Metal-coated film forming apparatus and metal-coated film forming method

Abstract

The present invention provides a metal-coated film forming apparatus and a metal-coated film forming method, which can reduce the occurrence of discoloration or deterioration of a metal-coated film caused by drying of electrolyte solution remaining on the surface of the metal-coated film. A metal-coated film forming apparatus (1) of the present invention, in which a space (B) in which a metal-coated film (F) exists is enclosed between a housing (14) and a placement table (15) in a state in which a solid electrolyte film (12) is in contact with the metal-coated film (F), is provided with a water supply portion (40) that supplies cleaning water (A) to the enclosed space (B) so that the cleaning water (A) flows to the surface of the metal-coated film (F) in the state in which the solid electrolyte film (12) is in contact with the metal-coated film (F), and a water discharge portion (50) that discharges the cleaning water (A) from the enclosed space (B) so that the cleaning water (A) that has flowed to the surface of the metal-coated film (F) flows from the surface of the metal-coated film (F).

Description

TECHNICAL FIELD

[0001] The present application relates to a film formation apparatus and a film formation method for forming a metal coating film on a surface of a base material by metal ions. BACKGROUND

[0002] For example, in Patent Literature 1, a film formation apparatus equipped with an anode, a solid electrolyte film disposed between the anode and a base material that becomes a cathode, a power supply section that applies a voltage between the anode and the base material, and a placement stage on which the base material is placed is proposed. In this film formation apparatus, a current can be passed between the anode and the base material that becomes a cathode in a state in which the base material is pushed by the solid electrolyte film that closes a housing chamber, and a metal coating film is formed on a surface of the base material by metal ions derived from an electrolyte solution housed in the housing chamber of the housing.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT LITERATURE

[0005] Patent Literature 1: Japanese Patent No. 5605517 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] However, in the film formation apparatus of Patent Literature 1, there is a case in which a small amount of electrolyte solution remains on a surface of the metal coating film formed. When the electrolyte solution that remains dries on the surface of the metal coating film, there is a concern that the metal coating film discolors or deteriorates.

[0008] The present application is made in view of such a problem, and as the present application, a film formation apparatus and a film formation method for a metal coating film are provided, which can reduce occurrence of discoloration or deterioration of the metal coating film caused by drying of electrolyte solution that remains on a surface of the metal coating film formed.

[0009] MEANS FOR SOLVING THE PROBLEMS

[0010] In view of the problem, a metal film forming apparatus according to the present application is provided with at least: an anode; a solid electrolyte film disposed between the anode and a base material that is a cathode; a power supply section that applies a voltage between the anode and the base material; a housing that forms a housing chamber in which an electrolyte solution and the anode are housed, and in which the solid electrolyte film is installed so as to close the housing chamber; and a placement table disposed opposite the housing and on which the base material is placed, in a state in which the surface of the base material is pushed by the solid electrolyte film using the hydraulic pressure of the electrolyte solution in the housing chamber, the voltage is applied, and a metal film is formed on the surface of the base material from metal ions contained in the electrolyte solution, characterized in that, in a state in which the solid electrolyte film is in contact with the metal film, the space in which the metal film is present is closed between the housing and the placement table, and the apparatus is further provided with a water supply section that supplies cleaning water to the closed space so that the cleaning water flows to the surface of the metal film in the state of contact with the solid electrolyte film, and a drain section that drains the cleaning water from the closed space so that the cleaning water that has flowed to the surface of the metal film flows from the surface of the metal film.

[0011] According to the present application, the voltage can be applied between the anode and the base material in a state in which the surface of the base material is pushed by the solid electrolyte film using the hydraulic pressure of the electrolyte solution in the housing chamber, and the metal ions contained in the electrolyte solution housed in the housing chamber can be caused to pass through the solid electrolyte film and precipitate on the surface of the base material. Thus, a metal film can be formed on the surface of the base material.

[0012] Here, according to the present application, in a state in which the solid electrolyte film is in contact with the metal film, the space in which the metal film is present can be closed between the housing and the placement table, and the metal film can be cleaned in the closed space. Specifically, the cleaning water can be caused to flow to the surface of the metal film in the state of contact with the solid electrolyte film in the closed space using the water supply section. On the other hand, the cleaning water that has flowed to the surface of the metal film can be caused to flow out from between the solid electrolyte film and the metal film using the drain section.

[0013] Thus, even if the electrolyte solution remains on the metal film formed, the electrolyte solution can be prevented from drying in contact with the atmosphere or the like, and the remaining electrolyte solution can be washed off from the surface of the metal film and discharged from between the solid electrolyte film and the metal film together with the cleaning water. As a result, the occurrence of discoloration or deterioration of the metal film caused by drying of the electrolyte solution remaining on the surface of the metal film can be reduced.

[0014] Here, the cleaning of the metal coating film by the water supply portion and the drain portion can also be performed manually, and there is no particular limitation as long as the metal coating film can be cleaned. However, as a more preferable mode, the film formation device is further provided with a liquid discharge mechanism that discharges the electrolyte from the housing chamber, and a control device that controls at least the discharge of the electrolyte by the liquid discharge mechanism and the supply of the cleaning water from the water supply portion. The control device causes the liquid discharge mechanism to discharge the electrolyte in the housing chamber, and causes the water supply portion to supply the cleaning water.

[0015] After the film formation of the metal coating film is completed, when the control device causes the liquid discharge mechanism to discharge the electrolyte from the housing chamber, the liquid pressure acting on the solid electrolyte film decreases due to the weight, and thus the pushing force of the solid electrolyte film against the base material decreases. Thus, the solid electrolyte film easily deforms and separates from the base material. Therefore, in this mode, by causing the water supply portion to supply the cleaning water together with the discharge of the electrolyte, the solid electrolyte film is deformed to separate from the surface of the base material, and the cleaning water easily flows between the solid electrolyte film and the metal coating film.

[0016] In particular, in a case where the solid electrolyte film is pushed from above the base material to perform the film formation, the liquid pressure easily acts on the solid electrolyte film toward the base material side by the weight of the electrolyte housed in the housing chamber. According to this mode, since the liquid pressure acting on the solid electrolyte film by the weight decreases by the discharge of the electrolyte, the cleaning water easily flows between the solid electrolyte film and the metal coating film.

[0017] Here, there is no particular limitation on the structure of the water supply portion and the drain portion as long as the metal coating film can be cleaned with the cleaning water. However, according to a more preferable mode, a housing recess that houses the base material is formed in the placement table, the water supply portion has a water supply groove on the surface of the placement table, the drain portion has a drain groove on the surface of the placement table, and the water supply groove and the drain groove are formed at positions opposite each other across the housing recess.

[0018] According to this mode, since the water supply groove and the drain groove are formed at positions opposite each other across the housing recess, when the cleaning water is supplied to the enclosed space via the water supply groove, the cleaning water easily flows from one side to the entire metal coating film, and the inflowing cleaning water can be uniformly discharged from the enclosed space via the drain groove of the metal coating film on the other side.

[0019] A metal film forming method according to the present application is a method of forming a metal film on a base material by applying a voltage between an anode and the base material to be a cathode in a state where the base material is pressed by a solid electrolyte film using a hydraulic pressure of an electrolyte solution accommodated in an accommodation chamber of a housing, and a metal film is formed on a surface of the base material from metal ions contained in the electrolyte solution, characterized by comprising: a step of placing the base material on a placement table disposed opposite to the housing; a step of bringing the base material placed on the placement table into contact with the solid electrolyte film and pressing the base material by the solid electrolyte film using the hydraulic pressure; a step of forming the metal film on the surface of the base material by applying a voltage between the anode and the base material in a state where the solid electrolyte film is pressed; and a step of closing a space in which the metal film exists between the housing and the placement table in a state where the solid electrolyte film is in contact with the metal film, and cleaning the metal film in the closed space, wherein cleaning water is supplied to the closed space to flow to a surface of the metal film in the state of contact with the solid electrolyte film, and the cleaning water flowed to the surface of the metal film is discharged from the closed space.

[0020] According to the present application, in the step of forming the metal film, a voltage is applied between the anode and the base material in a state where the surface of the base material is pressed by the solid electrolyte film by the hydraulic pressure of the electrolyte solution of the accommodation chamber. Thus, metal ions contained in the electrolyte solution accommodated in the accommodation chamber can be caused to pass through the solid electrolyte film and precipitate on the surface of the base material. As a result, the metal film can be formed on the surface of the base material.

[0021] Further, according to the present application, in a state where the solid electrolyte film is in contact with the metal film, a space in which the metal film exists is closed between the housing and the placement table. Thus, after the step of forming the metal film, in the step of cleaning, by supplying cleaning water to the closed space, the cleaning water can be caused to flow between the metal film in the state of contact with the solid electrolyte film and the solid electrolyte film, and the cleaning water flowed to the surface of the metal film is discharged from the closed space.

[0022] Thus, even if the electrolyte solution remains on the formed metal film, the electrolyte solution can be prevented from drying in contact with the atmosphere or the like, and the remaining electrolyte solution can be washed away from the surface of the metal film by the cleaning water, and the electrolyte solution can be discharged together with the cleaning water from between the solid electrolyte film and the metal film. As a result, occurrence of discoloration or deterioration of the metal film caused by drying of the electrolyte solution remaining on the surface of the metal film can be reduced.

[0023] As a more preferable mode, in the process of performing the cleaning, the electrolytic solution is discharged from the housing chamber while the cleaning water is supplied to the space that is enclosed.

[0024] According to this mode, since the electrolytic solution is discharged from the housing chamber while the cleaning water is supplied to the space that is enclosed, the solid electrolyte film is easily deformed to be separated from the surface of the base material by the hydraulic pressure of the cleaning water, and the cleaning water is easily made to flow between the solid electrolyte film and the metal coating film. In particular, in the case where the solid electrolyte film is pushed from above the base material to perform the film formation, since such hydraulic pressure is reduced by the discharge of the electrolytic solution, the cleaning water is easily made to flow between the solid electrolyte film and the metal coating film.

[0025] Further, as a preferable mode, a housing recess that houses the base material is formed in the placement table, a water supply groove and a water discharge groove are formed at positions that are opposite across the housing recess, and in the process of performing the cleaning, the cleaning water is supplied to the space that is enclosed via the water supply groove, and the cleaning water is discharged from the space that is enclosed via the water discharge groove.

[0026] According to this mode, since the water supply groove and the water discharge groove are formed at positions that are opposite across the housing recess, when the cleaning water is supplied to the space that is enclosed via the water supply groove, the cleaning water can be made to flow on the entire metal coating film from one side of the metal coating film to the other side of the metal coating film, and thus, more uniform cleaning can be performed.

[0027] Effects of the Invention

[0028] The metal coating film forming apparatus and the metal coating film forming method according to the present application can reduce the occurrence of discoloration or deterioration of the metal coating film caused by drying of the electrolytic solution that remains on the surface of the metal coating film that is formed. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 is a schematic cross-sectional view that illustrates a state in which a base material is placed in a metal coating film forming apparatus according to an embodiment of the present application.

[0030] Figure 2 is a view of a placement table of the metal coating film forming apparatus shown in Figure 1 from the housing side.

[0031] Figure 3 is a view that illustrates a modification example of a water supply portion of the metal coating film forming apparatus shown in Figure 1

[0032] Figure 4 is a flowchart that illustrates a process of a metal coating film forming method using the metal coating film forming apparatus shown in Figure 1

[0033] ​​Figure 5 is a schematic conceptual view illustrating a film formation process of the metal coating film. Figure 4 is a schematic conceptual view illustrating a film formation process of the metal coating film.

[0034] Figure 6 is a schematic conceptual view illustrating a film formation process of the metal coating film. Figure 4 is a schematic conceptual view illustrating a film formation process of the metal coating film. DETAILED DESCRIPTION

[0035] Hereinafter, the metal coating film formation apparatus 1 according to the embodiment of the present application will be described with reference to the drawings. Figures 1 to 6 The metal coating film formation apparatus 1 according to the embodiment of the present application will be described with reference to the drawings.

[0036] 1. Structure of the film formation apparatus 1

[0037] The metal coating film formation apparatus 1 according to the embodiment of the present application will be described with reference to the drawings. Figure 1 Figure 2 The metal coating film formation apparatus 1 according to the embodiment of the present application will be described with reference to the drawings. The film formation apparatus 1 of the present embodiment is a film formation apparatus (plating apparatus) that forms a metal coating film F by solid electrolyte film solid electrolysis. When a metal coating film F is formed on the surface of a base material W with the base material W as a cathode, the film formation apparatus 1 is used. When a metal coating film F is continuously formed on the surfaces of a plurality of base materials W, the film formation apparatus 1 can also be used. The base material W that becomes the cathode can be a base material composed of a metal material such as copper, nickel, silver, or gold, or a base material in which a metal base layer of copper, nickel, silver, or gold is formed on the surface of a resin, ceramic, or the like. At the time of film formation of the metal coating film, the metal base layer is in conduction with the negative electrode of the power supply section 13 that will be described later and becomes the cathode.

[0038] As shown in FIG. 1, the film formation apparatus 1 is equipped with an anode 11, a solid electrolyte film 12 disposed between the anode 11 and a base material W, and a power supply section 13 that applies a voltage between the anode 11 and the base material W. The film formation apparatus 1 is also equipped with a housing 14 in which a housing chamber 14a that houses an electrolytic solution S is formed, and a placement table 15 that places the base material W. Figure 1

[0039] In the present embodiment, the anode 11 is electrically connected to the positive electrode of the power supply section 13, and the placement table 15 is electrically connected to the negative electrode of the power supply section 13. Since the placement table 15 is composed of an electrically conductive material, the base material W is in conduction with the negative electrode of the power supply section 13. Thus, by applying a voltage between the anode 11 and the base material W by the power supply section 13 in a state in which the solid electrolyte film 12 is in contact with the surface of the base material W, an electric current can be passed between them.

[0040] ​​In the present embodiment, the anode 11 is, for example, a plate-shaped metal plate, and can be any one of a soluble anode composed of the same material as the metal coating F (for example, Cu) or an anode composed of a material (for example, Ti) that is insoluble with respect to the electrolyte S.

[0041] The solid electrolyte film 12 is not particularly limited as long as it can impregnate (contain) metal ions inside by being in contact with the electrolyte S and can deposit metal derived from the metal ions on the surface of the cathode (base material W) when current is passed between the anode 11 and the cathode.

[0042] The solid electrolyte film 12 is set to have a thickness that is flexible by the hydraulic pressure of the electrolyte S, which will be described later, and the thickness of the solid electrolyte film 12 is, for example, preferably 1 μm to 200 μm. As the material of the solid electrolyte film 12, for example, fluorine-based resins such as Nafion (registered trademark) manufactured by DuPont, carbon (hydrocarbon)-based resins, polyamide acid resins, SELEMION (electrodialysis product, CMV, CMD, CMF series) manufactured by Asahi Glass Company, and the like having a cation exchange function can be listed.

[0043] The electrolyte S is a liquid that contains the metal of the metal coating F in an ionic state, and as the metal thereof, Cu, Ni, Zn, Ag, Sn, Au, or the like can be listed. The electrolyte S is a liquid in which these metals are dissolved (ionized) with an acid such as nitric acid, phosphoric acid, succinic acid, sulfuric acid, or pyrophosphoric acid.

[0044] In the present embodiment, the case 14 is composed of a material that is insoluble with respect to the electrolyte S. In the case 14, a housing chamber 14a that houses the electrolyte S together with the anode 11 is formed. In the case 14, the solid electrolyte film 12 is installed so as to close the housing chamber 14a that is open downward. Specifically, the anode 11 is disposed apart from the solid electrolyte film 12 in the housing chamber 14a, and the electrolyte S is housed in contact with the anode 11 and the solid electrolyte film 12.

[0045] In the present embodiment, in the end surface 14c of the side wall 14b of the case 14, an insertion groove 14d into which the solid electrolyte film 12 is inserted in a state where the periphery thereof is bent is formed. The insertion groove 14d is formed so as to surround the opening of the housing chamber 14a. By inserting the solid electrolyte film 17 in the solid electrolyte film 17 in a state where the periphery of the solid electrolyte film 12 is bent into the insertion groove 14d, the housing chamber 14a that is open downward can be closed with the solid electrolyte film 12 by the periphery of the solid electrolyte film 12 being pushed by the solid electrolyte film 17 that is elastically deformed.

[0046] In the housing 14, a supply port 14e that supplies the electrolytic solution S and a discharge port 14f that discharges the electrolytic solution S are formed. The supply port 14e and the discharge port 14f are connected to the container 21 via pipes. Between the container 21 and the supply port 14e, an electrolytic solution pressure feeding pump 22 that pressure-feeds the electrolytic solution S of the container 21 is provided. Thus, the electrolytic solution S fed from the container 21 by the electrolytic solution pressure feeding pump 22 can flow into the accommodation chamber 14a from the supply port 14e, the electrolytic solution S that has flowed in can be discharged from the discharge port 14f, and the electrolytic solution S that has been discharged can be returned to the container 21.

[0047] Further, in the present embodiment, on the downstream side of the discharge port 14f, a pressure adjusting valve 23 is provided, and the electrolytic solution S in the accommodation chamber 14a can be pressurized to a prescribed pressure by the pressure adjusting valve 23 and the electrolytic solution pressure feeding pump 22. In this way, at the time of film formation, the base material W that is in contact with the solid electrolyte membrane 12 can be pushed against by the solid electrolyte membrane 12 by means of the hydraulic pressure of the electrolytic solution S (refer to FIG. 2). Figure 5 Thus, the metal coating film F can be formed on the base material W while the base material W is uniformly pressurized by the solid electrolyte membrane 12. In the present specification, the pressure adjusting valve 23 and the electrolytic solution pressure feeding pump 22 correspond to a pushing mechanism 20.

[0048] On the placement table 15, an accommodation recess 15a that corresponds to the shape of the base material W is formed. In the present embodiment, as one example, it is preferable that, in a state in which the base material W is accommodated in the accommodation recess 15a, there is no gap between the side wall surface of the accommodation recess 15a and the side surface of the base material W, and it is more preferable that the surface 15c of the placement table 15 and the surface of the base material W are formed on the same plane. Thus, it is easy to cause the cleaning water A to flow to the surface of the metal coating film F by the water supply portion 40 that will be described later and to discharge the flowing cleaning water A by the water discharge portion 50 that will be described later.

[0049] Further, in the present embodiment, the film formation device 1 is also equipped with a lifting device 16 that is connected to the upper portion of the housing 14. The lifting device 16 is a device that lifts the housing 14 in the range from a position at which the solid electrolyte membrane 12 and the base material W are separated to a position at which the solid electrolyte membrane 12 and the base material W are in contact. The lifting device 16 is not limited as long as it can lift the housing 14, and, for example, it can be constituted by a hydraulic or pneumatic cylinder, an electric actuator, a linear guide, a motor, or the like.

[0050] In the present embodiment, the film formation apparatus 1 is further provided with a liquid discharge mechanism 30 that discharges the electrolyte S housed in the housing chamber 14a. Specifically, the liquid discharge mechanism 30 is provided with a communication passage 30a that communicates with the housing chamber 14a, an open / close valve 31 such as a solenoid valve installed in the communication passage 30a, and a housing tank 32 that houses the electrolyte S discharged from the housing chamber 14a.

[0051] The housing tank 32 is connected to the communication passage 30a formed in the side wall 14b of the housing 14 via a pipe, and between the communication passage 30a and the housing tank 32, the open / close valve 31 is disposed. The open / close valve 31 discharges the electrolyte S from the housing chamber 14a in an open state, and ensures the airtightness of the housing chamber 14a in a closed state. In addition, after the open / close valve 31 or the pressure adjusting valve 23 is opened, air can be supplied to the housing chamber 14a from the supply port 14e of the housing 14 by an air pump (not shown) to discharge the electrolyte S in the housing chamber 14a from the discharge port 14f.

[0052] However, there are cases where, at the time of film formation, the electrolyte S passes through the solid electrolyte membrane 12, and a small amount of the electrolyte S remains on the surface of the metal coating film F. Since the remaining electrolyte S is an acidic solution, there is a concern that the metal coating film F is discolored or deteriorated when it is dried on the surface. In view of this, in the present embodiment, the following device structure is employed.

[0053] In the present embodiment, the film formation apparatus 1 is further provided with a sealing member 18 for a closed space, a water supply portion 40, and a drain portion 50. As shown in FIG. 1, in a state where the solid electrolyte membrane 12 is in contact with the metal coating film F, the space where the metal coating film F exists between the housing 14 and the placement table 15 is closed by the sealing member 18 for a closed space. The space where the metal coating film F exists is a space that is closed in a manner of surrounding the metal coating film F. Figure 5

[0054] The sealing member 18 for a closed space is not particularly limited in structure as long as it can form such a closed space (closed space B), and can be a frame-shaped member made of rubber or resin, or can form a mechanical seal by the housing 14 and the placement table 15. In the present embodiment, the sealing member 18 for a closed space is disposed on the placement table 15, but for example, it can be disposed on the housing 14.

[0055] As shown in FIG. 1, the water supply portion 40 is provided with a water supply passage 41 that communicates with the closed space B, and a water supply valve 42 such as a solenoid valve installed in the water supply passage 41. The water supply valve 42 is opened in the open state to supply water to the closed space B, and is closed in the closed state to ensure the airtightness of the closed space B. Figure 2 ​As shown, the closed space sealing member 18 is arranged on the surface 15c of the placement table 15 so as to surround the water supply groove 41, the housing recess 15a, and the drain groove 51 to be described later. In the present embodiment, when the housing 14 is lowered by the lifting device 16, the closed space sealing member 18 is sandwiched by the housing 14 and the placement table 15 and is compressed and deformed. Thus, between the housing 14 and the placement table 15, a closed space B surrounded by the closed space sealing member 18 is formed (see FIG. 2). Figure 5

[0056] The water supply portion 40 supplies the cleaning water A to the closed space B so as to cause the cleaning water A to flow to the surface of the metal coating F in a state of being in contact with the solid electrolyte membrane 12. The water supply portion 40 has the water supply groove 41 formed on the surface 15c of the placement table 15, and the water supply passage 42 formed in the placement table 15, the water supply groove 41 communicating with the water supply passage 42 via the water supply connecting portion 42a. In the present embodiment, the water supply groove 41 is provided, but, for example, one or a plurality of end portions of the water supply passage 42 can be provided as a water supply port on the surface 15c of the placement table 15 instead of the water supply groove 41.

[0057] The water supply portion 40 is not particularly limited in structure as long as it can cause the cleaning water A to flow to the surface of the metal coating F in a state of being in contact with the solid electrolyte membrane 12. That is, the water supply portion 40 is not particularly limited in structure as long as it can ensure a pressure at which the cleaning water A can flow between the solid electrolyte membrane 12 and the metal coating F in contact with each other.

[0058] More preferably, the water supply portion 40 is further equipped with a water supply tank 44 that houses the cleaning water A, and a cleaning water pressure feeding pump 43 that pressure-feeds the cleaning water A from the water supply tank 44 to the water supply passage 42. Thus, the cleaning water A in the water supply tank 44 is pressure-fed into the closed space B by the cleaning water pressure feeding pump 43, and the cleaning water A is easily caused to flow between the solid electrolyte membrane 12 and the metal coating F. In addition, the cleaning water A is not particularly limited as long as it can clean the surface of the metal coating F, but is more preferably pure water containing almost no impurities.

[0059] The drain portion 50 drains the cleaning water A from the closed space B so as to cause the cleaning water A that has flowed to the surface of the metal coating F to flow from the surface of the metal coating F. The drain portion 50 has the drain groove 51 formed on the surface 15c of the placement table 15, and the drain passage 52 formed in the placement table 15, the drain groove 51 communicating with the drain passage 52 via the drain connecting portion 52a. In the present embodiment, the drain groove 51 is provided, but, for example, one or a plurality of end portions of the drain passage 52 can be provided as a drain port on the surface 15c of the placement table 15 instead of the drain groove 51.

[0060] ​More preferably, the drainage portion 50 is further provided with a suction pump 53 that suctions the cleaning water A in the enclosed space B via the drainage passage 52, and a drainage tank 54 that stores the suctioned cleaning water A. Thereby, it is easy to suction the cleaning water A that flows between the solid electrolyte membrane 12 and the metal coating film F with the suction pump 53, and to discharge it from the enclosed space B.

[0061] Here, as shown in FIG. 1, in the present embodiment, the water supply groove 41 and the drainage groove 51 are formed apart from the peripheral edge 15b of the housing recess 15a. Further, the water supply groove 41 and the drainage groove 51 are formed at positions opposite across the housing recess 15a. Thereby, when the cleaning water A is supplied to the enclosed space B via the water supply groove 41, since it is possible to make the cleaning water A flow over the entire metal coating film F from one side of the metal coating film F to the other side of the metal coating film F, it is possible to perform more uniform cleaning. Figure 2

[0062] Here, as shown in FIG. 1, in the present embodiment, the water supply groove 41 and the drainage groove 51 are formed apart from the peripheral edge 15b of the housing recess 15a. Further, the water supply groove 41 and the drainage groove 51 are formed at positions opposite across the housing recess 15a. Thereby, when the cleaning water A is supplied to the enclosed space B via the water supply groove 41, since it is possible to make the cleaning water A flow over the entire metal coating film F from one side of the metal coating film F to the other side of the metal coating film F, it is possible to perform more uniform cleaning. Figure 1 Figure 2 Here, as shown in FIG. 1, in the present embodiment, the water supply groove 41 and the drainage groove 51 are formed apart from the peripheral edge 15b of the housing recess 15a. Further, the water supply groove 41 and the drainage groove 51 are formed at positions opposite across the housing recess 15a. Thereby, when the cleaning water A is supplied to the enclosed space B via the water supply groove 41, since it is possible to make the cleaning water A flow over the entire metal coating film F from one side of the metal coating film F to the other side of the metal coating film F, it is possible to perform more uniform cleaning. Figure 3

[0063] In the present embodiment, the film formation device 1 forms the enclosed space B between the housing 14 and the placement table 15 in a state in which the solid electrolyte membrane 12 and the metal coating film F are in contact. Thereby, at the time of cleaning, it is possible to prevent leakage of the cleaning water A that is supplied between the housing 14 and the placement table 15. Further, when the cleaning water A is supplied between the housing 14 and the placement table 15, the hydraulic pressure of the cleaning water A becomes high, and the cleaning water A becomes easy to enter between the solid electrolyte membrane 12 and the base material W.

[0064] Further, in the present embodiment, the film formation device 1 is further provided with a control device 60 that controls the start and stop of the electrolyte hydraulic pump 22 of the pressing mechanism 20, the supply of the cleaning water A by the water supply portion 40, the drainage of the cleaning water A by the drainage portion 50, the discharge of the electrolyte S by the liquid discharge mechanism 30, and the application and stop of the voltage by the power supply portion 13. Specifically, the control device 60 transmits a control signal to the electrolyte hydraulic pump 22 of the pressing mechanism 20, the cleaning water hydraulic pump 43 that pressurizes the cleaning water A to the water supply portion 40, the suction pump 53 that suctions the cleaning water A, the on-off valve 31 of the liquid discharge mechanism 30, and the power supply portion 13, and controls them.

[0065] ​​​The control device 60 has a CPU or the like as an arithmetic device, a RAM, a ROM, or the like as a storage device as a basic structure. The control signals to be sent to the electrolyte pressure feeding pump 22, the cleaning water pressure feeding pump 43, the suction pump 53, the on-off valve 31, and the power supply section 13 are calculated by the arithmetic device, and the signals are sent. In the storage device, for example, the discharge time set in advance is stored.

[0066] As described above, in the film formation, since there is a case where the electrolyte S remains on the surface of the metal coating film F in a small amount, in the present embodiment, the control device 60 discharges the electrolyte S in the housing chamber 14a to the liquid discharge mechanism 30, and supplies the cleaning water A to the water supply section 40. In addition, the control by the control device 60 will be described in detail when each process of the film formation method of the metal coating film F shown in Figure 4

[0067] According to the film formation device 1 of the present embodiment, in the state where the solid electrolyte film 12 is in contact with the metal coating film F, the space where the metal coating film F exists between the housing 14 and the placement table 15 is closed, and in the closed space (closed space B), the metal coating film F can be cleaned. Specifically, the cleaning water A can be made to flow to the surface of the metal coating film F in the state of being in contact with the solid electrolyte film 12 in the closed space B by the water supply section 40. On the other hand, the cleaning water A flowing to the surface of the metal coating film F can be made to flow out from between the solid electrolyte film 12 and the metal coating film F by the water discharge section 50. In particular, since the control device 60 discharges the electrolyte S in the housing chamber 14a by the liquid discharge mechanism 30, and supplies the cleaning water A to the water supply section 40, it is further easy to make the cleaning water A flow between the solid electrolyte film 12 and the metal coating film F.

[0068] By the flow of the cleaning water A from such a water supply section 40 to a water discharge section 50, even if the electrolyte S remains on the surface of the formed metal coating film F, the electrolyte S can be prevented from drying by contacting with the atmosphere or the like, and the remaining electrolyte S can be washed away from the surface of the metal coating film F. The washed electrolyte S can be discharged from between the solid electrolyte film 12 and the metal coating film F together with the cleaning water A. As a result, the occurrence of discoloration or deterioration of the metal coating film F caused by drying of the electrolyte S remaining on the surface of the metal coating film F can be reduced.

[0069] 2. Film formation method of metal coating film F

[0070] Referring to Figures 4 to 6 The film formation method of the metal coating film F according to the present embodiment will be described. In addition, hereinafter, the film formation method will be described in accordance with the flow of the processes shown in Figure 4

[0071] ​​2-1. Placement process S1 of base material W

[0072] In the film forming method of the metal coating film F according to the present embodiment, first, the placement process S1 of the base material W is performed. In this process, the base material W is placed on the placement table 15 (refer to Figure 1 ). Specifically, in a state where the housing 14 is disposed above the placement table 15, the base material W is housed in the housing recess 15a of the placement table 15. Thereby, the base material W is disposed at a position opposite to the solid electrolyte film 12.

[0073] In addition, in the present embodiment, the water supply groove 41 and the water discharge groove 51 are formed at positions opposite across the housing recess 15a, and a frame-shaped sealing member 18 for a closed space is disposed around the periphery of the placement table 15 in a manner of enclosing them. Therefore, by housing the base material W in the housing recess 15a, a state is formed in which the water supply groove 41, the base material W, and the water discharge groove 51 are enclosed within the frame of the sealing member 18 for a closed space (refer to Figure 2 ).

[0074] 2-2. Pushing process S2 of solid electrolyte film 12

[0075] Next, the pushing process S2 of the solid electrolyte film 12 is performed. In this process, as shown in Figure 5 , the solid electrolyte film 12 mounted to the housing 14 is brought into contact with the base material W in a state of being placed, and the solid electrolyte film 12 is pushed against the base material W by hydraulic pressure.

[0076] Specifically, the housing 14 in which the housing chamber 14a in which the electrolytic solution S is housed is formed is moved toward the base material W by the lifting device 16, and the solid electrolyte film 12 mounted to the housing 14 opposite to the base material W is brought into contact with the surface of the base material W. At this time, since the sealing member 18 for a closed space is sandwiched by the housing 14 and the placement table 15, a closed space B surrounded by the sealing member 18 for a closed space is formed between the housing 14 and the placement table 15.

[0077] The electrolyte pressure pump 22 is controlled by the control device 60 to supply the electrolyte S from the container 21 to the housing chamber 14a, and the base material W is pressed by the solid electrolyte membrane 12 with the aid of the pressing mechanism 20 (the electrolyte pressure pump 22 and the pressure adjusting valve 23) under the pressure conditions under which the metal coating film F is formed. In addition, the on-off valve 31 is in the closed state in order to ensure the airtightness of the housing chamber 14a during the pressing. As a result, the electrolyte S is pressurized by the electrolyte pressure pump 22, the solid electrolyte membrane 12 follows the shape of the base material W, and the electrolyte S in the case 14 is brought to a constant pressure set by the pressure adjusting valve 23. That is, the solid electrolyte membrane 12 can uniformly press the surface of the base material W with the aid of the hydraulic pressure of the electrolyte S in the case 14.

[0078] 2-3. Metal Coating Film Forming Process S3

[0079] Next, the metal coating film forming process S3 is performed. As shown in Figure 5 this process, in a state in which the solid electrolyte membrane 12 is pressed, a voltage is applied between the anode 11 and the base material W by control of the power supply section 13 by the control device 60, and a metal coating film F is formed on the surface of the base material W. Since a metal derived from the metal ions contained in the solid electrolyte membrane 12 is deposited by application of this voltage, the metal coating film F derived from the metal ions can be formed on the surface of the base material W. After the film thickness of the metal coating film F is formed to a desired thickness (specifically, after a constant current is passed between the anode 11 and the base material W for a prescribed time), the application of the voltage between the anode 11 and the base material W is stopped by control of the power supply section 13 by the control device 60. Thus, the formation of the metal coating film F is completed. In this embodiment, in a state in which the solid electrolyte membrane 12 is in contact with the formed metal coating film F, the surface of the metal coating film F is cleaned as will be described later.

[0080] 2-4. Metal Coating Film Cleaning Process S4

[0081] Next, the metal coating film cleaning process S4 is performed. As shown in Figure 6 this process, the cleaning water A is supplied to the closed space B by the water supply section 40 so as to flow to the surface of the metal coating film F in a state in which the solid electrolyte membrane 12 is in contact therewith. On the other hand, the cleaning water A that has flowed to the surface of the metal coating film F is drained from the closed space B by the water drain section 50. In this embodiment, the control device 60 is used to start the suction pump 53 after the cleaning water A is supplied to the closed space B, and to control the drainage of the cleaned cleaning water A by the water drain section 50.

[0082] Here, the closed space surrounded by the closed space seal 18 is made airtight by the closed space seal 18 between the housing 14 and the placement table 15. Therefore, when the cleaning water A is supplied between the housing 14 and the placement table 15 by the water supply portion 40 inside the closed space seal 18, the hydraulic pressure of the cleaning water A is raised.

[0083] As a result, even in a state where the solid electrolyte film 12 is in contact with the metal coating film F, the cleaning water A is easily caused to flow between the solid electrolyte film 12 and the metal coating film F. The cleaning water A thus flowing in flows out from between the solid electrolyte film 12 and the metal coating film F and is drained from the closed space B by the drain portion 50.

[0084] Here, preferably, the cleaning water A is supplied to the closed space B while the electrolyte solution S is drained from the housing chamber 14a. Specifically, the control device 60 causes the liquid draining mechanism 30 to drain the electrolyte solution S in the housing chamber 14a and causes the water supply portion 40 to supply the cleaning water A. In the present embodiment, the control device 60 sends a control signal to the electrolyte solution pressure feeding pump 22 in order to stop the electrolyte solution pressure feeding pump 22 of the pressing mechanism 20 in order to stop the supply of the electrolyte solution S from the container 21 to the housing chamber 14a. In addition, the control device 60 sends a control signal to the on-off valve 31 in order to open the on-off valve 31 in the closed valve state in order to drain the electrolyte solution S in the housing chamber 14a. Furthermore, the control device 60 sends a control signal to the cleaning water pressure feeding pump 43 in order to start the cleaning water pressure feeding pump 43 in order to supply the cleaning water A.

[0085] Thus, since the hydraulic pressure acting on the solid electrolyte film 12 is lowered when the control device 60 causes the liquid draining mechanism 30 to drain the electrolyte solution S of the housing chamber 14a after the film formation of the metal coating film F is completed, the pressing force of the solid electrolyte film 12 against the base material W is also lowered. Thus, the solid electrolyte film 12 is easily deformed to be separated from the base material W. Therefore, in the present embodiment, the solid electrolyte film 12 is deformed to be separated from the surface of the base material W by supplying the cleaning water A to the water supply portion 40 at the same time as the draining of the electrolyte solution S, and the cleaning water A is easily caused to flow between the solid electrolyte film 12 and the metal coating film F. Thus, the cleaning efficiency of the metal coating film F can be improved.

[0086] Here, in the present embodiment, the solid electrolyte film 12 closes the housing chamber 14a from below. Thus, when the electrolyte solution S housed in the housing chamber 14a is drained to the housing groove 32, the pressure caused by the weight of the electrolyte solution S acting on the solid electrolyte film 12 is also reduced. Thus, the cleaning water A can be more easily caused to flow between the solid electrolyte film 12 and the metal coating film F.

[0087] Alternatively, the water supply unit 40 may start supplying the cleaning water A during the period from the start of draining the electrolyte S from the storage chamber 14a to the completion of the draining. This allows the replacement of the electrolyte S in the storage chamber 14a (specifically, draining the electrolyte S) and the cleaning of the metal coating S with the cleaning water A to be completed in a shorter time.

[0088] The control device 60 may also stop the water supply from the water supply unit 40 after a predetermined period of time has passed since the electrolyte S within the housing 14 has been drained. Specifically, when the water supply is stopped, the control device 60 sends a control signal to the wash water pressure pump 43 to stop the wash water pressure pump 43. Furthermore, the control device 60 sends a control signal to the suction pump 53 to stop the drainage of the wash water A. Furthermore, if necessary, the control device 60 may send a control signal to the on-off valve 31 to close the on-off valve 31 if it is open. This ensures that the wash water A can easily flow between the solid electrolyte membrane 12 and the metal film F, allowing the metal film F to be cleaned.

[0089] In addition, here, an example of discharging the electrolyte S by controlling the on-off valve 31 is described, but the electrolyte S can also be discharged using a suction pump (not shown in the figure) arranged downstream of the on-off valve 31 so that the electrolyte S can be discharged into the storage tank 32.

[0090] 2-5. Base Material Removal Step S5

[0091] Next, the substrate removal step S5 is performed. In this step, the substrate W in the state where the metal coating F has been cleaned is removed from the film forming apparatus 1. Specifically, the housing 14 is raised to a predetermined height (see Figure 1 ), the solid electrolyte membrane 12 is peeled off from the base material W in a state where the surface of the metal film F has been cleaned.

[0092] In this embodiment, even if the electrolyte S remains on the surface of the metal film F during film formation, since the surface of the metal film F is cleaned as described above, there is almost no residual electrolyte S on the metal film F. Therefore, even if the solid electrolyte membrane 12 is peeled off from the base material W and the metal film F is exposed to the air, discoloration and deterioration of the metal film F caused by drying of the electrolyte S can be suppressed.

[0093] Example

[0094] Hereinafter, the present invention will be described using examples.

[0095] <Example 1>

[0096] As a base material on which a film is formed on the surface, a base material on which a Cu film was to be formed on the surface of a glass epoxy base material (10 cm x 10 cm x Cu film thickness 500 nm) was prepared. Next, using the film forming apparatus shown in Fig. 1, a Cu film was formed according to the film forming method shown in Fig. 2. The electrolyte solution was a copper sulfate plating solution containing a brightener, the anode was a Cu plate, and the solid electrolyte film was Nafion N212 (manufactured by DuPont) having a film thickness of 8 μm. Figure 1 Figure 4

[0097] As the test conditions, a Cu film having a film thickness of 10 μm was formed at a temperature of 42°C, a current density of 18 A / dm 2 , a hydraulic pressure of 0.6 MPa, and a film forming time of 388 seconds. Next, after the pushing pressure by the hydraulic pressure was released, the electrolyte solution in the housing was discharged, and the supply of pure water was started from the water supply section. After the discharge of the electrolyte solution in the housing was completed, the water supply by the water supply section was stopped. Thereafter, the housing was raised, the base material was taken out, and drying was performed, whereby a test piece on which a Cu film was formed on the surface of the base material was produced.

[0098] <Comparative Example 1>

[0099] A test piece of Comparative Example 1 was produced in the same manner as in Example 1. However, in Comparative Example 1, the water supply by the water supply section was not performed, unlike in Example 1. Specifically, after the pushing pressure by the hydraulic pressure was released, the supply by the water supply section was not performed, and the discharge of the electrolyte solution in the housing was performed. After the discharge, the housing was raised, and after the base material was taken out, the surface of the metal film was washed with pure water, and drying was performed, whereby a test piece was produced.

[0100] <Results and Considerations>

[0101] The appearance of the test pieces of Example 1 and Comparative Example 1 was observed. In the test piece of Example 1, no color unevenness was recognized, and a metal film having a color which was uniform as a whole was formed. On the other hand, in the test piece of Comparative Example 1, color unevenness of a red discoloration was recognized. This can be considered to be due to the fact that, in Example 1, the electrolyte solution remaining on the surface of the metal film was not dried in the state in which the solid electrolyte film was in contact with the metal film after the film formation, and the electrolyte solution was washed away from the metal film.

[0102] The foregoing has been described in detail for one embodiment of the present application, but the present application is not limited to the described embodiment, and various design modifications can be made within the scope of the present application recited in the claims.

[0103] Explanation of Reference Numerals

[0104] ​​1: film forming apparatus, 11: anode, 12: solid electrolyte film, 13: power supply unit, 14: housing, 14a: accommodation chamber, 15: placement table, 15a: accommodation recess, 15c: surface, 40: water supply unit, 50: water discharge unit, 15b: peripheral edge, 18: seal for closed space, 41: water supply groove, 51: water discharge groove, 20: pushing mechanism, 30: liquid discharge mechanism, 60: control device, A: cleaning water, B: space (closed space), S: electrolyte, F: metal coating, W: base material, S1: process of performing placement, S2: process of performing pushing, S3: process of performing film formation, S4: process of performing cleaning.

Claims

1. A metal film forming device, comprising at least: anode; a solid electrolyte membrane disposed between the anode and a substrate serving as a cathode; a power supply unit configured to apply a voltage between the anode and the base material; a housing forming a receiving chamber for receiving the electrolyte together with the anode, the solid electrolyte membrane being mounted so as to seal the receiving chamber; as well as A mounting table is arranged opposite to the housing and is used to mount the base material. A receiving recess for receiving the base material is formed on the mounting table. The voltage is applied while the solid electrolyte membrane is pressing the surface of the base material using the hydraulic pressure of the electrolyte in the receiving chamber, and a metal film is formed on the surface of the base material by the metal ions contained in the electrolyte, characterized in that: In a state where the solid electrolyte membrane is in contact with the metal film, the space where the metal film is located is sealed between the housing and the mounting table. The film forming device is also equipped with a sealing member for a closed space, a water supply unit and a drainage unit. The water supply unit includes a water supply groove formed on the surface of the mounting table and a water supply passage formed in the mounting table, the water supply groove being connected to the water supply passage via a water supply connection portion, and the water supply unit supplies cleaning water to the enclosed space so that the cleaning water flows to the surface of the metal film in contact with the solid electrolyte membrane. The drain portion includes a drain groove formed on the surface of the mounting table and a drain passage formed in the mounting table. The drain groove is connected to the drain passage via a drain connection portion. The drain portion discharges the washing water from the enclosed space so that the washing water flowing onto the surface of the metal coating flows out from the surface of the metal coating. The water supply groove and the drainage groove are formed at opposite positions across the receiving recess. The closed space seal is arranged on the surface of the mounting table so as to surround the water supply groove, the storage recess, and the drain groove, thereby forming a closed space surrounded by the closed space seal between the housing and the mounting table.

2. The metal film forming device according to claim 1, wherein: The film forming device is also equipped with a liquid discharge mechanism and a control device, The liquid discharge mechanism discharges the electrolyte from the storage chamber, The control device controls at least the discharge of the electrolyte by the liquid discharge mechanism and the supply of the washing water by the water supply unit. The control device causes the liquid discharge mechanism to discharge the electrolyte in the storage chamber and causes the water supply unit to supply the washing water.

3. A film formation method of a metal coating film, using the film formation apparatus of a metal coating film according to claim 1, in a state where a substrate material is pushed by a solid electrolyte film that closes a housing chamber in which an electrolyte solution is housed, using a hydraulic pressure of the electrolyte solution, a voltage is applied between an anode and the substrate material that becomes a cathode, and a metal coating film is formed on a surface of the substrate material from metal ions contained in the electrolyte solution, characterized by, the film formation method comprising: a process of placing the substrate material on a placement table that is disposed opposite the housing; a process of bringing the substrate material in a state of being placed on the placement table into contact with the solid electrolyte film, and pushing the substrate material by the solid electrolyte film using the hydraulic pressure; a process of forming the metal coating film on the surface of the substrate material by applying a voltage between the anode and the substrate material in a state of pushing the solid electrolyte film; and a process of closing a space in which the metal coating film exists between the housing and the placement table in a state where the solid electrolyte film and the metal coating film are in contact, and cleaning the metal coating film in the closed space, in the process of performing the cleaning, supplying cleaning water to the closed space so that the cleaning water flows to a surface of the metal coating film in a state of being in contact with the solid electrolyte film, and discharging the cleaning water that flows to the surface of the metal coating film from the closed space.

4. The film formation method of a metal coating film according to claim 3, characterized by, in the process of performing the cleaning, supplying cleaning water to the closed space while discharging the electrolyte solution from the housing chamber.

5. The film formation method of a metal coating film according to claim 3 or 4, characterized by, in the placement table, a housing recess that houses the substrate material is formed, a water supply groove and a water discharge groove are formed at positions opposite each other across the housing recess, in the process of performing the cleaning, cleaning water is supplied to the closed space via the water supply groove, and the cleaning water is discharged from the closed space via the water discharge groove.

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