material B.Base material B in the present embodiment is the base material be made up of the metallic substance of such as aluminium, or master metal coating formation surface treated resin thereon or silicon substrate.
Film deposition system 1A at least comprises the anode 11, solid electrolyte film 13 and the power supply unit 14 that are made of metal.The position of solid electrolyte film 13 between anode 11 and the base material B being used as negative electrode is configured on the surface of anode 11.Power supply unit 14 applies voltage between anode 11 and the base material B being used as negative electrode.
Anode 11 is incorporated in anode 11 and supplies in the outer cover (metal ion supply unit) 15 of the solution L (hereinafter referred to as " metallic solution ") comprising metal ion formed for film.Outer cover 15 has the breakthrough part of through along the vertical direction outer cover 15, and anode 11 is incorporated in the internal space of outer cover 15.Solid electrolyte film 13 has the recess of the bottom surface covering anode 11.Solid electrolyte film 13 covers the open lower side of the breakthrough part of outer cover 15 under the bottom of anode 11 is incorporated in the state in solid electrolyte film 13.
In the breakthrough part of outer cover 15, be configured with the contact pressurization part (metallic punch) 20 of pressurizeing with antianode 11 that to contact with the end face of anode 11.Contact pressurization part 20 is pressurizeed via anode 11 pairs of solid electrolyte films 13, is pressurizeed by solid electrolyte film 13 in the surface of base material B.Particularly, the surface-pressure corresponding with the film-forming region E that the surface of base material B will be formed metallic membrane F of contact pressurization part 20 antianode 11, makes film-forming region E be pressurizeed equably.
In the present embodiment, the bottom surface of anode 11 has the size consistent with the film-forming region E of base material B, and the end face of anode 11 is identical with the size of bottom surface.Therefore, when (all) end faces of anode 11 be touched press section 20 utilize the thrust applied by pressure exerting device 16 (illustrating after a while) to pressurize time, (all) film-forming region E of base material B are pressurizeed via solid electrolyte film 13 equably by (all) bottom surfaces of anode 11.
In addition, NaOH solution tank NaOH 17 is connected with the side of outer cover 15 via supply-pipe 17a, and waste liquid tank 18 is connected with the opposite side of outer cover 15 via sewer pipe 18a.Metallic solution L is stored in NaOH solution tank NaOH 17, and waste liquid---that is the metallic solution L after using---is collected in waste liquid tank 18.
Supply-pipe 17a is connected with the supply passageway 15a of outer cover 15, and metallic solution L is fed into anode 11 through described supply passageway 15a.Sewer pipe 18a is connected with the drain passageway 15b of outer cover 15, and metallic solution L is discharged in waste liquid tank 18 through described drain passageway.As shown in Figure 2, the anode 11 be made of porous materials is configured in the path be connected to each other by the supply passageway 15a of outer cover 15 and drain passageway 15b.
Due to this structure, the metallic solution L be stored in NaOH solution tank NaOH 17 is supplied in outer cover 15 through supply-pipe 17a.In outer cover 15, metallic solution L flows through supply passageway 15a, then flows into anode 11 from supply passageway 15a.The metallic solution L passed through from anode 11 flows through drain passageway 15b and is sent to waste liquid tank 18 through sewer pipe 18a.
In addition, pressure exerting device 16 with contact pressurization part 20 and connect.Solid electrolyte film 13 is pressed against on the film-forming region E of base material B by making anode 11 move towards base material B by pressure exerting device 16.The example of pressure exerting device 16 comprises hydro-cylinder and pneumatic linear actuator.Film deposition system 1A also comprises pedestal 21, and base material B is fixed on this pedestal.Pedestal 21 is used for regulating base material B relative to the alignment of anode 11.
Anode 11 by allow metallic solution L from wherein by and make to the porous material that solid electrolyte film 13 supplies metal ion.Porous material is not limited to any specific porous material, as long as (1) this porous material has the erosion resistance of opposing metallic solution L, (2) this porous material has sufficiently high electric conductivity to be used as anode, (3) this porous material allows metallic solution L from wherein passing through, and (4) this porous material can be pressurizeed via above-mentioned contact pressurization part 20 by pressure exerting device 16.The example of porous material comprises the ionization tendency (or higher electropotential) lower than having with plated metal Ion Phase and the metal foam be made up of the open celled foam with open pores, such as titanium foam.
When using metal foam, metal foam is not limited to any special metal foam, as long as this metal foam meets above-mentioned condition (3).But, preferably use the metal foam of thickness with the porosity of by volume about 50% to 95%, the aperture of about 50 to 600 μm and about 0.1 to 50mm.
Solid electrolyte film 13 is not limited to any particular solid dielectric film, as long as solid electrolyte film 13 can be infiltrated by metal ion when solid electrolyte film 13 contacts with metallic solution L and the metal derived by metal ion can be separated out on the surface of base material B in response to the applying of voltage.The example of the material of solid electrolyte film 13 comprises and such as being manufactured by E.I.Du Pont Company
fluoro-resin, hydrocarbon resin, polyamic acid resin and the resin with ion exchanging function of SELEMION (comprise CMV, CMD and CMF series) that such as manufactured by Asahi Glass Glass Co., Ltd..
In the present embodiment, use porous material as the anode 11 of the device for the formation of metallic membrane F.But, as long as metal ion can be supplied to solid electrolyte film 13, just can form gap between anode and solid electrolyte film and metallic solution can be supplied in this gap, as described later.
Hereinafter, be used for using film deposition system 1A to form the metal film formation method of metallic membrane by illustrating.First, as depicted in figs. 1 and 2, base material B is placed on pedestal 21, regulates base material B relative to the alignment of anode 11, and regulate the temperature of base material B.Next, solid electrolyte film 13 is configured on the surface of the anode 11 be made of porous materials, and solid electrolyte film 13 is contacted with base material B.
Next, by pressure exerting device 16, anode 11 is moved towards base material B, solid electrolyte film 13 is compressed against on the film-forming region E of base material B.Therefore, pressurize via anode 11 pairs of solid electrolyte films 13, and therefore solid electrolyte film 13 fits the surface of the film-forming region E pasting base material B equably.In other words, by use keep solid electrolyte film 13 to contact (being pressed against thereon) with base material B by the anode that pressurizes of contact pressurization part 20 as back lining materials time, define thickness evenly metallic membrane F.
Next, power supply unit 14 applies voltage between anode 11 and the base material B being used as negative electrode, and the metal ion that metal is comprised from solid electrolyte film 13 is separated out on the surface of base material B.Anode 11 directly contacts with the contact pressurization part 20 be made of metal, and therefore anode 11 conducts with contacting between pressurization part 20.Therefore, power supply unit 14 can apply voltage between anode 11 and base material B.
In the case, metallic membrane is formed when making metallic solution L flow through anode 11.The anode 11 be made of porous materials is used to allow metallic solution L to pass through from anode 11.Therefore, metallic solution L is fed into solid electrolyte film 13 together with metal ion.Therefore, in the process forming metallic membrane, metallic solution L is by constant and be stably supplied in the anode 11 that is made of porous materials.The metallic solution L of such supply passes through from anode 11 and contacts with the solid electrolyte film 13 that contiguous anode 11 configures, and therefore solid electrolyte film 13 is infiltrated by metal ion.
When voltage is applied between anode 11 and the base material B being used as negative electrode, the metal ion comprised in solid electrolyte film 13 moves to base material B side from anode 11 side, and the metal ion that then metal comprises from solid electrolyte film 13 is separated out on the surface of base material B.As a result, metallic membrane F is formed on the surface of base material B.
Like this, the film-forming region E of base material B is pressurizeed equably by solid electrolyte film 13, and under the state of therefore fitting the film-forming region E of subsides base material B at solid electrolyte film 13 equably, metallic membrane F is formed on base material B.As a result, the homogeneous metal film F with the less uniform thickness of change is formed on the surface of film-forming region E of base material B.
Metallic solution L comprises solvent and under ionic condition, is dissolved in the metal (metal ion) in this solvent.In the present embodiment, the hydrogen ion concentration of metallic solution is in 0 to 10 at 25 DEG C
-7.85in the scope of mol/L.
When the hydrogen ion concentration of metallic solution L is maintained in above-mentioned scope, the total amount moving to the hydrogen ion (proton) of cathode side from the anode side of solid electrolyte film 13 reduces.Therefore, can suppress to produce hydrogen being positioned between solid electrolyte film 13 contacting one another and base material B.
Hydrogen ion concentration is that the solvent of 0mol/L is not for comprise hydrionic solvent.The example of this solvent comprises protophobic solvent, such as tetrahydrofuran (THF) (THF), acetonitrile, DMF (DMF) and dimethyl sulfoxide (DMSO).Because these solvents have polarity, so these solvents can comprise the metal being in ionic condition, such as nickel, tin or copper (illustrating after a while).
Hydrogen ion concentration is 10
-7.85the example of the solvent of the metallic solution of below mol/L (at 25 DEG C) comprises alcoholic solvent.The solvent obtained by adding water to alcoholic solvent can be used, as long as this solvent meets the above-mentioned condition relevant with hydrogen ion concentration.
Can comprise be in the such as nickel of ionic condition, the example of alcoholic solvent of the metal of tin or copper and so on comprises methyl alcohol, ethanol, propyl alcohol (1-propyl alcohol or 2-propyl alcohol) and the solvent that obtains by being mixed by least two kinds in these solvents.Even if when adding the water of seldom amount to this alcoholic solvent, water molecules and alcohol molecule are bonded to each other to suppress to produce free hydrogen in solvent.
The hydrogen ion concentration comprising the metallic solution of nickel, tin or copper is substantially equal to the hydrogen ion concentration of alcoholic solvent (or moisture alcoholic solvent).
The metal that will dissolve in a solvent being in ionic condition is put in the solvent in ionizable metallic salt form, is then dissolved in this solvent under ionic condition.The example of this metal comprises cobalt, iron, nickel, tin, copper and silver.Among these metals, preferably use nickel and the tin with the ionization tendency higher than the ionization tendency of hydrogen.
When using this metal, there is the metal of the ionization tendency higher than the ionization tendency of hydrogen by applying voltage and separate out on the surface of base material B between anode 11 and base material B.As a result, the possibility producing hydrogen in the process forming metallic membrane F is low, and therefore obtains uniform metallic membrane F.
Hereinafter with reference to following example, the present invention is described.
Example 1
Nickelous chloride (metal-salt) is dissolved in methyl alcohol (solvent) to prepare 0.1M nickel solution (metallic solution).Solid electrolyte (is manufactured by E.I.Du Pont Company; NafionN117) and nickel porous flaggy be stacked in Copper base material, and supply this 0.1M nickel solution to nickel porous plate.Then, nickel porous plate is electrically connected with Copper base material, and applies the constant voltage 60 seconds of 2.4V.Like this, nickel film is formed in Copper base material.
Example 2
Nickel film is formed in the mode similar to example 1.Be to use ethanol as solvent with the difference of example 1.
Example 3
Nickel film is formed in the mode similar to example 1.Be to use propyl alcohol (1-propyl alcohol) as solvent with the difference of example 1.
Example 4
Nickel film is formed in the mode similar to example 1.With the difference of example 1 be to use the mixed solution of first alcohol and water (comprise by volume 90% methyl alcohol and by volume 10% the mixed solution of water) as solvent.
Comparative example 1
Nickel film is formed in the mode similar to example 1.With the difference of example 1 be to use the mixed solution of first alcohol and water (comprise by volume 85% methyl alcohol and by volume 15% the mixed solution of water) as solvent.
Comparative example 2
Nickel film is formed in the mode similar to example 1.Be to use water as solvent with the difference of example 1.
Comparative example 3
Nickel film is formed in the mode similar to example 1.Be to use butanols (n-butyl alcohol) as solvent with the difference of example 1.
The visual inspection of film
Visual inspection is carried out to the nickel film obtained in example 1 to 4 and comparative example 1 to 3.Result illustrates in Table 1.Table 1 also show the value (theoretical value) calculated of the hydrogen ion concentration of film forming metallic solution (solvent) at 25 DEG C in example 1 to 4 and comparative example 1 to 3.
Table 1
Result
As the result of the visual inspection to the nickel film obtained in each example 1 to 4, observe the precipitation of nickel and the uniform hue of the nickel of separating out, and therefore confirm to obtain uniform nickel film.Fig. 3 A is the photo of the nickel film obtained in example 2.
As the result of the visual inspection to the nickel film obtained in comparative example 1, observe the precipitation of nickel, but the tone of the nickel of separating out is spot blocky, this reveals that the existence in space.
As the result of the visual inspection to the nickel film obtained in comparative example 2, the tone of nickel film is spot blocky, this reveals that the existence in space.Spot blocky is than more obvious (see Fig. 3 B) in comparative example 1.
The reason presumption obtaining the result of comparative example 1 and 2 is as follows.In comparative example 1 and 2, the amount of free hydrogen is greater than the amount of the free hydrogen in example 1 to 4.Therefore, hydrogen ion (proton) is reduced when voltage is applied between anode and base material.As a result, between solid electrolyte film and base material, hydrogen is produced.Therefore, hydrogen is accumulated in the precipitation disturbing nickel between solid electrolyte film and base material, and produces space (not separating out part), thus causes the film formed in spot blocky.
In comparative example 3, nickelous chloride does not dissolve in a solvent, and does not observe the precipitation of nickel film.Its reason may be as follows.Along with the carbon amounts formed in the molecule of solvent increases, the polarity of molecule declines, and therefore nickel cannot dissolve in a solvent under ionic condition.
Although describe embodiments of the invention in detail, the present invention is not limited to above-described embodiment, but can implement with other embodiment various within the scope of the invention.
In the above-described embodiments, the anode be made of porous materials is employed.But, porous material need not be used as anode, as long as nickel ion is supplied suitably solid electrolyte film.Such as, nickel solution can be supplied in the gap between anode and solid electrolyte film.
Claims (5)
1. one kind for when film forming to the film forming metallic solution of solid electrolyte film supply metal ion, when film forming, described solid electrolyte film is configured between anode and the base material as negative electrode, and described solid electrolyte film contacts with described base material and voltage is applied between described anode and described base material with the metal ion comprised from described solid electrolyte film precipitating metal on the surface of described base material, thus on the surface of described base material, form the metallic membrane of described metal, the feature of described film forming metallic solution is:
Described film forming metallic solution comprises solvent and under ionic condition, is dissolved in the metal in described solvent; And
The hydrogen ion concentration of described film forming metallic solution is in 0 to 10 at 25 DEG C
-7.85in the scope of mol/L.
2. film forming metallic solution according to claim 1, wherein, described solvent is comprise the alcoholic solvent of at least one being selected from methyl alcohol, ethanol and propyl alcohol or comprise the solvent of described alcoholic solvent and water.
3. film forming metallic solution according to claim 1 and 2, wherein, described metal has the ionization tendency higher than the ionization tendency of hydrogen.
4. film forming metallic solution according to claim 3, wherein, described metal is nickel.
5. the metal film formation method for using film forming metallic solution according to any one of claim 1 to 4 to form metallic membrane, it is characterized in that, when by making described film forming metallic solution contact with described solid electrolyte film to supply described metal ion to described solid electrolyte film, between described anode and described base material, apply voltage to form described metallic membrane on the surface of described base material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-148867 | 2014-07-22 | ||
| JP2014148867A JP6065886B2 (en) | 2014-07-22 | 2014-07-22 | Metal film deposition method |
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| Publication Number | Publication Date |
|---|---|
| CN105274584A true CN105274584A (en) | 2016-01-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510426952.4A Pending CN105274584A (en) | 2014-07-22 | 2015-07-20 | Film-forming metal soution and metal film-forming method |
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| Country | Link |
|---|---|
| US (1) | US20160024675A1 (en) |
| EP (1) | EP2977488A1 (en) |
| JP (1) | JP6065886B2 (en) |
| KR (1) | KR20160011594A (en) |
| CN (1) | CN105274584A (en) |
| BR (1) | BR102015017213A2 (en) |
| RU (1) | RU2614655C2 (en) |
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| CN108624924A (en) * | 2017-03-23 | 2018-10-09 | 丰田自动车株式会社 | The forming method of nickel epithelium and nickel solution for this method |
| CN109416326A (en) * | 2016-06-30 | 2019-03-01 | 国立大学法人京都大学 | The manufacturing method and probe of probe |
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| JP2020132948A (en) * | 2019-02-20 | 2020-08-31 | トヨタ自動車株式会社 | Film forming apparatus for metal film |
| JP7151673B2 (en) | 2019-09-13 | 2022-10-12 | トヨタ自動車株式会社 | Method for forming metal plating film |
| JP7238712B2 (en) * | 2019-09-18 | 2023-03-14 | トヨタ自動車株式会社 | Wiring board manufacturing method and wiring board |
| JP2022066011A (en) | 2020-10-16 | 2022-04-28 | トヨタ自動車株式会社 | Film deposition method of metal plating film and film deposition apparatus |
| JP7472770B2 (en) * | 2020-12-15 | 2024-04-23 | トヨタ自動車株式会社 | Metal plating film forming apparatus and method |
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- 2015-07-17 BR BR102015017213A patent/BR102015017213A2/en not_active Application Discontinuation
- 2015-07-20 CN CN201510426952.4A patent/CN105274584A/en active Pending
- 2015-07-21 KR KR1020150102888A patent/KR20160011594A/en active IP Right Grant
- 2015-07-22 EP EP15177944.4A patent/EP2977488A1/en not_active Withdrawn
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Also Published As
| Publication number | Publication date |
|---|---|
| RU2614655C2 (en) | 2017-03-28 |
| BR102015017213A2 (en) | 2016-01-26 |
| EP2977488A1 (en) | 2016-01-27 |
| JP6065886B2 (en) | 2017-01-25 |
| RU2015128877A (en) | 2017-01-23 |
| US20160024675A1 (en) | 2016-01-28 |
| JP2016023338A (en) | 2016-02-08 |
| KR20160011594A (en) | 2016-02-01 |
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