Patent Grant
10920331
1. Field of the Invention
The invention relates to a film deposition device and a film deposition method of a metal film, in particular, a film deposition device and a film deposition method of a metal film, which can deposit a thin metal film uniformly on a surface of a base material.
2. Description of Related Art
Heretofore, when an electronic circuit base material or the like is manufactured, in order to form a metal circuit pattern, a metal film is deposited on a surface of a base material. For example, as a film deposition method of such a metal film, a film deposition technique in which a metal film is deposited on a surface of a semiconductor base material such as Si by plating such as electroless plating or the like (see Japanese Patent Application Publication No. 2010-037622 (JP 2010-037622 A), for example) and a film deposition technique in which a metal film is deposited by a PVD method such as sputtering have been proposed.
However, in the case where plating such as the electroless plating was applied, water cleansing was necessary after the plating, and an waste liquid after water cleansing was necessary to be treated. Further, when a film was deposited on a surface of a base material by a PVD method such as sputtering, since an internal stress was formed in a deposited metal film, a film thickness was limited from being thickened, in particular, in the case of sputtering, in some cases, the film deposition was possible only under high vacuum.
In view of points like this, for example, a film deposition method of a metal film, which uses a positive electrode, a negative electrode, a solid electrolyte membrane disposed between the positive electrode and negative electrode, and a power supply part that applies a voltage between the positive electrode and negative electrode is proposed (see JP 2012-219362 A, for example).
Here, the solid electrolyte membrane is formed in such a manner that a solution containing a precursor of a solid electrolyte is spin coated on a surface of a base material in advance and cured, and metal ions to be coated on the solid electrolyte membrane are impregnated. Then, the solid electrolyte membrane is faced to the positive electrode and the base material is disposed so as to be electrically connected with the negative electrode. By applying a voltage between the positive electrode and negative electrode, the metal ions impregnated inside the solid electrolyte are precipitated on a negative electrode side. Thus, a metal film made of the metal described above can be deposited.
However, when the technique disclosed in Japanese Patent Application Publication No. 2012-219362 (JP 2012-219362 A) was used, in some cases, an oxide was formed in the metal film and a deposited metal film and the solid electrolyte membrane were closely stuck. In particular, when a metal film was deposited by setting a flowing current at a high current density in order to deposit the metal film at high-speed, such a phenomenon became remarkable.
The present invention provides a film deposition device and a film deposition method of a metal film, which can reduce formation of an oxide in a deposited metal film and can suppress the metal film from closely sticking to a solid electrolyte membrane during film deposition.
After vigorous investigation, the present inventors considered the reason why the oxide is formed as follows. Specifically, in the proximity of an interface between the solid electrolyte membrane and the metal film, a velocity by which metal ions are supplied from the solid electrolyte membrane becomes slower with respect to a velocity by which the metal ions decrease due to metal precipitation, as a result thereof, a concentration of the metal ions decreases in the proximity of the interface. Thus, activity of the metal ions becomes lower and reduction of hydrogen ions (generation of hydrogen) prevails over reduction of metal ions (precipitation of metal). The metal hydroxide is dewatered thereafter and finally metal oxide is formed.
On the other hand, the reason why the deposited metal film and the solid electrolyte membrane closely stick was similarly considered as follows. In the proximity of an interface between the solid electrolyte membrane and the metal film, since a concentration of the metal ions decreases, a metal precipitation process becomes a rate-determining process due to material transfer from a rate-determining process due to charge transfer, and dendrite-like metal is precipitated. As a result thereof, irregularity increases on a surface of the metal film, thus the solid electrolyte membrane is likely to closely stick to the metal film due to an anchoring effect.
Then, the present inventors considered that in order to suppress the concentration of metal ions from decreasing in the proximity of an interface between the solid electrolyte membrane and the metal film like this, a water content of the solid electrolyte membrane is important. That is, it is considered that by making a water content contained in the solid electrolyte membrane rich, metal ions are diffused in a water cluster formed in the solid electrolyte membrane, and the metal ions can be conducted thereby.
A first aspect of the present invention relates to a film deposition device of a metal film, which includes a positive electrode, a solid electrolyte membrane, and a power supply part that applies a voltage between the positive electrode and a base material to be a negative electrode. The solid electrolyte allows a water content to be 15% by mass or more and is capable of containing metal ions. The power supply part applies a voltage between the positive electrode and the base material in a state where the solid electrolyte membrane is disposed on a surface of the positive electrode such that metal is precipitated on a surface of the base material from the metal ions contained inside the solid electrolyte membrane.
According to the film deposition device of the present invention, during film deposition, in a state where the solid electrolyte membrane is disposed on the positive electrode, the solid electrolyte membrane is brought into contact with the base material. When, in this state, a voltage is applied by the power supply part between the positive electrode and the base material to be a negative electrode, metal can be precipitated from the metal ions contained inside the solid electrolyte membrane on a surface of the base material. Thus, a metal film made of the metal of the metal ions can be deposited on a surface of the base material.
Here, by use of a solid electrolyte membrane of which water content is 15% by mass or more (a solid electrolyte membrane having a water containing capacity of 15% by mass or more as a water content) as the solid electrolyte membrane, the film deposition can be performed with the water content of the solid electrolyte membrane set to 15% by mass or more. Thus, when the water content of the solid electrolyte membrane is increased, an amount of water clusters can be increased.
As a result, since the metal ions are readily supplied from the solid electrolyte membrane to the proximity of an interface between the solid electrolyte membrane and the metal film, the concentration of the metal ions is suppressed from decreasing. Thus, since a local pH decrease accompanying the reduction of hydrogen ions is suppressed in the proximity of an interface between the solid electrolyte membrane and the metal film, generation of metal hydroxide is suppressed, and formation of metal oxide on a surface of the metal film becomes difficult thereby.
Further, in the precipitation process of the metal ions, since the charge transfer becomes faster than the material transfer, the dendrite-like metal is difficult to precipitate, the surface of the metal film becomes smooth, and the metal film becomes difficult to closely stick to the solid electrolyte membrane thereby.
Thus, even when a density of current that flows through the solid electrolyte membrane is high, since the transport velocity of the metal ions inside thereof is not lowered, the metal film can be more rapidly deposited. Here, in the case where the water content of the solid electrolyte membrane becomes less than 15% by mass, since the water content of the solid electrolyte membrane is low, the oxide is likely to be formed on a surface of the metal film, and the metal film tends to closely stick to the solid electrolyte membrane.
The positive electrode may be formed into a porous body through which a solution containing the metal ions is capable of transmitting such that the metal ions can be supplied to the solid electrolyte membrane. The positive electrode made of the porous body can transmit the solution containing the metal ions to the inside, and the transmitted solution (metal ions thereof) can be supplied to the solid electrolyte membrane. Thus, during film deposition, via the positive electrode that is a porous body, the solution containing the metal ions can be supplied as needed. The supplied solution transmits through the inside of the positive electrode and comes into contact with the solid electrolyte membrane adjacent to the positive electrode, the metal ions are impregnated in the solid electrolyte membrane and the water content of the solid electrolyte membrane can be held in the range described above.
As a result like this, the metal ions in the solid electrolyte membrane are precipitated during film deposition and can be stably supplied from the positive electrode side. Thus, without limiting an amount of metal that can be precipitated, a metal film having a desired film thickness can be continuously deposited on surfaces of a plurality of base materials.
The film deposition device may include a metal ion supply part that supplies a solution containing the metal ions to the positive electrode. When thus constituted, while supplying the solution containing metal ions from the metal ion supply part, metal films can continuously be deposited.
The film deposition device described above may include a pressing part that pressurizes the solid electrolyte membrane against the base material by moving the positive electrode toward the base material. Since the solid electrolyte membrane can be pressurized against the base material via the positive electrode by the pressing part, by making the electrolyte membrane uniformly follow a surface of the base material in a film deposition region, a metal film can be coated on a surface thereof. Thus, a homogeneous metal film having a uniform film thickness can be deposited on a surface of the base material.
A second aspect of the present invention relates to a metal film deposition method, which includes sandwiching the solid electrolyte membrane with the positive electrode and the base material to be a negative electrode such that the solid electrolyte membrane comes into contact with the positive electrode and the negative electrode; containing metal ions inside the solid electrolyte membrane; and depositing a metal film made of the metal on a surface of the base material by applying a voltage between the positive electrode and the negative electrode to precipitate the metal from metal ions contained inside the solid electrolyte membrane on a surface of the base material. By using a solid electrolyte membrane that is capable of containing a water content of 15% by mass or more as the solid electrolyte membrane, the film deposition is performed by setting the water content of the solid electrolyte membrane to 15% by mass or more.
According to the metal film deposition method, the solid electrolyte membrane is disposed on a surface of the positive electrode and the solid electrolyte membrane is brought into contact with the base material. In this state, a voltage is applied between the positive electrode and the base material to make the metal precipitate from metal ions contained inside the solid electrolyte membrane on a surface of the base material, and a metal film can be deposited on a surface of the base material thereby.
Here, since the film deposition is performed by setting the water content of the solid electrolyte membrane to 15% by mass or more, by increasing the water content of the solid electrolyte membrane, an amount of water clusters can be increased. As a result, since the metal ions from the solid electrolyte membrane become liable to be supplied to the proximity of an interface of the solid electrolyte membrane and the metal film, the concentration of the metal ions can be suppressed from decreasing. Thus, in the proximity of an interface of the solid electrolyte membrane and the metal film, since a local pH decrease accompanying the reduction of hydrogen ions can be suppressed, generation of metal hydroxide is suppressed, and oxide becomes difficult to be formed on a surface of the metal film.
Further, in the process of precipitation of the metal ions, since the charge transfer becomes faster than the material transfer, the dendrite-like metal becomes difficult to precipitate, a surface of the metal film becomes smooth, and the metal film is difficult to closely stick to the solid electrolyte membrane thereby.
Thus, even when a density of current that flows the solid electrolyte membrane is high, since a transport velocity of the metal ions inside thereof does not decrease, the metal film can be deposited at a higher speed. Here, in the solid electrolyte membrane of which water content is less than 15% by mass, since the water content is low, the oxide is likely to be formed on a surface of the metal film, and the metal film tends to closely stick to the solid electrolyte membrane thereby.
As the positive electrode, a porous body through which a solution containing the metal ions can transmit such that the metal ions are supplied to the solid electrolyte membrane may be used. Here, by using the positive electrode made of the porous body, the solution containing the metal ions can be transmitted to the inside thereof, and the transmitted solution can be supplied to the solid electrolyte membrane. Thus, during film deposition, via the positive electrode that is a porous body, the solution containing the metal ions can be supplied as needed. The solution containing the supplied metal ions transmits the inside of the positive electrode, comes into contact with the solid electrolyte membrane adjacent to the positive electrode, the metal ions are impregnated in the solid electrolyte membrane, and the water content of the solid electrolyte membrane can be maintained in the range described above thereby.
As a result like this, the metal ions in the solid electrolyte membrane are precipitated during film deposition and, at the same time, can be stably supplied from the positive electrode side. Therefore, without limiting an amount of metal that can be precipitated, the metal film having a desired film thickness can be continuously deposited on surfaces of a plurality of base materials.
The metal film may be deposited while supplying the solution containing the metal ions to the positive electrode. When thus performed, while supplying the solution containing the metal ions to the positive electrode, the metal films can be continuously deposited.
The solid electrolyte membrane may be pressurized against a film deposition region of the base material by moving the positive electrode toward the base material. When thus performed, since the solid electrolyte membrane can be pressurized via the positive electrode, by making the solid electrolyte membrane uniformly follow a surface of the base material in a film deposition region, a metal film can be coated on the surface.
According to the present invention, oxide formation on a metal film to be deposited can be reduced and, at the same time, the metal film can be suppressed from closely sticking to the solid electrolyte membrane.
Features, advantages, and technical and industrial significance of exemplary embodiments of the invention will be described below with reference to the accompanying drawings, in which like numerals denote like elements, and wherein:
As shown in
The film deposition device 1A includes at least a positive electrode 11 made of metal, a solid electrolyte membrane 13 disposed on a surface of the positive electrode 11, and a power supply part 14 for applying a voltage between the positive electrode 11 and a base material B to be a negative electrode.
Further, on an upper surface of the positive electrode 11, a metal ion supply part 15 for supplying a solution containing metal ions (hereinafter, referred to as a metal ion solution) L to the positive electrode 11 is disposed. In a bottom part of the metal ion supply part 15, an opening is formed, and, in an internal space of the metal ion supply part 15, the positive electrode 11 is housed in a state engaged with an inner wall 15b.
A solution tank 17 in which the metal ion solution L is housed is connected via a supply tube 17a to one side of the metal ion supply part 15, and, to the other side thereof, a waste liquid tank 18 that recovers a waste liquid after use is connected via a waste liquid tube 18a.
When constituted like this, the metal ion solution L housed in the solution tank 17 can be supplied via the supply tube 17a to the inside of the metal ion supply part 15 and the waste liquid after use can be sent via the waste liquid tube 18a to the waste liquid tank 18.
Further, since the positive electrode 11 is housed in a state engaged with the inner wall 15b in an internal space of the metal ion supply part 15, the metal ion solution L supplied from above of the internal space can be supplied to the positive electrode 11. Here, the positive electrode 11 is made of a porous body that transmits the metal ion solution L and supplies metal ions to the solid electrolyte membrane. As such a porous body, as long as it has (1) corrosion resistance against the metal ion solution L, (2) the electric conductivity capable of operating as a positive electrode, (3) permeability of the metal ion solution L, and (4) capability of being pressed with a pressing part 16 described below, there is no particular restriction. For example, a foamed metal body made of a foam having continuous open cells, which has an ionization tendency lower than that of the film deposited metal (or higher in an electrode potential), such as foamed titanium can be used.
Further, regarding the condition of (3) described above, in the case where a foamed metal body is used, for example, it is preferable that the foamed metal body has the porosity of about 50 to 95% by volume, a pore diameter of about 50 to 600 μm, and a thickness of about 0.1 to 50 mm.
Further, a pressing part 16 is connected to a cap part 15a of the metal ion supply part 15. The pressing part 16 pressurizes the solid electrolyte membrane 13 against a film deposition region E of the base material B by moving the positive electrode 11 toward the base material B. For example, as the pressing part 16, a hydraulic or air cylinder and so on can be used.
Further, the film deposition device 1A includes a pedestal 21 that fixes the base material B and adjusts alignment of the base material B to be a negative electrode with respect to the positive electrode 11 and a temperature controller 22 that adjusts temperature of the base material B via the pedestal 21.
As the metal ion solution L, an aqueous solution that contains ions of, for example, copper, nickel, silver or the like can be used. For example, in the case of copper ion, a solution containing copper sulfate, copper pyrophosphate or the like can be used. As the solid electrolyte membrane 13, a membrane, a film or the like made of a solid electrolyte can be used.
The solid electrolyte membrane 13 is a membrane made of a solid electrolyte having the water content of 15% by mass or more, which, when brought into contact with the metal ion solution L described above, can impregnate the metal ions in the inside thereof, and in which the metal ions move on a surface of the base material B when a voltage is applied, and a metal derived from the metal ions is reduced and can be precipitated.
As a material of the solid electrolyte membrane, a fluororesin such as Nafion (registered trade mark) manufactured by DuPont, a hydrocarbon resin, or a resin having an, ion exchange function such as SELEMION (CMV, CMD, CMF series) manufactured by ASAHI GLASS Co., Ltd. can be used. By properly selecting a kind and a ratio of a functional group of a produced resin, a solid electrolyte (resin) of which a water content can be set to 15% by mass or more can be obtained. In general, as the number of the ion exchange groups increases, the water content of the solid electrolyte membrane can be increased, and these can be manufactured according to a generally well-known method. For example, by varying a hot-press time of these resins, the water content can be adjusted. In particular, as the resin that satisfies such a range of the water content, a resin such as a perfluorosulfonic acid resin can be used. Further, the upper limit of the water content of the solid electrolyte membrane is preferably 80% by mass or less, and, in this range, both of the metal ions and the water content can be preferably impregnated while maintaining the film strength.
Hereinafter, a film deposition method according to the present embodiment will be described. Firstly, on the pedestal 21, the base material B is disposed, alignment of the base material B is adjusted with respect to the positive electrode 11, and a temperature of the base material B is adjusted by a temperature controller 22. Next, as shown in
Then, by means of the pressing part 16, the positive electrode 11 is moved toward the base material B, and the solid electrolyte membrane 13 is pressurized against the film deposition region E of the base material B thereby. Thus, since the solid electrolyte membrane 13 can be pressurized via the positive electrode 11, the solid electrolyte membrane 13 is made to uniformly follow a surface of the base material B of the film deposition region. That is, by electrical energization with the power supply part 14 described below while contacting (pressurizing) the solid electrolyte membrane 13 with the base material by use of the positive electrode 11 as a backup material, a metal film F having a more uniform film thickness can be deposited.
Next, by use of the power supply part 14, a voltage is applied between the positive electrode 11 and the base material B to be a negative electrode to precipitate metal from the metal ions contained inside the solid electrolyte membrane 13 on a surface of the base material B. At this time, the metal film F is deposited while supplying the metal ion solution L to the positive electrode 11.
As a result like this, by use of the positive electrode 11 made of a porous body, the metal ion solution L can be transmitted to the inside thereof, and the transmitted solution L can be supplied to the solid electrolyte membrane 13 together with the metal ions. Thus, during film deposition, the metal ion solution L can be supplied as needed to the solid electrolyte membrane 13 via the positive electrode 11 that is a porous body. The supplied metal ion solution L transmits the inside of the positive electrode 11 and comes into contact with the solid electrolyte membrane 13 adjacent to the positive electrode 11, and, the metal ions are impregnated in the solid electrolyte membrane 13 and the water content of the solid electrolyte membrane 13 can be maintained at 15% by mass or more.
Then, when a voltage is applied between the positive electrode 11 and the base material B to be a negative electrode, the metal ions inside the solid electrolyte membrane 13, which are supplied from the positive electrode side move from the positive electrode 11 side to the base material B side, and metal from the metal ions contained in the inside of the solid electrolyte membrane 13 is precipitated on a base material side. Thus, a metal film F can be deposited on a surface of the base material B.
According to the present embodiment, as the solid electrolyte membrane 13, a solid electrolyte membrane having the water content of 15% by mass or more (a solid electrolyte membrane having water containing capacity of 15% by mass or more as the water content) is used, and a film deposition is performed by setting the water content of the solid electrolyte membrane 13 to 15% by mass or more.
Here, the conduction of the metal ions in the solid electrolyte membrane is considered to be performed not by ion hopping like proton but by ion diffusion in a water cluster. By increasing the water content of the solid electrolyte membrane 13 (by setting to the water content described above), an amount of water cluster can be increased. Thus, a region in which a transition metal ion having a high valence can move is increased, and a transportation amount of ions per unit area can be increased.
As result like this, since the metal ions are made to be readily supplied from the solid electrolyte membrane 13 to the proximity of an interface between the solid electrolyte membrane 13 and the metal film F, a concentration of the metal ions can be suppressed from becoming lower. Thus, since in the proximity of an interface between the solid electrolyte membrane 13 and the metal film F, a local pH decrease accompanying the reduction of hydrogen ions can be suppressed from occurring, generation of metal hydroxide derived from the metal ions is suppressed and formation of oxide on a surface of the metal film F becomes difficult.
Further, in the process of precipitation of metal ions, since the charge transfer becomes faster than the material transfer, the dendrite-like metal is difficult to be precipitated, a surface of the metal film F becomes smooth, and the metal film F is difficult to closely stick to the solid electrolyte membrane 13.
Thus, even when a density of current that flows the solid electrolyte membrane 13 is high, since a transport velocity of the metal ions inside thereof does not decrease, the metal film F can be deposited at a higher speed.
Here, in the case where the water content of the solid electrolyte membrane 13 becomes less than 15% by mass, since the water content of the solid electrolyte membrane 13 is low, oxide is likely to be formed on a surface of the metal film F, and the metal film F tends to closely stick to the solid electrolyte membrane 13 thereby.
Further, since the metal ion solution L can be supplied as needed via the positive electrode 11 that is a porous body, without limiting an amount of metal that can be precipitated, a metal film F having a desired film thickness can be continuously deposited on surfaces of a plurality of base materials B.
The present invention will be described with reference to the following examples.
By use of a device shown in
A mass of a solid electrolyte membrane in a dry state (dry mass) was measured, after immersing this in pure water, moisture attached on a surface thereof was wiped, in this state, a mass of the solid electrolyte membrane (mass in wet base) was measured, and the water content (% by mass) was calculated according to the following formula.
(Mass in wet base−Dry mass)/Mass in wet base
As a metal ion solution, a solution of 1 mol/L copper sulfate was prepared, while pressurizing under 0.5 MPa from above the positive electrode, at normal temperature for a treatment time of 30 minutes, a copper film was deposited on a surface of a base material. At this time, the limiting current density during film deposition (the maximum current density that does not generate film abnormality) was measured. The results are shown in the following Table 1 and
In the same manner as Example 1, a copper film was manufactured on a surface of the base material. Specifically, the solid electrolyte membrane of Example 2 had the water content of 30% by mass, the solid electrolyte membrane of Example 3 had the water content of 28% by mass, the solid electrolyte membrane of Example 4 had the water content of 28% by mass, and the solid electrolyte membrane of Example 5 had the water content of 23% by mass.
With film deposition devices of these Examples 2 to 5, in the same manner as Example 1, the limiting current density during film deposition (the maximum current density that does not generate film abnormality) was measured. The results are shown in the following Table 1 and
In the same manner as Example 1, a copper film was formed on a surface of a base material. Except Example 2, the water content was different from that of Example 1 (capacity that can contain water is different). Specifically, a solid electrolyte membrane of Comparative Example 1 had the water content of 11% by mass and a solid electrolyte membrane of Comparative Example 2 had the water content of 9% by mass.
With film deposition devices of Comparative Example 1 and 2, in the same manner as Example 1, the limiting current density during film deposition (the maximum current density that does not generate film abnormality) was measured. The results are shown in the following Table 1 and
(Results) As shown in
In the above, Embodiments of the present invention were described in more detail. However, the present invention is not limited to the embodiments described above, and various design modifications can be applied.
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