JP2018150599A - Method of forming metal coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of uniformly forming a metal coating on a surface of a base plate B even when the base plate B is brought into contact with a surface of a solid electrolyte membrane 13.SOLUTION: A metal coating is formed by: arranging a solid electrolyte membrane 13 between an anode 11 and a base plate B; supplying a chamber 15 with a metallic solution L while sealing a housing space G of the chamber 15 where the metallic solution L is housed with the solid electrolyte membrane 13; deforming the solid electrolyte membrane 13 in a convex shape by pressing the metallic solution L housed in the chamber 15 so that the solid electrolyte membrane 13 is elevated upward from the central part thereof; by pressing the surface of the base plate B onto the solid electrolyte membrane 13 deformed in a convex shape from above the solid electrolyte membrane 13; and by applying a voltage between the anode 11 and the base plate B.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metal film forming method for forming a metal film made of a metal of a metal solution on a surface of a substrate using a solid electrolyte film.

  Conventionally, by applying a voltage to the anode and the cathode while the substrate is in contact with the solid electrolyte membrane between the anode and the substrate corresponding to the cathode and disposed above the anode, the surface of the substrate is obtained. A method of forming a metal film on the surface is used.

  As such a technique, for example, in Patent Document 1, a metal film is formed on the surface of a substrate by disposing a substrate via a solid electrolyte membrane below the anode and applying a voltage between the anode and the substrate. A film forming method for forming a film is disclosed. In this film forming method, a film forming apparatus provided with a solution storage portion for storing a metal solution containing metal ions is used so that the metal solution is in contact with both the anode and the solid electrolyte membrane disposed below the anode. .

  During film formation, when a voltage is applied between the anode and the substrate, the metal ions contained in the metal solution accommodated in the solution accommodating portion move in the solid electrolyte membrane in the direction from the anode toward the substrate, Reduced at the surface. Thereby, a metal film can be formed on the surface of the substrate.

JP 2014-051701 A

  However, in the film forming method shown in Patent Document 1, when the solid electrolyte film is replaced after the metal film is formed, the solid electrolyte film is disposed below the anode. , It flows down from the solution container and leaks.

  In view of such points, for example, as shown in FIG. 5, if a solid electrolyte membrane 13 is disposed above the anode 11 and a chamber (solution storage portion) 15 for storing the metal solution L together with the anode 11 is provided. The state in which the metal solution L is accommodated in the chamber 15 can be maintained regardless of the removal of the solid electrolyte membrane 13.

  However, when such a structure is adopted, for example, as shown in FIG. 5, the solid electrolyte membrane 13 is recessed downward due to the surface tension of the metal solution L, and the substrate B is brought into contact with the solid electrolyte membrane 13 from above. Even so, a gap S is formed between the substrate B and the solid electrolyte membrane 13. In this state, even if a voltage is applied between the anode 11 and the substrate B by the power supply unit 14 to form a metal film on the surface of the substrate B, the surface portion of the substrate B where the gap S is formed Since the air is entrained, the flow of metal ions is obstructed. As a result, the metal film cannot be formed and the metal film cannot be formed uniformly.

  The present invention has been made in view of these points, and the object of the present invention is to uniformly apply a metal film to the surface of the substrate even when the substrate is brought into contact with the solid electrolyte film. An object of the present invention is to provide a method for forming a metal film that can be formed.

  In view of the above problems, the metal film forming method according to the present invention is a solid electrolyte in which the surface of the substrate is in contact between the anode and the substrate disposed above the anode and corresponding to the cathode. A voltage is applied between the anode and the substrate in a state where a film is disposed and a metal solution containing metal ions is disposed between the solid electrolyte film and the anode so as to be in contact therewith. In this way, the metal film is formed by depositing a metal film made of the metal of the metal solution on the surface of the substrate.

  In the film formation method, the metal film is formed using a solution storage unit that stores the metal solution so that the metal solution is in contact with the anode and the solid electrolyte film disposed above the anode. To do.

  In the film formation method, the solid electrolyte membrane is disposed between the anode and the substrate, and a storage space in which the metal solution in the solution storage portion is stored is sealed with the solid electrolyte membrane, and the solution storage A liquid supply step for supplying the metal solution to the portion; and after the liquid supply step, the solid electrolyte membrane is raised upward from the center of the solid electrolyte membrane by pressurizing the metal solution stored in the solution storage portion A membrane deformation step of deforming the solid electrolyte membrane into a convex shape, and pressing the surface of the substrate from above the solid electrolyte membrane against the solid electrolyte membrane deformed into a convex shape after the membrane deformation step And a film forming process for forming the metal film by applying a voltage between the anode and the substrate after the pressing process.

  According to the metal film deposition method of the present invention, the metal film is deposited on the surface of the substrate while pressing the surface of the substrate from above the solid electrolyte membrane on the solid electrolyte membrane deformed into a convex shape. Therefore, the metal film can be uniformly formed on the surface of the substrate.

It is typical sectional drawing for demonstrating the film-forming method of the metal film which concerns on 1st Embodiment of this invention. It is a flowchart for demonstrating the film-forming method of the metal film which concerns on 1st Embodiment. It is typical sectional drawing for demonstrating the film-forming method of the metal film which concerns on 2nd Embodiment of this invention. It is a flowchart for demonstrating the film-forming method of the metal film which concerns on 2nd Embodiment. It is typical sectional drawing for demonstrating the film-forming method of the metal film used as the comparison with 1st Embodiment of this invention.

  Hereinafter, with reference to FIGS. 1 to 4, a method for forming a metal film according to the first and second embodiments of the present invention will be described.

1. Metal Film Film Forming Apparatus 1 First, the metal film film forming apparatus 1 will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view for explaining the metal film forming method according to the first embodiment of the present invention, and shows a state immediately before a pressing step S3 described later.

  As shown in FIG. 1, a film forming apparatus 1 according to this embodiment is an apparatus that deposits a metal from metal ions and forms a metal film made of the deposited metal on the surface of a substrate B. Here, the substrate B includes a substrate made of a metal material such as aluminum, a substrate in which a metal underlayer is formed on a processing surface of a resin or silicon substrate, or a semiconductor substrate (diode) in which current flows in one direction. be able to.

  The film forming apparatus 1 is configured such that a voltage is applied between the anode 11 and the substrate B, and the solid electrolyte membrane 13 disposed between the metal anode 11 and the substrate B disposed above the anode 11 and serving as the cathode. And a power supply unit 14 to be applied.

  The anode 11 is electrically connected to the positive electrode of the power supply unit 14 via a chamber (solution storage unit) 15, and the substrate B serving as a cathode is connected via a holding jig 17 made of a conductive material, for example. The power supply unit 14 is electrically connected to the negative electrode. The chamber 15 is made of a material that is insoluble in the metal solution L described later. The holding jig 17 has a structure capable of holding the substrate B.

  Examples of the anode 11 include ruthenium oxide, platinum, and iridium oxide that are insoluble in the metal solution L, and may be an anode in which these metals are coated on a copper plate or the like. In the present embodiment, the anode 11 may be a soluble anode made of the same metal as the metal of the metal film (metal ion metal of the metal solution L).

  The solid electrolyte membrane 13 can be impregnated with metal ions by being brought into contact with the above-described metal solution L, and a metal ion-derived metal can be deposited on the surface of the substrate B when a voltage is applied. If it is, it will not specifically limit. Examples of the material for the solid electrolyte membrane include ion exchange such as fluorine resin such as Nafion (registered trademark) manufactured by DuPont, hydrocarbon resin, polyamic acid resin, and selemion manufactured by Asahi Glass (CMV, CMD, CMF series). A resin having a function can be mentioned.

  In the present embodiment, the chamber (solution storage unit) 15 stores the metal solution L, and a storage space G for storing the metal solution L is formed therein. Examples of the metal solution L include an electrolytic solution containing ions such as copper, nickel, and silver. In the metal solution L, a metal that forms a metal film is present in an ion state.

  An anode 11 is disposed in a storage space G that stores the metal solution L, and an opening 15 a that is the same as or larger than the surface of the anode 11 is formed above the chamber 15. The solid electrolyte membrane 13 is disposed in the opening 15a so as to cover it. Specifically, the solid electrolyte membrane 13 is attached to the chamber 15 to such an extent that the opening 15a can be sealed in a state where the liquid pressure of the metal solution L pressurized by the pressurizing device 19 described later is applied. Yes.

  In the present embodiment, the film forming apparatus 1 includes a pressurizing device 19 that pressurizes the metal solution L accommodated in the chamber 15. Examples of the pressurizing device 19 include a pump and a piston. The pressurizing device 19 not only supplies the metal solution L into the chamber 15 but also pressurizes the metal solution L accommodated in the chamber 15, so that the solid electrolyte membrane 13 rises upward from the center of the solid electrolyte membrane 13. As described above, the solid electrolyte membrane 13 can be deformed into a convex shape.

  In this way, the solid electrolyte membrane 13 is arranged so that the surface of the substrate B is in contact with the anode 11 and the substrate B disposed above the anode 11 and corresponding to the cathode. A metal solution L can be placed between them so as to be in contact with the anode 11. Then, the substrate B can be pressed against the solid electrolyte membrane 13, and a voltage can be applied between the anode 11 and the substrate B to form a metal film made of metal of the metal solution L on the surface of the substrate B. Below, the film-forming method of a metal film is demonstrated easily.

2. About the film-forming method of a metal film Below, the film-forming method of the metal film which concerns on this embodiment is demonstrated below with reference to FIG. FIG. 2 is a flowchart for explaining the metal film forming method according to the present embodiment. In this film forming method, first, a liquid supply step S1 is performed as shown in FIG. In the liquid supply step S <b> 1, the solid electrolyte membrane 13 is disposed between the anode 11 and the substrate B, and the metal solution L is supplied to the chamber 15.

  Specifically, the opening 15 a of the chamber 15 is covered with the solid electrolyte membrane 13, and the opening 15 a is sealed with the solid electrolyte membrane 13. Thereby, the accommodation space G in which the metal solution L of the chamber 15 is accommodated can be sealed with the solid electrolyte membrane 13. In this embodiment, the metal solution L is supplied after the solid electrolyte membrane 13 is arranged. However, this order may be reversed, and these may be performed simultaneously.

  Next, the metal solution L is supplied from the tank (not shown) to the accommodation space G of the chamber 15 using the pressurizing device 19. Specifically, the storage space G is filled with the metal solution L while the air in the storage space G is discharged from the exhaust port (not shown) of the chamber 15.

  Next, the film deformation step S2 is performed. In the membrane deformation step S2, the metal electrolyte L accommodated in the chamber 15 is pressurized by the pressure device 19 after the liquid supply step S1, so that the solid electrolyte membrane 13 rises upward from the center of the solid electrolyte membrane 13. Next, the solid electrolyte membrane 13 is deformed into a convex shape. Specifically, the solid electrolyte membrane 13 is expanded upward by the hydraulic pressure of the metal solution L. The liquid pressure of the metal solution L is preferably 100 kPa or less so that the solid electrolyte membrane 13 is greatly stretched and is not damaged. The liquid pressure can be measured with a pressure gauge 18 shown in FIG.

  Next, the pressing step S3 is performed. In the pressing step S3, the surface of the substrate B is pressed from above the solid electrolyte membrane 13 against the solid electrolyte membrane 13 deformed into a convex shape after the membrane deformation step S2. Specifically, the surface of the substrate B is pressed against the solid electrolyte membrane 13 from the upper side to the lower side of the solid electrolyte membrane 13 via a holding jig 17 attached to an elevating device (not shown).

  Thereby, the center of the substrate B comes into contact with the center of the solid electrolyte membrane 13 having a convex shape, and the edge from the center of the substrate B gradually contacts the edge from the center of the solid electrolyte membrane 13 as the pressing force increases. To do. As a result, the surface of the substrate B can be brought into contact with the solid electrolyte membrane 13 while extruding air existing between them from the center of the substrate B toward the edge thereof, so the solid electrolyte membrane 13 and the substrate B The air can be prevented from being caught between the two.

  Further, when the solid electrolyte membrane 13 has wrinkles, the wrinkles formed on the solid electrolyte membrane 13 are extended so that the surface of the substrate B can be brought into uniform contact with the solid electrolyte membrane 13. In addition, after the surface of the substrate B is completely in contact with the solid electrolyte membrane 13, the surface of the substrate B may be further pressed against the solid electrolyte membrane 13 with a pressure that is a film forming condition.

  Next, a film forming step S4 is performed. In the film forming step S4, a metal film is formed by applying a voltage between the anode 11 and the substrate B after the pressing step S3. When a voltage is applied between the anode 11 and the substrate B, metal ions of the metal solution L accommodated in the chamber 15 flow in the solid electrolyte film 13 from the anode 11 toward the substrate B, and on the surface of the substrate B. This is reduced and the metal is deposited. Thereby, a metal film can be formed on the surface of the substrate B.

  According to the present embodiment, in the pressing step S3, the surface of the substrate B can be uniformly brought into contact with the solid electrolyte membrane 13 while suppressing air entrainment between the solid electrolyte membrane 13 and the substrate B. For this reason, a metal film can be uniformly formed on the surface of the substrate B without hindering movement of metal ions flowing through the solid electrolyte membrane 13.

[Second Embodiment]
Hereinafter, a method for forming a metal film according to the second embodiment of the present invention will be described. FIG. 3 is a schematic cross-sectional view for explaining a metal film deposition method according to the second embodiment of the present invention, and FIG. 4 explains a metal film deposition method according to the second embodiment. FIG. FIG. 3 is a schematic cross-sectional view in the damage determination step S21 shown in FIG.

  The film forming method according to the present embodiment is different from the film forming method according to the first embodiment in that the sensor 16 detects the swelling of the solid electrolyte film 13 and determines damage of the solid electrolyte film 13. The difference is that step S21 is further added. Since other processes are the same, detailed description is omitted.

  In the present embodiment, the film forming apparatus 1 includes a sensor 16 that detects the swelling of the solid electrolyte membrane 13. The sensor 16 detects the bulge of the solid electrolyte membrane 13 when the solid electrolyte membrane 13 is deformed into a convex shape or detects the amount of the bulge, for example, by using light rays such as infrared rays or laser light.

  In the film forming method of the present embodiment, a damage determination step S21 for determining damage to the solid electrolyte membrane 13 is performed after the film deformation step S2. Specifically, in the damage determination step S21, when the bulge of the solid electrolyte membrane 13 is detected by the sensor 16 after the membrane deformation step S2, or when the bulge amount is within a predetermined range, the solid electrolyte membrane 13 is damaged. It judges that there is no, and progresses to press process S3.

  On the other hand, when the swelling of the solid electrolyte membrane 13 cannot be detected or the amount of swelling is smaller than a predetermined range in the damage determination step S21, it is determined that the solid electrolyte membrane 13 is damaged, and the metal solution L is solid electrolyte membrane. 13 can be estimated as leaking. In this case, pressurization by the pressurization device 19 is stopped, the liquid pressure of the metal solution L is reduced, and the solid electrolyte membrane 13 is replaced. Thereby, it is possible to prevent the excessive metal solution from leaking due to further damage of the solid electrolyte membrane 13.

  The embodiment of the present invention has been described in detail with reference to the drawings. However, the specific configuration is not limited to this embodiment, and there are design changes and the like without departing from the gist of the present invention. They are also included in the present invention.

  In the second embodiment, the amount of swelling of the solid electrolyte membrane was measured by the sensor and the damage of the solid electrolyte membrane was determined, but the amount of swelling of the solid electrolyte membrane was measured by the sensor, and the solid electrolyte membrane was measured from the measured amount of swelling. The lifetime may be predicted.

  DESCRIPTION OF SYMBOLS 1: Film-forming apparatus, 11: Anode, 13: Solid electrolyte membrane, 14: Power supply part, 15 chamber (solution processing part), 19: Pressurization apparatus

Claims (1)

A solid electrolyte membrane is disposed between the anode and a substrate disposed above the anode and corresponding to the cathode so that the surface of the substrate is in contact with the anode, and is in contact with the solid electrolyte membrane and the anode Thus, in a state where a metal solution containing metal ions is disposed between them, a voltage is applied between the anode and the substrate to form a metal film made of the metal of the metal solution on the surface of the substrate. A metal film forming method for forming a film on
In the film formation method, the metal film is formed using a solution storage unit that stores the metal solution so that the metal solution is in contact with the anode and the solid electrolyte film disposed above the anode. Is what
In the film formation method, the solid electrolyte membrane is disposed between the anode and the substrate, and a storage space in which the metal solution in the solution storage portion is stored is sealed with the solid electrolyte membrane, and the solution storage A liquid supply step of supplying the metal solution to the section;
After the liquid supplying step, the solid electrolyte membrane is deformed into a convex shape by pressurizing the metal solution accommodated in the solution accommodating portion so that the solid electrolyte membrane protrudes upward from the center of the solid electrolyte membrane. A membrane deformation step to be
A pressing step of pressing the surface of the substrate from above the solid electrolyte membrane to the solid electrolyte membrane deformed into a convex shape after the membrane deformation step;
A film forming method for forming a metal film, comprising at least a film forming process for forming the metal film by applying a voltage between the anode and the substrate after the pressing step.

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