US20160024675A1 - Film-forming metal soution and metal film-forming method - Google Patents

Film-forming metal soution and metal film-forming method Download PDF

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Publication number
US20160024675A1
US20160024675A1 US14/805,721 US201514805721A US2016024675A1 US 20160024675 A1 US20160024675 A1 US 20160024675A1 US 201514805721 A US201514805721 A US 201514805721A US 2016024675 A1 US2016024675 A1 US 2016024675A1
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Prior art keywords
metal
film
substrate
solid electrolyte
electrolyte membrane
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Abandoned
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US14/805,721
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English (en)
Inventor
Motoki Hiraoka
Hiroshi Yanagimoto
Yuki Sato
Kensuke Akamatsu
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Toyota Motor Corp
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Toyota Motor Corp
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Assigned to TOYOTA JIDOSHA KABUSHIKI KAISHA reassignment TOYOTA JIDOSHA KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AKAMATSU, KENSUKE, HIRAOKA, MOTOKI, SATO, YUKI, YANAGIMOTO, HIROSHI
Publication of US20160024675A1 publication Critical patent/US20160024675A1/en
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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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to a film-forming metal solution for forming a nickel film, and a metal film-forming method of forming a metal film using the film-forming metal solution. More specifically, the invention relates to a film-forming metal solution suitable for forming a metal film on a surface of a substrate by bringing a solid electrolyte membrane into contact with the substrate, and a metal film-forming method of forming a metal film using the film-forming metal solution.
  • a nickel film is conventionally formed on a surface of a substrate to form a nickel circuit pattern.
  • Proposed techniques of forming such metal films include a technique of forming, on a surface of a semiconductor substrate made of silicon (Si) or the like, a metal film by plating such as electroless plating (see, for example, Japanese Patent Application Publication No. 2010-037622 (JP 2010-037622 A)), and a technique of forming a metal film by physical vapor deposition (PVD) such as sputtering.
  • PVD physical vapor deposition
  • plating such as electroless plating creates the need for aqueous cleaning of a substrate after the plating and the need for treatment of waste liquid resulting from the aqueous cleaning.
  • PVD such as sputtering
  • internal stress is generated in the formed metal film. This imposes a limit on an increase in the film thickness.
  • a film may be formed only under high vacuum.
  • a film-forming apparatus including at least an anode 11 , a solid electrolyte membrane 13 and an electric power supply (not illustrated) is proposed (see, for example, WO2013/125643).
  • the anode 11 is made of a porous material.
  • the solid electrolyte membrane 13 is disposed between the anode 11 and a substrate B, which serves as a cathode, such that an aqueous solution containing metal ions comes into contact with the anode 11 -side portion of the solid electrolyte membrane 13 .
  • the electric power supply places a voltage between the anode 11 and the substrate B.
  • a housing 15 of the film-forming apparatus has a reservoir 19 in which the aqueous solution containing the metal ions is stored.
  • the anode 11 and the solid electrolyte membrane 13 are disposed such that the aqueous solution containing the metal ions stored in the reservoir 19 can be supplied to the solid electrolyte membrane 13 via the anode 11 .
  • a metal film F made of metal is formed on a surface of the substrate B. Specifically, the metal film F is formed on the surface of the substrate B when the electric power supply places a voltage between the anode 11 and the substrate B, so that a metal is precipitated on the surface of the substrate B from the metal ions contained in the solid electrolyte membrane 13 .
  • hydrogen gas may be generated between the solid electrolyte membrane 13 and the substrate B, and the thus generated hydrogen gas may be accumulated between the solid electrolyte membrane 13 and the substrate B.
  • the accumulated hydrogen gas remains, as illustrated in FIG. 4 , in the form of bubbles between the solid electrolyte membrane 13 and the substrate B, which has been brought into contact with the solid electrolyte membrane 13 under pressure.
  • the metal precipitation may be inhibited at the locations where the hydrogen gas bubbles are formed.
  • non-precipitated portions (voids) where a metal is not precipitated are formed in the metal film F, and such voids make the metal film F non-uniform.
  • the invention provides a film-forming metal solution with which generation of hydrogen gas between a solid electrolyte membrane and a substrate placed in contact with each other is inhibited, and a metal film-forming method of forming a metal film using the film-forming metal solution.
  • the present inventors presumed that when a solvent in which a metal is dissolved in an ionic state is water, hydrogen ions (free hydrogen) present due to the self-ionization of the water are reduced when the metal is precipitated on a surface of a substrate that serves as a cathode, resulting in generation of hydrogen gas. Based on this presumption, the present inventors have obtained a novel finding that using a solvent having a lower hydrogen ion concentration than that of water makes it possible to inhibit generation of hydrogen gas more reliably than in a case where water is used as a solvent.
  • a first aspect of the invention relates to a film-forming metal solution for supplying metal ions to a solid electrolyte membrane in film formation in which 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 to form a metal film of the metal 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° C.
  • the total amount of hydrogen ions (protons) that migrate from the anode side to the cathode side of the solid electrolyte membrane is decreased by maintaining the hydrogen ion concentration of the film-forming metal solution within the above-described range.
  • a hydrogen ion concentration of 0 mol/L means that the film-forming metal solution contains no hydrogen ions, and the upper limit value of the hydrogen ion concentration, 10 ⁇ 7.85 mol/L (at 25° C.), is lower than a hydrogen ion concentration of 10 ⁇ 7 mol/L, attained at the time of self-ionization of water. It has been found, as a result of experiments made by the present inventors, that when the hydrogen ion concentration exceeds 10 ⁇ 7.85 mol/L (at 25° C.), a uniform metal film is not formed due to generation of hydrogen gas.
  • a hydrogen ion concentration of the film-forming metal solution is equal to a hydrogen ion concentration of the solvent. Because metal salts of most of metals used to form films contain no hydrogen, the hydrogen ion concentration of the film-forming metal solution is equal to the hydrogen ion concentration of the solvent.
  • Such a solvent preferably has a lower hydrogen ion concentration than that of water at the time of self-ionization, and examples of the solvent include an aprotic solvent and an alcoholic solvent.
  • a metal is present in an ionic state (namely, a metal can be dissolved in these solvents in an ionic state).
  • the solvent may be an alcoholic solvent containing at least one selected from methanol, ethanol and propanol (1-propanol or 2-propanol), or a solvent containing the alcoholic solvent and water.
  • the hydrogen ion concentrations of methanol, ethanol and propanol are respectively 10 ⁇ 8.35 mol/L, 10 ⁇ 8.55 mol/L and 10 ⁇ 8.25 mol/L, all of which are lower than the above-described upper limit concentration of 10 ⁇ 7.85 mol/L (at 25° C.), and therefore hydrogen gas is less likely to be generated between the solid electrolyte membrane and the substrate.
  • a metal such as nickel, tin or copper can be dissolved in the solvent in an ionic state.
  • the hydrogen ion concentration is 10 ⁇ 7.85 mol/L or less (at 25° C.)
  • the alcoholic solvent may contain water.
  • the metal to be dissolved in the solvent may have a higher ionization tendency than that of hydrogen.
  • hydrogen is easily generated during precipitation of the metal.
  • it is particularly effective to limit the hydrogen ion concentration as in the aspect of the invention.
  • hydrogen gas is less likely to be generated during precipitation of the metal, and hence a uniform metal film is formed.
  • a metal having a higher oxidation-reduction potential than that of hydrogen such as copper or silver
  • hydrogen gas may be generated during precipitation under certain film-forming conditions.
  • the above aspect of the invention offers the effect of inhibiting generation of hydrogen gas.
  • the metal having a higher ionization tendency than that of hydrogen is nickel.
  • a uniform nickel film is obtained by using a solution containing nickel ions and having a hydrogen ion concentration that falls within the above-described range.
  • a second aspect of the invention relates to a metal film-forming method for forming a metal film using the film-forming metal solution described above.
  • a 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 metal ions contained in the solid electrolyte membrane to form a metal film of the metal on the surface of the substrate.
  • FIG. 1 is a schematic conceptual diagram of a metal film-forming apparatus according to an embodiment of the invention
  • FIG. 2 is a schematic sectional view for describing a metal film-forming method performed by the metal film-forming apparatus illustrated in FIG. 1 ;
  • FIG. 3A is a photograph of a nickel film obtained in Example 2.
  • FIG. 3B is a photograph of a nickel film obtained in Comparative Example 2.
  • FIG. 4 is a diagram for describing a problem in forming a film using a conventional film-forming apparatus including a solid electrolyte membrane.
  • FIG. 1 is a schematic conceptual diagram of a metal film-forming apparatus 1 A (hereinafter, referred simply to as “film-forming apparatus 1 A”) according to the embodiment of the invention.
  • FIG. 2 is a schematic sectional view for describing a metal film-forming method performed by the film-forming apparatus 1 A to form a metal film F illustrated in FIG. 1 .
  • the film-forming apparatus 1 A precipitates a metal from metal ions to form, on a surface of a substrate B, a metal film made of the precipitated metal.
  • the substrate B in the present embodiment is a substrate made of a metal material such as aluminum, or a surface-treated resin or silicon substrate on which a metal primary coating is formed.
  • the film-forming apparatus 1 A includes at least an anode 11 made of metal, a solid electrolyte membrane 13 , and an electric power supply 14 .
  • the solid electrolyte membrane 13 is disposed on a surface of the anode 11 , at a position between the anode 11 and the substrate B that serves as a cathode.
  • the electric power supply 14 places a voltage between the anode 11 and the substrate B, which serves as the cathode.
  • the anode 11 is housed in a housing (metal ion supplying portion) 15 that supplies, to the anode 11 , a solution L containing metal ions for film formation (hereinafter, referred to as “metal solution”).
  • the housing 15 has a perforated portion that vertically passes through the housing 15 , and the anode 11 is housed in the inner space of the housing 15 .
  • the solid electrolyte membrane 13 has a recessed portion that covers a bottom surface of the anode 11 .
  • the solid electrolyte membrane 13 covers the lower opening of the perforated portion of the housing 15 with a lower portion of the anode 11 housed in the solid electrolyte membrane 13 .
  • a contact pressurizing portion metal punch
  • the contact pressurizing portion 20 pressurizes the solid electrolyte membrane 13 via the anode 11 , so that the surface of the substrate B is pressurized with the solid electrolyte membrane 13 .
  • the contact pressurizing portion 20 pressurizes the surface of the anode 11 corresponding to a film-forming region E on the surface of the substrate B where the metal film F is to be formed, such that the film-forming region E is uniformly pressurized.
  • the bottom surface of the anode 11 has a size that coincides with that of the film-forming region E of the substrate B, and the top surface and the bottom surface of the anode 11 are in the same size.
  • a solution tank 17 is connected to one side of the housing 15 via a supply pipe 17 a, and a waste liquid tank 18 is connected to the other side of the housing 15 via a waste liquid pipe 18 a.
  • the metal solution L is stored in the solution tank 17 , and waste liquid, that is, the used metal solution L, is collected into the waste liquid tank 18 .
  • the supply pipe 17 a is connected to a supply passage 15 a of the housing 15 , through which the metal solution L is supplied to the anode 11 .
  • the waste liquid pipe 18 a is connected to a discharge passage 15 b of the housing 15 , through which the metal solution L is discharged into the waste liquid tank 18 .
  • the anode 11 made of a porous material is disposed in a passage that connects the supply passage 15 a and the discharge passage 15 b of the housing 15 to each other.
  • the metal solution L stored in the solution tank 17 is supplied through the supply pipe 17 a into the housing 15 .
  • the metal solution L flows through the supply passage 15 a and then flows from the supply passage 15 a into the anode 11 .
  • the metal solution L that has passed through the anode 11 flows through the discharge passage 15 b to be delivered to the waste liquid tank 18 through the waste liquid pipe 18 a.
  • the pressurizing device 16 is connected to the contact pressurizing portion 20 .
  • the pressurizing device 16 presses the solid electrolyte membrane 13 against the film-forming region E of the substrate B by moving the anode 11 toward the substrate B.
  • Examples of the pressurizing device 16 include a hydraulic cylinder and a pneumatic cylinder.
  • the film-forming apparatus 1 A further includes a base 21 on which the substrate B is fixed. The base 21 is used to adjust the alignment of the substrate B with respect to the anode 11 .
  • the anode 11 is made of a porous material that allows the metal solution L to pass therethrough and that supplies metal ions to the solid electrolyte membrane 13 .
  • the porous material is not limited to any particular porous materials as long as (1) the porous material has corrosion resistance against the metal solution L, (2) the porous material has an electrical conductivity high enough to serve as an anode, (3) the porous material allows the metal solution L to pass therethrough, and (4) the porous material can be pressurized by the pressurizing device 16 via the contact pressurizing portion 20 described above.
  • the porous material include metal foams, such as a titanium foam, having a lower ionization tendency (or a higher electrode potential) than that of plating metal ions and made of open-cell foams having open pores.
  • the metal foam is not limited to any particular metal foams as long as the metal foam satisfies the condition (3) described above.
  • a metal foam having a porosity of approximately 50 to 95% by volume, a pore diameter of approximately 50 to 600 ⁇ m and a thickness of approximately 0.1 to 50 mm is preferably used.
  • the solid electrolyte membrane 13 is not limited to any particular solid electrolyte membranes as long as the solid electrolyte membrane 13 can be impregnated with the metal ions when the solid electrolyte membrane 13 is brought into contact with the metal solution L and a metal derived from the metal ions can be precipitated on the surface of the substrate B in response to application of a voltage.
  • the material of the solid electrolyte membrane 13 include fluorine resins such as Nafion® manufactured by DuPont, hydrocarbon resins, polyamic acid resins, and resins having an ion exchange function such as SELEMION (including CMV, CMD and CMF series) manufactured by Asahi Glass Co., Ltd.
  • a porous material is used as the anode 11 of the apparatus for forming the metal film F.
  • metal ions can be supplied to the solid electrolyte membrane 13 , a gap may be formed between an anode and a solid electrolyte membrane and a metal solution may be supplied into the gap, as described later.
  • the substrate B is placed on the base 21 , the alignment of the substrate B with respect to the anode 11 is adjusted, and the temperature of the substrate B is adjusted.
  • the solid electrolyte membrane 13 is disposed on a surface of the anode 11 made of a porous material, and the solid electrolyte membrane 13 is brought into contact with the substrate B.
  • the anode 11 is moved toward the substrate B by the pressurizing device 16 , so that the solid electrolyte membrane 13 is pressed against the film-forming region E of the substrate B.
  • the solid electrolyte membrane 13 is pressurized via the anode 11 , and hence the solid electrolyte membrane 13 uniformly conforms to the surface of the film-forming region E of the substrate B.
  • the anode 11 pressurized by the contact pressurizing portion 20 the metal film F having a more uniform thickness is formed.
  • the electric power supply 14 places a voltage between the anode 11 and the substrate B, which serves as the cathode, so that the metal is precipitated on the surface of the substrate B from the metal ions contained in the solid electrolyte membrane 13 .
  • the anode 11 is in direct contact with the contact pressurizing portion 20 made of metal, and thus there is electrical continuity between the anode 11 and the contact pressurizing portion 20 .
  • the electric power supply 14 can place a voltage between the anode 11 and the substrate B.
  • a metal film is formed while the metal solution L is caused to flow through the anode 11 .
  • the anode 11 made of a porous material allows the metal solution L to pass through the anode 11 .
  • the metal solution L is supplied, together with the metal ions, to the solid electrolyte membrane 13 .
  • the metal solution L is constantly and stably supplied into the anode 11 made of a porous material.
  • the metal solution L thus supplied passes through the anode 11 to come into contact with the solid electrolyte membrane 13 disposed adjacent to the anode 11 , and thus the solid electrolyte membrane 13 is impregnated with the metal ions.
  • the metal ions contained in the solid electrolyte membrane 13 migrate from the anode 11 side to the substrate B side, and then the metal is precipitated, on the surface of the substrate B, from the metal ions contained in the solid electrolyte membrane 13 .
  • the metal film F is formed on the surface of the substrate B.
  • the film-forming region E of the substrate B is uniformly pressurized with the solid electrolyte membrane 13 , and thus the metal film F is formed on the substrate B while the solid electrolyte membrane 13 uniformly conforms to the film-forming region E of the substrate B.
  • the uniform metal film F having a uniform thickness with less variations is formed on the surface of the film-forming region E of the substrate B.
  • the metal solution L contains a solvent and a metal (metal ions) dissolved in the solvent in an ionic state.
  • a hydrogen ion concentration of the metal solution is within a range of 0 to 10 ⁇ 7.85 mol/L at 25° C.
  • the hydrogen ion concentration of the metal solution L When the hydrogen ion concentration of the metal solution L is maintained within the above-described range, the total amount of hydrogen ions (protons) that migrate from the anode side to the cathode side of the solid electrolyte membrane 13 is decreased. Thus, it is possible to inhibit generation of hydrogen gas between the solid electrolyte membrane 13 and the substrate B placed in contact with each other.
  • a solvent having a hydrogen ion concentration of 0 mol/L is a solvent that contains no hydrogen ions.
  • a solvent examples include polar aprotic solvents such as tetrahydrofuran (THF), acetonitrile, N,N-dimethylformamide (DMF) and dimethyl sulfoxide. Because these solvents have polarities, these solvents can contain a metal such as nickel, tin or copper (described later) in an ionic state.
  • Examples of a solvent of a metal solution having a hydrogen ion concentration of 10 ⁇ 7.85 mol/L or less (at 25° C.) include alcoholic solvents.
  • a solvent obtained by adding water to an alcoholic solvent may be used as long as the solvent satisfies the above-described condition on a hydrogen ion concentration.
  • a hydrogen ion concentration of a metal solution containing nickel, tin or copper is substantially equal to a hydrogen ion concentration of an alcoholic solvent (or an alcoholic solvent containing water).
  • a metal to be dissolved in a solvent in an ionic state is charged into the solvent in the form of ionizable metal salt and is then dissolved in the solvent in an ionic state.
  • a metal include cobalt, iron, nickel, tin, copper and silver.
  • nickel and tin which have a higher ionization tendency than that of hydrogen, are preferably used.
  • the metal having a higher ionization tendency than that of hydrogen is precipitated on the surface of the substrate B by placing a voltage between the anode 11 and the substrate B.
  • hydrogen gas is less likely to be generated in the course of forming the metal film F, and thus a uniform metal film F is obtained.
  • Nickel chloride metal salt
  • methanol solvent
  • a solid electrolyte manufactured by DuPont; Nafion N117
  • a porous nickel plate were stacked on a copper substrate, and the 0.1 M nickel solution was supplied to the porous nickel plate. Then, the porous nickel plate was electrically connected to the copper substrate, and a constant voltage of 2.4 V was applied for 60 seconds. In this way, a nickel film was formed on the copper substrate.
  • a nickel film was formed in a manner similar to that in Example 1. The difference from Example 1 is that ethanol was used as a solvent.
  • a nickel film was formed in a manner similar to that in Example 1. The difference from Example 1 is that propanol (1-propanol) was used as a solvent.
  • a nickel film was formed in a manner similar to that in Example 1. The difference from Example 1 is that a mixed liquid of methanol and water (a mixed liquid containing 90% methanol by volume and 10% water by volume) was used as a solvent.
  • a nickel film was formed in a manner similar to that in Example 1. The difference from Example 1 is that a mixed liquid of methanol and water (a mixed liquid containing 85% methanol by volume and 15% water by volume) was used as a solvent.
  • a nickel film was formed in a manner similar to that in Example 1. The difference from Example 1 is that water was used as a solvent.
  • a nickel film was formed in a manner similar to that in Example 1. The difference from Example 1 is that butanol (1-butanol) was used as a solvent.
  • FIG. 3A is a photograph of the nickel film obtained in Example 2.
  • Comparative Examples 1 and 2 The reason why the results of Comparative Examples 1 and 2 were obtained is presumed as follows.
  • the amount of free hydrogen was larger than that in Examples 1 to 4.
  • hydrogen ions protons
  • the hydrogen gas was generated between the solid electrolyte membrane and the substrate.
  • the hydrogen gas was accumulated between the solid electrolyte membrane and the substrate to disturb the precipitation of nickel, and voids (non-precipitated portions) were generated, resulting in formation of a film in a patchy pattern.
  • the anode made of a porous material is used.
  • a porous material need not be used as the anode as long as nickel ions are appropriately supplied to the solid electrolyte membrane.
  • a nickel solution may be supplied to a gap between the anode and the solid electrolyte membrane.
US14/805,721 2014-07-22 2015-07-22 Film-forming metal soution and metal film-forming method Abandoned US20160024675A1 (en)

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JP2014-148867 2014-07-22
JP2014148867A JP6065886B2 (ja) 2014-07-22 2014-07-22 金属皮膜の成膜方法

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BR (1) BR102015017213A2 (ja)
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JP2020132948A (ja) * 2019-02-20 2020-08-31 トヨタ自動車株式会社 金属皮膜の成膜装置
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JP2022066011A (ja) 2020-10-16 2022-04-28 トヨタ自動車株式会社 金属めっき皮膜の成膜方法及び成膜装置

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