The present invention relates to a film forming method and a film forming apparatus, for forming a film by accelerating powder of a material, together with gas, spraying and depositing the powder onto a surface of a substrate with the powder being kept in a solid state.
In recent years, a film forming method called, “cold spray method”, has been known. A cold spray method is a method of: jetting out powder of a metallic material in a state where the metallic material is at its melting point or softening point or lower, together with inert gas, such as helium, argon, or nitrogen, from a nozzle; causing the powder kept in its solid state to collide with a substrate to be subjected to film formation; and forming a film on a surface of the substrate (for example, see Patent Literature 1). In the cold spray method, differently from a thermal spraying method (for example, see Patent Literature 2) of melting powder of a material and spraying the powder onto a substrate, film formation is performed at comparatively low temperature. Therefore, by the cold spray method, an influence of thermal stress is able to be alleviated and a metallic film with no phase transformation and suppressed oxidation is able to be obtained. In particular, if the material to be the substrate and film is metallic, when the powder of the metallic material collides with the substrate (or the film that has been formed first), since plastic deformation occurs between the powder and substrate to provide anchor effect, the oxide films are mutually destroyed, and metallic bonding is generated between the newly formed surfaces, a layered body having high adhesive strength is able to be obtained.
Normally, the cold spray method is conducted in the atmosphere. Further, in the cold spray method, since the powder is accelerated to high speed by compressed gas, a nozzle having a hole diameter small as compared with the substrate is used. Therefore, a film that has been already formed on an area, which is other than an area where the powder jetted out from the nozzle is being sprayed on for film formation, is exposed to oxygen in the atmosphere and may be oxidized. As a result, film formation is further conducted over the oxidized film and bonding between the top layer and the bottom layer becomes insufficient, influencing bonding strength and film properties, such as electric properties.
In order to suppress the exposure of the film to oxygen, film formation within a decompressed chamber may be considered. However, in that case, an exhaust device is required to be provided in the chamber and thus the configuration of the apparatus becomes complicated and cost of the apparatus becomes expensive. Further, a long period of time is required to achieve the decompressed atmosphere after the substrate is arranged in the chamber, and thus start of film formation is delayed. Furthermore, in order to replace the substrate, a sequence of releasing the decompressed atmosphere, replacing the substrate, decompressing again, and the like, becomes necessary, and this sequence problematically requires time and effort.
As another means for suppressing the exposure of the film to oxygen, film formation without oxygen by filling the inert gas into the chamber may be considered. However, in this case also, a device for supplying the inert gas needs to be separately provided in the chamber, increasing the cost of the apparatus. Further, time for replacing the atmosphere in the chamber with the inert gas after arranging the substrate in the chamber is required, and thus time and effort are again required to replace the substrate.
The present invention has been made in view of the above, and an object thereof is to provide a film forming method and a film forming apparatus, which are able to achieve: suppression of oxidation of a film being formed; a simple and inexpensive apparatus configuration; and replacement of a substrate to be subjected to film formation without time and trouble.
To solve the above-described problem and achieve the object, a film forming method according to the present invention forms a film by accelerating powder of a material with gas and spraying and depositing the powder onto a surface of a substrate with the powder being kept in a solid state, and the film forming method includes: a substrate arrangement step of arranging the substrate in a chamber; and a film forming step of forming a film. The film forming step includes: jetting out the powder and inert gas from a nozzle towards the substrate; causing inside of the chamber to be under positive pressure by the inert gas; and depositing the powder on the surface of the substrate.
In the above-described film forming method, the film forming step is performed while the inert gas is exhausted from the chamber.
In the above-described film forming method, the film forming step is performed while flow of the inert gas in the chamber is regulated.
In the above-described film forming method, the flow of the inert gas is regulated by supplying inert gas into the chamber, separately from the nozzle.
A film forming apparatus according to the present invention forms a film by accelerating powder of a material with gas and spraying and depositing the powder onto a surface of a substrate with the powder being kept in a solid state, and includes: a chamber; a holding unit that is provided in the chamber and configured to hold the substrate; a nozzle configured to jet out the powder with inert gas; and a moving mechanism configured to move any one of the nozzle and the holding unit with respect to other one of the nozzle and the holding unit, wherein inside of the chamber is caused to be under positive pressure by the inert gas jetted out from the nozzle.
The above-described film forming apparatus further includes an exhaust unit configured to exhaust gas from the chamber.
The above-described film forming apparatus further includes a flow regulating mechanism configured to regulate flow of the inert gas inside the chamber.
In the above-described film forming apparatus, the flow regulating mechanism is a gas supplying unit configured to supply the inert gas into the chamber.
In the above-described film forming apparatus, the flow regulating mechanism is a flow regulating member arranged in the chamber.
In the above-described film forming apparatus, the chamber comprises: a container including the holding unit provided in the chamber; and a lid portion attached to the nozzle.
In the above-described film forming apparatus, the chamber comprises a cover that is attached to the nozzle and configured to cover the holding unit.
According to the present invention, since powder of a material and inert gas are jetted out towards a substrate, inside of a chamber is caused to be under positive pressure by the inert gas, and the powder is deposited on a surface of the substrate; the substrate is prevented from being exposed to oxygen and oxidation of a film being formed is able to be suppressed. Further, according to the present invention, since an additional device, such as an exhaust device or an inert gas supplying device, is not required to be provided in the chamber, the apparatus is able to be configured simply and inexpensively. Furthermore, according to the present invention, since an additional operation, such as decompressing the chamber or replacing the gas, is not required before film formation, the substrate is able to be replaced without time and effort.
Hereinafter, modes for carrying out the present invention will be described in detail, with reference to the drawings. The present invention is not limited by the following embodiments. Further, each drawing referred to in the following description just schematically illustrates shapes, sizes, and positional relations so as to allow contents of the present invention to be understood. That is, the present invention is not limited only to the shapes, sizes, and positional relations exemplified in each drawing.
The chamber 10 has: a container 10a that is formed in a bottomed column shape; and a lid portion 10b that covers an opening of the container 10a. The specific shape of the container 10a is not particularly limited, and in the first embodiment, is a shape, in which a flange extending outwards from the opening is provided in the bottomed column. Further, a shape of the lid portion 10b is prescribed according to a shape of the opening of the container 10a, and in the first embodiment, is a disc shape.
The lid portion 10b is attached to the spray nozzle 12 by fastening, bonding, welding, or the like, and is supported by a non-illustrated support mechanism of the spray nozzle 12 to be three dimensionally movable. Further, as illustrated in
A diameter of the lid portion 10b is designed to be larger than a diameter of the opening of the container 10a, according to a movable range of the spray nozzle 12, such that the opening of the container 10a is not exposed even if the lid portion 10b is moved in the plane parallel to the opening plane 10c upon film formation.
The holding unit 11 is provided, for example, at a bottom portion of the container 10a. The holding unit 11 includes a holding mechanism, such as an electrostatic chuck, and holds the substrate 1 in a state where a film forming surface 1a of the substrate 1 faces the spray nozzle 12. Although
The spray nozzle 12 accelerates the powder 2 supplied from the powder supplying unit 13, by the inert gas supplied via the gas heating unit 14, and jets out the powder 2 at supersonic speed of, for example, 340 m/s or higher.
Compressed gas formed of inert gas, such as helium, argon, or nitrogen, which has been compressed, is supplied from the outside to the powder supplying unit 13 and gas heating unit 14. A non-illustrated valve for adjusting a feed rate of the compressed gas is provided in each of the powder supplying unit 13 and gas heating unit 14.
The powder 2 of a metal or an alloy, which is the material of the film, is contained in the powder supplying unit 13. The powder supplying unit 13 supplies the powder 2, together with the inert gas supplied from the outside, to the spray nozzle 12, via the powder piping 13a.
The gas heating unit 14 heats up the inert gas supplied from the outside to a predetermined temperature and supplies the heated inert gas to the spray nozzle 12 via the gas piping 14a. The temperature to which the inert gas is heated up is, for example, equal to or higher than 50° C., and according to a type of the powder 2, is set (for example, to about 300° C. to 900° C.) such that the powder 2 does not melt.
The drive unit 15 is provided at the spray nozzle 12, and is a part of a moving mechanism that moves the spray nozzle 12 together with the lid portion 10b. A well known general technique is applicable as the moving mechanism and in
Next, a film forming method according to the first embodiment will be described.
First, in Step S1, the substrate is arranged in the chamber 10. A material to be used as the substrate 1 is not particularly limited, and may be: a metal or an alloy, such as copper, copper alloy, zinc, zinc alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, nickel, nickel alloy, iron, iron alloy, titanium, titanium alloy, chromium, chromium alloy, niobium, niobium alloy, molybdenum, molybdenum alloy, silver, silver alloy, tin, tin alloy, tantalum, tantalum alloy, or the like; or a ceramic, such as alumina, zirconia, yttria, yttria stabilized zirconia, or the like. A surface treatment may be performed as appropriate in advance on the substrate 1 formed of any of these materials. In the chamber 10, the substrate 1 is fixed by being held by the holding unit 11.
At subsequent Step S2, the powder 2, which is a material of a film to be formed on the substrate 1, is filled into the powder supplying unit 13. A type of the powder 2 is not particularly limited, and according to use of the film, a metal or an alloy, such as copper, copper alloy, zinc, zinc alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, nickel, nickel alloy, iron, iron alloy, titanium, titanium alloy, chromium, chromium alloy, niobium, niobium alloy, molybdenum, molybdenum alloy, silver, silver alloy, tin, tin alloy, tantalum, tantalum alloy, or the like may be selected as appropriate. Further, a mean particle diameter of the powder 2 is not particularly limited as long as the mean particle diameter is of a size (for example, about 5 μm to 100 μm) that enables cold spraying.
At subsequent Step S3, the film forming apparatus 100 is activated. Thereby, supply of the compressed gas (inert gas) to the powder supplying unit 13 and gas heating unit 14 is started and the powder 2 and heated inert gas are supplied to the spray nozzle 12. In the spray nozzle 12, the powder 2 is charged into the supersonic flow of the compressed inert gas and accelerated, and jetted out with its solid state being kept, together with the inert gas, from the spray nozzle 12.
Thereby, the atmosphere is exhausted from the gap 10d by the inert gas jetted out from the spray nozzle 12 and the inside of the chamber 10 is caused to be under positive pressure. Therefore, the inert gas jetted out from the spray nozzle 12 collides with the surface of the substrate 1, thereafter circulates inside the chamber 10, and is exhausted to the outside of the chamber 10 from the gap 10d, as illustrated with the broken lines in
Pressure of the inert gas supplied to the spray nozzle 12 is preferably 1 MPa to 5 MPa. This is because, by adjusting the pressure like this, the inside of the chamber 10 is able to be made under positive pressure by the inert gas at an early stage, and in later Step S4, improvement of adhesive strength between the substrate 1 and the film formed thereon is able to be achieved.
At Step S4, a film is formed on the substrate 1. That is, while the powder 2 is being jetted out from the spray nozzle 12 to be sprayed onto the film forming surface 1a, the spray nozzle 12 is moved in the horizontal direction to deposit the powder 2 onto the film forming surface 1a. When that is done, since the inside of the chamber 10 is filled with the inert gas jetted out from the spray nozzle 12, the film on the film forming surface 1a is prevented from being exposed to oxygen and oxidation of the film is able to be suppressed.
After a film of a desired thickness is formed on the film forming surface 1a, the film forming apparatus 100 is stopped (Step S5). Thereafter, at Step S6, the lid portion 10b is removed from the container 10a, and the substrate 1 is taken out. Thereby, a film formed by the cold spray method is obtained. Thereafter, another substrate may be held by the holding unit 11 of the film forming apparatus 100 and film formation may be performed continuously.
As described above, according to the first embodiment, since the inside of the chamber 10 is filled with the inert gas jetted out from the spray nozzle 12 to be under positive pressure and film formation is performed, oxidation of the formed film by the formed film being exposed to oxygen in the atmosphere is able to be suppressed. Therefore, physical properties in the film, such as the bonding strength and electric properties, are able to be improved.
Further, according to the first embodiment, since an additional device (such as an exhaust device or gas supplying device) for removing the atmosphere from the inside of the chamber 10 is not required to be provided, a configuration of the apparatus is able to be simplified and increase in cost of the apparatus is able to be suppressed.
Furthermore, according to the first embodiment, since the inside of the chamber 10 is caused to be under positive pressure by the inert gas jetted out from the spray nozzle 12, an additional operation (exhaust, gas replacement, or the like) for removing the atmosphere from the chamber 10 and waiting time, after arrangement of the substrate 1 in the chamber 10, become unnecessary. Therefore, replacement of the substrate 1 becomes easy and film formation is able to be conducted efficiently.
Next, a first modified example of the first embodiment will be described.
The flow regulating unit 17 is formed by bending one end of a cylindrical member inwards and is provided near the bottom portion of the container 10a to surround the holding unit 11. The flow regulating unit 17 regulates the flow of the inert gas jetted out from the spray nozzle 12 so that the flow circulates inside the chamber 10 to be exhausted out from the gap 10d.
The gas supplying unit 18 includes a gas jetting port 18a provided near the bottom portion of the container 10a and forms flow of the inert gas circulating inside the chamber 10 by supplying the inert gas into the chamber 10. By flowing the inert gas along an inner wall surface from near the bottom portion of the container 10a, the inert gas is able to be efficiently circulated inside the chamber 10.
By providing the flow regulating unit 17 and gas supplying unit 18, exhaust of the atmosphere remaining in the chamber 10 is able to be achieved earlier and the inside of the chamber 10 is able to be filled with the inert gas jetted out from the spray nozzle 12 promptly. Therefore, oxidation of the film formed on the substrate 1 is able to be suppressed even more effectively.
In the film forming apparatus 110, only one of the flow regulating unit 17 and the gas supplying unit 18 may be provided. Further, a shape and arrangement of the flow regulating unit 17 are not limited to the example illustrated in
Next, a second modified example of the first embodiment will be described.
Although the gap 10d provided between the container 10a and the lid portion 10b serves as the exhaust port in the above described first embodiment, a form of the exhaust port is no limited to the example illustrated in
Next, a second embodiment of the present invention will be described.
Functions and operations of the holding unit 11, the spray nozzle 12, the powder supplying unit 13 and powder piping 13a, the gas heating unit 14 and gas piping 14a, the drive unit 15, and the control unit 16, which are illustrated in
In the second embodiment, the holding unit 11 is directly provided on the base 20 and the cover unit 21 is arranged to cover the holding unit 11. The cover unit 21 may be formed of a hard member (a member difficult to be deformed), such as a metal, a ceramic, a glass, or an acrylic, or may be formed of a flexible member (a member easy to be deformed), such as rubber, or polyethylene. Or, the cover unit 21 may be formed of a combination of the hard member and the soft member. For example, the cover unit 21 may be formed by forming a framework with a hard member such as a metal, and covering the framework with a flexible member such as polyethylene sheet.
At an upper portion (at a position higher than the substrate 1 being held by the holding unit 11) of the cover unit 21, one opening 21a or a plurality of openings 21a (two in
When a film is formed by the film forming apparatus 200, the substrate 1 is held by the holding unit 11 and the powder 2 of the material and inert gas are jetted out from the spray nozzle 12. Thereby, inside of the cover unit 21 is filled with the inert gas and is caused to be under positive pressure. By moving the spray nozzle 12 together with the cover unit 21 in a plane parallel to the base 20 while spraying the powder 2 towards the film forming surface 1a of the substrate 1, the powder 2 is deposited on the film forming surface 1a. As a result, without exposing the film formed on the film forming surface 1a to oxygen, film formation is able to be performed.
As described above, according to the second embodiment, since the chamber is formed of the cover unit 21 attached to the spray nozzle 12, a configuration of the film forming apparatus 200 is able to be simplified. For example, the film forming apparatus 200 is able to be realized by adding the cover unit 21 to a cold spray apparatus having a general configuration.
The flow regulating unit 17 and gas supplying unit 18 may be provided further in the film forming apparatus 200, similarly to the first embodiment.
In the above described first and second embodiments, although the substrate 1 is fixed and the spray nozzle 12 is moved, as long as one of them is able to be moved with respect to the other, any of the substrate 1 and spray nozzle 12 may be moved. For example, the spray nozzle 12 may be fixed and the substrate 1 may be moved, or both of them may be moved.
Hereinafter, a working example of the present invention will be described.
As a working example, a pure copper film was formed on the substrate 1 by using the film forming apparatus 100 according to the first embodiment. When this was done, pressure of inert gas in the spray nozzle 12 was changed to form films of a plurality of types. By cutting out these films to make test pieces of 2 mm×2 mm×40 mm, conductivity thereof was measured by four-terminal method. In contrast, as a comparative example, a pure copper film was formed in the atmosphere by using a general cold spray apparatus. Similarly to the working example, test pieces were made to measure the conductivity.
As illustrated in
Number | Date | Country | Kind |
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2012-225535 | Oct 2012 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2013/077391 | 10/8/2013 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
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WO2014/057951 | 4/17/2014 | WO | A |
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