Method and apparatus for manufacturing functional materials

Abstract

In conventional methods for manufacturing functional materials, a problem has been that when the material thin film is separated from the support and powdered, the active portion of the functional material thin film comes into rapid contact with oxygen and moisture, causing heat generation and material degradation. The objective is to provide a method for manufacturing functional powder materials without impairing their activity. [Solution] By recovering the material film from the support by peeling or scraping it off, or immediately after recovery, under a CVD atmosphere, the new active surface created by powderization is also subjected to CVD film formation, thus preventing loss of activity.

Description

Technical Field

[0001] The present disclosure relates to a method and a manufacturing apparatus for producing a functional material using a vacuum film formation method. In particular, the present disclosure relates to a method and a manufacturing apparatus for producing a functional material by pulverizing a material film produced through a composite thin-film forming step of raw materials into powder in a stable state.

Background Art

[0002] Functional materials produced through a composite thin-film forming step of raw materials are used in various fields such as materials for various energy devices including batteries, various ceramic devices, and carbon material devices, and are indispensable for many industrial products. For example, high-capacity secondary batteries such as lithium-ion batteries are widely used in many fields because of their high energy density and capability of repeated charge and discharge. Specifically, they are used in various fields including driving power sources for electric vehicles such as electric vehicles and hybrid vehicles, the mobility field such as drones, batteries for portable electronic devices such as smartphones and tablet terminals, and energy storage systems for efficiently storing and supplying electric power in conjunction with renewable energy such as photovoltaic power generation.

[0003] Various materials have been researched as negative electrode materials for high-capacity secondary batteries for the purpose of improving energy density. Among them, Si / C-based negative electrode materials have attracted much attention because by combining the characteristics of silicon (Si) and carbon (C), they overcome the problems of single silicon and single graphite to a certain extent and exhibit high performance. Several methods have been proposed as methods for producing negative electrode materials.

[0004] Silicon has an extremely high theoretical capacity and a high lithium storage capacity, so it enables realization of high-capacity batteries. However, since it repeatedly expands and contracts during charging and discharging, it has a problem that this leads to structural destruction.

[0005] Various methods have been employed to suppress expansion and contraction. For example, a method has been disclosed in which porous carbon fine powder is used, and silicon is deposited in the porous pores using thermal CVD (chemical vapor deposition) with silane (SiH4) gas to absorb the expanded volume (Patent Document 1).

[0006] Furthermore, a method for producing functional materials without using silane gas has also been disclosed. In this method, an ionic liquid is provided on the surface of a polymer film substrate, then a thin film of metal or a metal compound is formed to obtain a laminate, and the obtained laminate is heated to a point above the melting point of the ionic liquid to peel the ionic liquid and the thin film from the substrate, separating and recovering the ionic liquid and the thin film (Patent Document 2). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Special Publication No. 2018-534720 [Patent Document 2] Japanese Patent Publication No. 2015-096628 [Overview of the project] [Problems that the invention aims to solve]

[0008] The method described in Patent Document 1 requires the use of silane gas. Silane gas is known to have extremely high flammability and the risk of explosion, as well as corrosiveness and toxicity, posing safety problems. Therefore, there is a need to develop a method that can achieve equivalent or better performance without using silane gas. Furthermore, the invention described in Patent Document 2 does not require the use of silane gas, but when separating the material thin film from the support, the active part of the material thin film comes into rapid contact with oxygen and water molecules in the air, causing heat generation and material degradation. The object of this invention is to provide a method for forming a powder without using silane gas and without impairing the activity of the obtained material during the manufacturing process, and for removing it from the manufacturing equipment. In particular, the object is to provide a method for powdering without impairing the function. [Brief explanation of the drawing]

[0009] [Figure 1] A schematic diagram showing the configuration of the manufacturing apparatus for functional materials in Embodiment 1. [Figure 2] A flowchart showing an example of a method for manufacturing a functional material in Embodiment 1. [Figure 3] A schematic diagram showing the configuration of the manufacturing apparatus for functional materials in Embodiment 2. [Figure 4] A schematic diagram showing the crushing device of the functional material manufacturing apparatus in Embodiment 2. [Figure 5] A flowchart showing an example of a method for manufacturing a functional material in Embodiment 2. [Modes for carrying out the invention]

[0010] The following description focuses on functional materials used in anode materials for high-capacity secondary batteries, particularly Si / C-based (silicon-carbon composite) anode materials. However, the description is not limited to these, and the materials can be suitably used as manufacturing methods and equipment for functional materials constructed through a composite thin-film process of raw materials, such as functional materials used in various energy devices including batteries, various ceramic devices, and carbon material devices. Specifically, these materials can be used not only for Si / C-based anode materials but also for hydrogen storage alloys and the like.

[0011] The following explanation will be given with reference to the drawings, but the present invention is not limited to the disclosures below. To manufacture various materials, the arrangement of the film-forming source can be changed or the order of film formation can be rearranged. Also, here, for convenience, we refer to it as "powder," but this is a general term for materials obtained by crushing a laminate with a formed film and functional properties, and includes not only powder but also somewhat larger pieces of the formed film.

[0012] Furthermore, when electrostatic deposition is performed using the carbon powder shown in the following examples, a film is not strictly formed. However, including these structures, the formed layered structure will be referred to here as a "film," the formed single layered structure will be referred to as a "film-deposited body," and the structure in which these are stacked will be referred to as a "laminated body." The process of forming a film, including the layered structure, will be referred to as the film-depositing step.

[0013] Here, "functional materials" refer to "stable powders with functional properties" manufactured through a composite thin-film formation process and CVD film deposition. Furthermore, the laminate produced through the composite thin-film formation process before CVD film deposition, although functional, is referred to as a material film or powder material because it is intended for the production of powder.

[0014] A method for producing a functional material according to one aspect of the present invention is characterized by comprising: a film deposition step of forming a film of a first material on a support in a vacuum; a recovery step of peeling or scraping off the film from the support and recovering it as a film-deposited recovery product in the form of powder; and a CVD step of forming a film on the film-deposited recovery product using a raw material gas ionized in a reduced pressure atmosphere, simultaneously with and / or after the recovery step.

[0015] Furthermore, a method for producing a functional material according to one aspect of the present invention is characterized by comprising the step of forming a second material in layers on the lower layer and / or upper layer of the film-forming body.

[0016] Furthermore, a method for producing a functional material according to one aspect of the present invention is characterized in that the first material contains silicon, or the second material contains carbon, or the raw material gas contains carbon.

[0017] Furthermore, an apparatus for producing a functional material according to an aspect of the present invention includes: a substrate moving functional unit that moves a cylindrical can rotating in vacuum or a substrate; a vapor deposition functional unit that evaporates at least one material by a vapor deposition method to form a film by evaporating the material on the cylindrical can or the substrate; a recovery functional unit that peels or scrapes off the laminate from the cylindrical can or the substrate; and a CVD functional unit that performs CVD film formation simultaneously with and / or after the peeling or scraping in the recovery functional unit.

[0018] Furthermore, the apparatus for producing a functional material according to an aspect of the present invention is characterized in that the CVD functional unit is provided in a vacuum chamber for film formation or in a vacuum chamber different from the vacuum chamber for film formation, and the recovery functional unit for recovering the laminate from the cylindrical can or the substrate is provided in the CVD functional unit.

[0019] Furthermore, the apparatus for producing a functional material according to an aspect of the present invention includes a second film-forming functional unit, wherein the second film-forming functional unit is a functional unit that forms a film from a material different from the material used in the vapor deposition functional unit, and is provided before and / or after the vapor deposition functional unit and before the CVD functional unit.

[0020] Furthermore, the apparatus for producing a functional material according to an aspect of the present invention is characterized in that the CVD functional unit is located in a vacuum chamber provided separately from the vacuum chamber for performing film formation, and the recovery functional unit performs crushing and peeling together with the film-formed substrate.

[0021] According to the present disclosure, when a vapor-deposited film is peeled off and recovered as powder, a newly generated surface can be immediately exposed to a CVD atmosphere and stabilized, thereby preventing the produced functional powder material from coming into abrupt contact with oxygen, moisture or the like to cause heat generation or deterioration.

[0022] [Embodiment 1] FIG. 1 is a diagram schematically showing the functional material manufacturing apparatus according to Embodiment 1. The diagram shows an apparatus for manufacturing a functional material by forming a laminate on a cylindrical can that revolves in a vacuum chamber. Around the cylindrical can that revolves in the vacuum chamber, an evaporation source, a film forming source, and a CVD functional unit are arranged. Each time the cylindrical can makes one revolution, materials are sequentially laminated from the evaporation source and the film forming source to manufacture a laminate.

[0023] Vapor deposition is performed in a vapor deposition functional unit. The evaporation source faces the peripheral surface of the cylindrical can, holds an evaporation raw material, and the heated evaporation material becomes vapor and travels toward the peripheral surface of the cylindrical can. Examples of the evaporation raw material include silicon oxide, silicon oxynitride, silicon nitride, organic silicon, nickel, titanium and the like. As the heating means, various methods such as resistance heating, electron beam heating and others can be used. The evaporation raw material deposited on the peripheral surface of the cylindrical can forms a powder material. The thickness of the material film is adjusted to a desired thickness by the evaporation rate of the evaporation material, the rotation speed of the cylindrical can, and the like. In addition, the thin film does not necessarily need to be a continuous film, and may be a perforated thin film or a discontinuous thin film. It may have unevenness. The vapor deposition functional unit, as a function of controlling vapor deposition film formation, has a configuration including an evaporation source, a heating means and the like necessary for performing vapor deposition, and a shutter capable of blocking adhesion of a vapor deposited substance is provided between the evaporation source and the cylindrical can.

[0024] In addition to the evaporation source, another film forming source as a second film forming functional unit may be arranged around the cylindrical can. The film forming source may be an evaporation source, or may be a film forming source using other film forming methods including a sputtering source, a transfer film forming source, an electrostatic coating source and the like. In the film forming source, for example, carbon powder or the like can be used as a film forming raw material. The second film forming functional unit, as a function of controlling film formation, has a configuration necessary for performing film formation, and a shutter capable of blocking adhesion of a film forming substance is provided between the film forming source and the cylindrical can.

[0025] By using the evaporation source 200 and the film deposition source 250 in combination, various material films such as multilayer thin films and composite films can be formed on the circumferential surface of a cylindrical can. The evaporation source 200 and film deposition source 250 on the cylindrical can can be repeated to deposit each component until the desired thickness is reached. Alternatively, either the evaporation source 200 or the film deposition source 250 may be used alone.

[0026] If the material film formed on the circumferential surface of the cylindrical can by the evaporation source 200 and the film formation source 250 has high material activity, there is a risk that the material film will be rapidly reacted to generate heat and deteriorate when exposed to an atmosphere containing oxygen and water vapor in order to produce powder using the material film formed in a vacuum. This risk is even higher in the process of peeling off the material film and further pulverizing it. To avoid the risk of deterioration in the process of peeling off and pulverizing the film, the apparatus of Embodiment 1 is provided with a CVD function unit 300. The process of peeling off the material film and further pulverizing it can be performed within the CVD function unit 300. Since a CVD film can be quickly formed on the surface created by peeling and pulverization, deterioration of the functional material can be prevented. The CVD step is performed, for example, by ionizing or thermally decomposing the raw material gas and introducing it to the CVD film formation surface. The CVD function unit is equipped with the necessary components for performing CVD film formation and components for controlling film formation.

[0027] As shown in Figure 1, the area covered by the CVD functional unit 300 may extend over a wide area of ​​the cylindrical can, or it may be limited to only the immediate vicinity of the peeling / scraping device 350. By making the CVD functional unit extensive, the surface of the material film after deposition and before peeling can be covered with a CVD film, and the material after peeling can also be covered with a CVD film. The recovery functional unit, equipped with a peeling device and a scraping device, is located within the CVD functional unit, allowing CVD film deposition to be performed simultaneously with or after recovery.

[0028] Various CVD methods, such as thermal CVD and plasma CVD, can be used to form CVD films. CVD is a gas reaction process with a relatively short mean free path, which has the advantage of easily forming dense and thin films regardless of surface irregularities. Therefore, it is possible to densely cover the surface of the material film with few coating defects, preventing degradation of the material due to oxygen and water vapor. Another advantage of CVD is the wide range of gas types that do not adversely affect the performance of the powder material.

[0029] When manufacturing Si / C-based anode materials, examples of gases used for CVD film formation include hydrocarbon gases such as acetylene gas and propane. The CVD film is formed on the surface of the material film formed on the circumferential surface of the cylindrical can by the evaporation source 200 and film formation source 250, as well as on the newly formed surface that has been peeled off and formed as powder. If the material of the material film formed on the circumferential surface of the cylindrical can by the evaporation source 200 and film formation source 250 is highly reactive, there is a high risk of the material film degrading due to rapid reaction caused by exposure to an atmosphere containing oxygen and water vapor when returning the material film formed in a vacuum to an atmospheric pressure environment to produce powder. To reduce this risk, it is effective to perform the process of peeling off the material film and further pulverizing it in the CVD functional unit 300, and to quickly form a CVD film on the newly formed surface. By covering the powder with a CVD film while producing it in a vacuum chamber, it is possible to suppress rapid reactions by preventing reactions with oxygen and water vapor. Therefore, a safe and high-quality functional powder material 1010 can be obtained.

[0030] Various methods and combinations thereof can be used to peel the material film from the circumferential surface of a cylindrical can. These include methods that utilize the physical properties of the material film, such as applying heat to the material film from a heat source and using the difference in thermal expansion to peel it off; methods that physically scrape it off using a jig like a scraper; methods that use vibration; and methods that use the internal stress of the material film to peel it off, including natural delamination. Here, all of these methods are referred to as "peeling." The recovery function unit is equipped with the components necessary for peeling and scraping, as well as the components necessary for recovery, and is also equipped with functions to control these components.

[0031] To obtain functional materials, it is also possible to apply a pulverization step to further pulverize the material film that has been peeled off. Part of the pulverization step may be removed from the CVD functional unit 300 and carried out in a vacuum chamber. As for the pulverization step, a roller mill, jet mill, hammer mill, vibratory mill, planetary mill, bead mill, etc., can be used as appropriate, but are not limited to these. Part of the pulverization step can be carried out in the vacuum chamber beforehand, or outside the vacuum chamber, before being removed from the vacuum chamber.

[0032] The peeling / scraping device 350 can be activated when the powder material 1000 formed on the circumferential surface of the cylindrical can by the evaporation source 200 and the film formation source 250 reaches the desired thickness. Alternatively, CVD film formation can be performed by the CVD functional unit 300 without activating the peeling / scraping device 350. For example, CVD film formation may be performed prior to the formation of a material film on the circumferential surface of the cylindrical can by the evaporation source 200 and the film formation source 250, or each time a material film is formed. In this embodiment, the functional material is peeled and recovered as powder under a CVD atmosphere, but the presence of a surface covered by the CVD film provides higher stability against oxygen, water vapor, etc.

[0033] According to the method of this embodiment, the surface created by peeling and pulverization begins to be covered with a CVD film almost immediately after its formation. Therefore, it is possible to suppress the rapid reaction on the newly formed surface and obtain high-quality powder.

[0034] Figure 2 shows an example of a method for manufacturing a functional material using the apparatus of Embodiment 1. Here, vapor deposition is performed first. When manufacturing a Si / C-based anode material, small lumps or granules of Si can be suitably used as the evaporation raw material. After vapor deposition, a second film deposition is performed. When manufacturing a Si / C-based anode material, carbon powder is used as the film deposition raw material. Vapor deposition and the second film deposition are repeated until a predetermined film thickness is reached. The film thickness of each layer can be controlled by the evaporation rate of the evaporation material and the rotation speed of the cylindrical can. Once the predetermined film thickness is reached, CVD film deposition is performed while peeling the functional material film from the cylindrical can under a CVD atmosphere. Therefore, the surface created by peeling is immediately covered with CVD. Thus, the powder surface can be covered with a stable material. After powder formation, the functional powder material 1010 can be removed from the vacuum chamber and further pulverized.

[0035] The flowchart shown in Figure 2 illustrates an example of a manufacturing method; for example, the order of vapor deposition and the second film deposition may be reversed. The order can be appropriately changed to suit the film being manufactured. Furthermore, in the vapor deposition and second film deposition steps, the CVD film may be laminated without peeling when it passes through the CVD functional section.

[0036] This describes a method for producing a functional material using the apparatus of Embodiment 1. [Example 1] (1) Silicon was used as the evaporation material, and a silicon thin film was formed on the circumferential surface of a cylindrical can by electron beam deposition. A silicon thin film of 0.5 microns was deposited with an electron beam output of 10 kW and a circumferential velocity of 0.5 m / min of the cylindrical can. (2) As a second film formation, carbon powder was used as the raw material, and a carbon layer with an average thickness of 0.5 microns was formed using electrostatic deposition. (3) Processes (1) and (2) above were repeated to form a laminate on the circumferential surface of the cylindrical can, and the laminate formation was terminated when the thickness of the laminate reached approximately 50 microns. (4) As a plasma CVD film, acetylene gas was used as the raw material gas, and the laminated material formed on the surface of the cylindrical can was peeled off using a peeling / scraping device 350 while operating a high-frequency plasma of 500W. The peeled laminated material was pulverized as appropriate to obtain powder of the desired size.

[0037] [Example 2] (1) Silicon was used as the evaporation material, and a silicon thin film was formed on the circumferential surface of a cylindrical can by electron beam deposition. A silicon thin film of 0.5 microns was deposited with an electron beam output of 10 kW and a circumferential velocity of 0.5 m / min of the cylindrical can. (2) As a plasma CVD film, acetylene gas was used as the raw material gas, and the silicon thin film already formed on the surface of the cylindrical can was peeled off using a peeling / scraping device 350 while operating a high-frequency plasma of 500W. The peeled silicon thin film was appropriately pulverized to obtain the desired powder.

[0038] Example 2 is an example of manufacturing a functional material by performing some of the steps in the flowchart shown in Figure 2 to form a film. As in Example 1, it is not necessary to perform all of the film formation steps shown in the figure; only the necessary steps should be performed depending on the purpose.

[0039] [Embodiment 2] Figure 3 is a schematic diagram showing a functional material manufacturing apparatus in Embodiment 2. The apparatus of Embodiment 2 is configured to form a film on a polymer substrate 120, with two cylindrical cans 110, 111 circulating in a vacuum chamber 100, unwinding rolls / winding rolls 130, 150, an evaporation source 200, a film formation source 250, and a CVD function unit 300. Although a polymer substrate is used here, thin films and substrates commonly used in this field, such as metal thin films, can be used. The substrate moving function unit includes a configuration for moving and controlling the cylindrical cans, unwinding rolls / winding rolls, etc.

[0040] The polymer substrate 120 is wound from the unwinding / winding roll 130 to the unwinding / winding roll 150 via the guide roller 140. Along the winding path, a laminate is formed by evaporation sources 200 and film deposition sources 250, which are positioned around two cylindrical cans, respectively. Specifically, while traveling along the cylindrical can 110, evaporation material is deposited from the evaporation source 200, which is positioned opposite the circumferential surface of the cylindrical can 110. The evaporation source 200 holds evaporation raw material 210, and the heated evaporation material 210 becomes vapor and moves toward the circumferential surface of the cylindrical can 110. Film deposition sources 250 other than the evaporation source 200 may also be positioned opposite the circumferential surface of the cylindrical can 110. The evaporation source 200 and film deposition source 250 may be configured to face the circumferential surface of the same cylindrical can, or, as shown in Figure 3, the evaporation source 200 and film deposition source 250 may be positioned facing the circumferential surfaces of separate cylindrical cans. By arranging the evaporation source 200 and the film deposition source 250 opposite each other on the circumferential surfaces of separate cylindrical cans, it becomes easier to optimize conditions such as substrate temperature, deposition atmosphere, and applied voltage according to the specific film formation process.

[0041] The film deposition source 250 may be an evaporation source, or it may be a film deposition source that uses other film deposition methods such as a sputtering source, a transfer deposition source, or an electrostatic coating source. This allows for the formation of various material films, such as multilayer thin films and composite films, on the polymer substrate 120. The cylindrical can may be operated in one direction or in both directions to stack the layers. By operating it in both directions, a laminate with the desired layers can be fabricated.

[0042] The thickness of the material film is adjusted to the desired thickness by the evaporation rate of the evaporation material and the running speed of the polymer substrate. Furthermore, the material film does not necessarily have to be a continuous film; it can be a perforated film, a discontinuous film, or even have irregularities. In addition, by providing a shutter between the evaporation source 200, the film formation source 250, and the cylindrical cans 110 and 111, a laminate with a desired layer structure can be formed.

[0043] In addition to forming a material film on the polymer substrate using the evaporation source 200 and the film formation source 250, the CVD functional unit 300 can also form a CVD film on the polymer substrate. The CVD film formation step is carried out, for example, by ionizing or thermally decomposing the raw material gas and guiding it to the CVD film formation surface.

[0044] The CVD film formation step can be performed either before or after forming the material film on the polymer substrate, or both, or, if multiple layers are being laminated, it can be performed each time a layer is laminated. For example, if it is performed immediately before forming the material film on the polymer substrate using the evaporation source 200 or the film formation source 250, the CVD film can be formed on the polymer substrate, the polymer substrate can be wound up, the polymer substrate with the CVD film formed on it can be unwound again, and then the material film can be formed. It is also possible to form another CVD film on top of the material film. In this case as well, the material film can be wound up, the polymer substrate with the material film formed on it can be unwound again, and then the CVD film can be formed.

[0045] The polymer substrate, on which a material film has been formed by the evaporation source 200 and the film formation source 250, is removed from the vacuum chamber 100 as a winding roll while still wound up. Subsequently, for example, in a CVD functional unit 300 constructed in another vacuum chamber 101 schematically shown in Figure 4, the substrate is pressurized by a crushing device 600, with the pressure direction being changed as appropriate, simultaneously with CVD film formation, thereby detaching a portion of the material film from the polymer substrate. The detached material film is recovered and, if necessary, pulverized.

[0046] Figure 5 is a flowchart showing an example of a method for manufacturing a functional material using the apparatus of Embodiment 2. Unwinding begins from the unwinding / winding roll 130, and the polymer substrate 120 is wound onto the unwinding / winding roll 150 while vapor deposition is performed by the evaporation source 200, followed by a second film formation by the film formation source 250. When manufacturing a Si / C-based anode material, small lumps or granules of Si can be suitably used as the film formation raw material for the evaporation source 200. When manufacturing a Si / C-based anode material, carbon powder can be used as the film formation raw material for the second film formation by the film formation source 250. After vapor deposition and second film formation of the polymer substrate are performed, and the polymer substrate 120 is completely wound onto the unwinding / winding roll 150, the cylindrical cans 110 and 111 begin to reverse. Unwinding begins from the unwinding / winding roll 150, the second film formation and vapor deposition are performed, and the polymer substrate 120 is wound onto the unwinding / winding roll 130. This process can be repeated until the desired film thickness is reached. Once the desired thickness is reached, the polymer substrate is removed and placed in the CVD functional section 301 of another vacuum chamber 101. In the CVD functional section 301, the crushing device 600 is operated under a CVD atmosphere to crush the functional thin film together with the polymer substrate, producing a powder. Because it is crushed under a CVD atmosphere to become a powder, any newly formed surface is also covered with the CVD film.

[0047] The flowchart shown in Figure 5 illustrates an example of a manufacturing method. For example, the order of vapor deposition and the second deposition may be reversed, or CVD deposition may be performed using the CVD function unit 300 in the vacuum chamber 100 before each vapor deposition deposition. The order can be changed or steps can be skipped depending on the type of film to be manufactured.

[0048] This describes a method for producing a functional material using the apparatus of Embodiment 2. [Example 3] (1) A silicon thin film was formed from an electron beam evaporation source while a PET film with a thickness of 20 microns and a width of 150 mm was transported along the circumferential surface of a first cylindrical can in a vacuum chamber 100. With an electron beam output of 10 kW and a circumferential speed of 1 m / min of the cylindrical can, a silicon thin film of 0.2 microns was deposited on the substrate. (2) Next, while conveying along the circumferential surface of the second cylindrical can, a second film was formed using carbon powder as the raw material and electrostatic deposition to create a carbon layer with an average thickness of 0.5 microns. (3) Once winding is complete, reverse the direction and wind the material onto the winding roll again. (4) Repeat steps (1) to (3), and when the thickness of the laminate reaches approximately 50 microns, the laminate formation is terminated and the laminate is removed together with the substrate. (5) The PET film with the material film already deposited was removed from the vacuum chamber 100 while still wound, with the core removed, and moved to another vacuum chamber 101 which has a built-in CVD function and crushing device. (6) With the CVD function activated, the crushing device was started and the coated PET film was pressed with a load of 10 tons multiple times, changing the direction of pressure, to peel the material film from the PET film and recover it as a coarse powder. If necessary, it was further pulverized to obtain a powder with the desired functionality.

[0049] Here, step (1) is performed in the first cylindrical can and step (2) is performed in the second cylindrical can, but it is also possible to perform only step (1), wind it onto a winding roll, reverse the direction of rotation, and then perform step (2). Alternatively, step (1) may be performed in the first cylindrical can and step (2) in the second cylindrical can, followed by reversing the direction of rotation. During the reversal, a second film deposition may be performed in the second cylindrical can, followed by vapor deposition in the first cylindrical can.

[0050] [Example 4] (1) A silicon thin film was formed from an electron beam evaporation source while a PET film with a thickness of 20 microns and a width of 150 mm was transported along the circumferential surface of a first cylindrical can in a vacuum chamber 100. A silicon thin film of 0.2 microns was deposited with an electron beam output of 10 kW and a circumferential speed of 1 m / min of the cylindrical can. (2) Next, while the PET film was running along the circumferential surface of the second cylindrical can in the vacuum chamber 100, carbon was deposited on the silicon thin film by plasma CVD. Using acetylene gas as the raw material gas, a carbon-based thin film with an average thickness of 0.005 microns was formed using a high-frequency plasma of 500 W. (3) The PET film was unwound and steps (1) and (2) above were repeated five times each. (4) The PET film with the material film already formed was removed from the vacuum chamber 100 while still wound, with the core removed, and moved to another vacuum chamber 101 which has a built-in CVD function and crushing device. (5) With the CVD function running, the crushing device was activated, and the pre-deposited PET film was pressed with a load of 10 tons multiple times, changing the direction of pressure, to peel off some of the material film from the PET film and recover it as coarse powder. If necessary, it was further pulverized to obtain the desired material powder.

[0051] As described above, the functional material manufactured in this embodiment is peeled and crushed under a CVD atmosphere, so the newly formed surface can also be covered with a CVD film. Therefore, even when the manufactured powder is removed from the vacuum chamber and exposed to the atmosphere, no degradation occurs. [Explanation of symbols]

[0052] 100, 101 Vacuum chamber 110, 111 Cylindrical can 120 Polymer substrate 130, 150 unwinding / rewinding rolls 140 Guide Rollers 200 Evaporation source 210 Raw materials for evaporation 250 Film deposition source 300, 301 CVD Functional Units 350 Stripping / Scraping Device 600 Crushing device 1000 powder material 1010 Functional powder materials

Claims

1. A film deposition step in which a film of a first material is formed on a support in a vacuum, A recovery step of peeling or scraping off the film-formed body from the support and recovering it as a film-formed recovery material containing powder, A method for producing a functional material, characterized by having a CVD step, simultaneously with and / or after the recovery step, in which a film is formed on the film-deposited recovered material using a raw material gas ionized in a reduced-pressure atmosphere.

2. A method for producing a functional material according to claim 1, characterized by comprising the step of forming a second material in layers on the lower layer and / or upper layer of the film-forming body.

3. A method for producing a functional material according to claim 1, comprising a laminate formation step of alternately forming layers of a first material and a second material on the upper layer of the film-forming body until a desired thickness is reached.

4. A method for producing a functional material according to claim 1, characterized in that the first material contains silicon.

5. The method for producing a functional material according to claim 2, characterized in that the second material contains carbon.

6. The method for producing a functional material according to claim 1, characterized in that the raw material gas contains carbon.

7. A method for producing a functional material according to claim 1, further comprising a pulverization step under a CVD atmosphere.

8. It is equipped with a cylindrical can that rotates within the vacuum chamber, or a substrate moving function that moves the substrate, A vapor deposition function unit that evaporates at least one material by vapor deposition to form a film on the cylindrical can or the substrate, A recovery function unit for peeling or scraping off the film-forming material from the cylindrical can or the substrate, A manufacturing apparatus for functional materials, characterized in that the recovery function unit has a CVD function unit that performs CVD film formation simultaneously with and / or after peeling or scraping.

9. Furthermore, it is equipped with a second film-forming function section, The second film-forming functional section is a functional section that forms a film using a material different from the material used in the vapor deposition functional section. The apparatus for manufacturing a functional material according to claim 8, characterized in that it is provided in a manner that allows for film formation before and / or after the vapor deposition function and before the CVD function, and that it forms a laminate.

10. The CVD function unit is It is provided in the vacuum chamber in which the film is formed, or in a vacuum chamber separate from the vacuum chamber in which the film is formed, The apparatus for manufacturing a functional material according to claim 8 or 9, characterized in that the recovery function unit for recovering the laminate from the cylindrical can or the substrate is provided within the CVD function unit.

11. The CVD function unit is located in a vacuum chamber separate from the vacuum chamber used for film formation. The apparatus for manufacturing a functional material according to claim 10, characterized in that the recovery function unit provided within the CVD function unit performs crushing and peeling of the film-formed substrate together.

Images