Method for producing article having metal film, and metal film production apparatus

Abstract

This method for producing an article having a metal film comprises: a step for vaporizing an organic compound containing a metal; and a step for forming a metal film by depositing the metal contained in the organic compound containing the vaporized metal on an object to be coated. This metal film production apparatus comprises: a chamber; a first heating part which is in the chamber and is for placing and heating an organic compound containing a metal in order to generate a gas of the organic compound containing the metal; and a second heating part which is in the chamber, faces the first heating part, and is for placing and heating an object to be coated.

Description

METAL FILM PRODUCTION APPARATUS AND METAL FILM PRODUCTION APPARATUS

[0001] The present disclosure relates to a method and an apparatus for manufacturing an article having a metal film, and in particular to a method and an apparatus for manufacturing an article having a metal film that does not require large-scale equipment and can easily form a film.

[0002] The formation of metal films is subject to various constraints, such as the method itself and the material of the object on which the metal film is to be formed. For example, for substrates for 5G / 6G / terahertz waves, it is necessary to form a copper film on a low-dielectric-constant material (polymer), and currently, hot pressing of copper foil is a candidate. However, hot pressing of copper foil requires large equipment, and furthermore, depending on the heating temperature, it may exceed the heat resistance temperature of the substrate. Other candidates include sputtering and vapor deposition, but both require high vacuum (up to 10 －４ A vacuum chamber of 1000 Pa is required.

[0003] Furthermore, there is a continuous method for producing copper-clad substrates in which a copper film is continuously formed on a polyimide film using copper formate (see, for example, Japanese Patent No. 2745677), but this method also requires large and complicated production equipment.

[0004] The formation of metal films plays an important role in achieving high integration, high functionality, and high reliability in semiconductor devices and electronic components. Therefore, there has been a demand for a technology that can form metal films more easily without requiring large, complex equipment.

[0005] In view of the above-mentioned problems, the present disclosure aims to provide a method for manufacturing an article having a metal film that can be easily formed without requiring large, complicated equipment, and a metal film manufacturing apparatus.

[0006] To achieve the above object, a method for manufacturing an article having a metal film according to a first aspect of the present disclosure includes the steps of vaporizing a metal-containing organic compound and depositing the metal contained in the vaporized metal-containing organic compound on an object to be coated to form a metal film. The "object to be coated" may be a component (object to be coated) included in the article, or a part or all of the object itself, such as a surface (a portion to be coated). This configuration allows for easy formation of a metal film by using an organic compound containing a metal that has a lower vaporization temperature than the metal itself.

[0007] A method for manufacturing an article having a metal film according to a second aspect of the present disclosure includes the steps of exposing a metal to a gas of an organic compound to produce a metal-containing organic compound, vaporizing the produced metal-containing organic compound, and depositing the metal contained in the vaporized metal-containing organic compound on a coating target to form a metal film. This configuration makes solid metal easy to handle, and enhances the safety of the manufacturing method.

[0008] A method for manufacturing an article having a metal film according to a third aspect of the present disclosure includes the steps of placing a metal-containing organic compound on a coating target, and depositing the metal contained in the metal-containing organic compound on the coating target to form a metal film. This configuration allows the metal-containing organic compound and the coating target to be placed very close to each other.

[0009] A fourth aspect of the present disclosure relates to a method for manufacturing an article having a metal film, which is the method for manufacturing an article having a metal film according to the first or second aspect of the present disclosure, and further relates to a method for manufacturing an article having a metal film, in which the metal-containing organic compound and the object to be coated are arranged facing each other in a chamber. With this configuration, the object to be coated is exposed to the vaporized metal-containing organic compound, and the metal can be easily deposited on the object to be coated.

[0010] A fifth aspect of the present disclosure relates to a method for producing an article having a metal film, and in the method for producing an article having a metal film according to the first or third aspect of the present disclosure, the metal-containing organic compound is in a paste or pellet form. This configuration makes it easier to handle the metal-containing organic compound during installation and also prevents dust generation.

[0011] A method for producing an article having a metal film according to a sixth aspect of the present disclosure is the method for producing an article having a metal film according to any one of the first to fifth aspects of the present disclosure, further comprising the step of removing water of hydration from the hydrate of the organic compound containing the metal at a temperature of 10° C. to 120° C. This configuration can improve the deposition rate of the metal film.

[0012] A seventh aspect of the present disclosure relates to a method for producing an article having a metal film, which is the method for producing an article having a metal film according to any one of the first to fifth aspects of the present disclosure, and further includes removing water of hydration from the hydrate of the metal-containing organic compound at room temperature. This configuration can improve the deposition rate of the metal film.

[0013] The method for producing an article having a metal film according to an eighth aspect of the present disclosure is the method for producing an article having a metal film according to the sixth or seventh aspect of the present disclosure, wherein the step of removing the hydration water is carried out under reduced pressure. With this configuration, the removal of the hydration water can be carried out more quickly than removal under atmospheric pressure.

[0014] A method for manufacturing an article having a metal film according to a ninth aspect of the present disclosure is the method for manufacturing an article having a metal film according to any one of the first to eighth aspects of the present disclosure, further comprising a step of heating the object to be coated. With this configuration, since the portion other than the metal of the metal-containing organic compound is organic, even if a substance other than the metal adheres to the object to be coated, it is decomposed by heat, and a metal film with higher purity can be formed.

[0015] A tenth aspect of the present disclosure relates to a method for producing an article having a metal film, which is the method for producing an article having a metal film according to any one of the first to ninth aspects of the present disclosure, wherein the metal contained in the metal-containing organic compound is at least one selected from the group consisting of copper, tin, cobalt, nickel, cadmium, lead, zinc, manganese, and magnesium. This configuration allows for the formation of a generally useful metal film.

[0016] A metal film manufacturing apparatus according to an eleventh aspect of the present disclosure includes a chamber, a first heating unit in the chamber for placing and heating an organic compound containing a metal to generate a gas of the organic compound containing the metal, and a second heating unit in the chamber opposite the first heating unit for placing and heating a coating target. With this configuration, a metal film manufacturing apparatus can be obtained that can easily form a metal film using an organic compound containing a metal that has a lower vaporization temperature than the metal itself.

[0017] A metal film manufacturing apparatus according to a twelfth aspect of the present disclosure includes a chamber, a first heating unit in the chamber for placing and heating a metal, a second heating unit in the chamber facing the first heating unit for placing and heating a coating target, and an organic compound supply unit for supplying a gas of an organic compound into the chamber. With this configuration, generation of the organic compound containing the metal, vaporization of the organic compound containing the metal, and formation of the metal film can be performed within the same chamber.

[0018] A metal film manufacturing apparatus according to a thirteenth aspect of the present disclosure includes a chamber and a first heating unit in the chamber for placing and heating a coating target and an organic compound containing a metal on the coating target. With this configuration, processes from placing the organic compound containing a metal to forming a metal film can be performed on the coating target.

[0019] A metal film manufacturing apparatus according to a fourteenth aspect of the present disclosure includes a chamber, a vaporizer for generating a gas of an organic compound containing a metal, a gas guide pipe fluidly connecting the chamber and the vaporizer, a first heating unit in the vaporizer for placing and heating the organic compound containing a metal to generate the gas of the organic compound containing the metal, and a second heating unit in the chamber for placing and heating a coating target. With this configuration, the vaporizer is independent of the chamber, thereby improving controllability and operability when vaporizing the organic compound containing a metal.

[0020] A metal film manufacturing apparatus according to a fifteenth aspect of the present disclosure includes a chamber, a vaporizer for generating a gas of an organic compound containing a metal, a gas guide pipe fluidly connecting the chamber and the vaporizer, and a second heating unit in the chamber for placing and heating a coating target, the second heating unit including a bubbling unit for generating the gas of the organic compound containing a metal using a carrier gas. With this configuration, since the vaporizer is independent from the chamber, controllability and operability can be improved when vaporizing the organic compound containing a metal.

[0021] A metal film manufacturing apparatus according to a sixteenth aspect of the present disclosure is the metal film manufacturing apparatus according to any one of the eleventh to fifteenth aspects of the present disclosure, further comprising a control unit that controls the pressure and the temperature of the heating unit within the chamber, and a plurality of control valves that operate to control the temperature and pressure within the chamber in response to control by the control unit. With this configuration, automation of the metal film manufacturing apparatus becomes possible.

[0022] According to the present disclosure, it is possible to obtain a method for manufacturing an article having a metal film and a metal film manufacturing apparatus that can be formed more easily without requiring large and complicated equipment.

[0023] 1 is a schematic diagram of a metal film manufacturing apparatus 1 according to an embodiment of the present disclosure. FIG. 2 is a flowchart illustrating the steps of a method for manufacturing an article having a metal film according to an embodiment of the present disclosure. FIG. 3 is a conceptual diagram of film formation in a method for manufacturing an article having a metal film according to an embodiment of the present disclosure. FIG. 4 is an exemplary temperature and pressure profile in a method for manufacturing an article having a metal film according to an embodiment of the present disclosure. FIG. 5 is a flowchart illustrating the steps of a method for manufacturing an article having a metal film according to another embodiment of the present disclosure. FIG. 6 is a schematic diagram of a metal film manufacturing apparatus 2 according to an embodiment of the present disclosure. FIG. 7 is a schematic diagram of a metal film manufacturing apparatus 3 according to an embodiment of the present disclosure. FIG. 8 is a diagram illustrating an example of a region where an electric field or plasma is generated in the metal film manufacturing apparatuses 2 and 3 according to an embodiment of the present disclosure. A, B, and C are diagrams illustrating examples of electrodes when an electric field or plasma is generated, respectively. FIG. 9 is a graph showing the relationship between a first predetermined temperature (dehydration temperature) and a film formation rate. FIG. 10 is a graph comparing the mass reduction rate of copper(II) formate tetrahydrate and the film formation rate.

[0024] This application is based on Japanese Patent Application No. 2022-122775, filed on August 1, 2022, the contents of which are incorporated herein by reference. The present invention will be more fully understood from the following detailed description. Further scope of application of the present invention will become apparent from the following detailed description. However, the detailed description and specific examples are preferred embodiments of the present invention and are described for illustrative purposes only. From this detailed description, various changes and modifications will be apparent to those skilled in the art within the spirit and scope of the present invention. The applicant does not intend to dedicate any of the described embodiments to the public, and modifications and alternatives that may not literally fall within the scope of the claims are considered part of the invention under the doctrine of equivalents.

[0025] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In the drawings, identical or similar reference numerals are used to designate identical or corresponding components, and redundant explanations will be omitted.

[0026] In the present disclosure, a compound composed of an organic compound and a metal (hereinafter referred to as a metal-containing organic compound) is used to form a metal film. For example, a complex or complex salt composed of an organic compound and a metal can be used as the metal-containing organic compound. In the present disclosure, it is preferable to use a metal-containing organic compound that vaporizes at a lower temperature than the metal itself. The metal film is formed by vaporizing the metal-containing organic compound and decomposing the organic compound in the metal-containing organic compound.

[0027] In the following, a compound generated from a carboxylic acid and a metal (hereinafter referred to as a metal carboxylate) will be used as an example of an organic compound containing a metal. A metal film is formed by utilizing the decomposition of the metal carboxylate to deposit the metal contained in the metal carboxylate on the target to be coated. Specifically, the metal carboxylate is heated and vaporized, and the metal is deposited on the target to be coated by decomposition of the vaporized metal carboxylate. Alternatively, a metal carboxylate is generated from a carboxylic acid and a metal, the generated metal carboxylate is heated and vaporized, and the metal is deposited on the target to be coated by decomposition of the vaporized metal carboxylate. Alternatively, a metal carboxylate is placed on the target to be coated, the target to be coated is heated, and the metal is deposited on the target to be coated by decomposition of the metal carboxylate on the target to be coated.

[0028] Generally, the temperature at which a metal vaporizes is several thousand degrees. For example, the boiling point of copper is 2571°C. Therefore, vaporizing a metal requires high-energy, highly heat-resistant equipment, which is extremely difficult. In contrast, metal carboxylates containing organic matter in their structure have a vaporization temperature that is much lower than that of the metal itself. For example, the vaporization temperature of copper formate is about 180°C. In this way, by using metal carboxylates, it is possible to easily form a metal film without requiring high-energy, highly heat-resistant equipment.

[0029] First, a metal film manufacturing apparatus 1 according to a first embodiment of the present disclosure will be described with reference to FIG. 1 . FIG. 1 is a schematic configuration diagram of the metal film manufacturing apparatus 1. The metal film manufacturing apparatus 1 includes a chamber 11, a heating unit 21 as a first heating unit, a heating unit 24 as a second heating unit, a gas supply unit 35, an exhaust unit 39, and a control device 50 as a control unit. The metal film manufacturing apparatus 1 may further include a formic acid supply unit 31 as a carboxylic acid (organic compound) supply unit. In the following description, copper formate S (e.g., copper(II) formate tetrahydrate) is used as a specific example of a carboxylic acid metal salt, and a substrate W is used as a specific example of a coating target.

[0030] The chamber 11 forms a space in which a metal film is formed. The chamber 11 has an upper lid 12 and a lower frame 13. The chamber 11 is configured so that the upper lid 12 can be moved toward and away from the lower frame 13 using an opening / closing mechanism (not shown), thereby opening and closing the chamber 11. The chamber 11 is configured so that it can be sealed when closed (when the upper lid 12 is brought into contact with the lower frame 13). The sealable chamber 11 is configured so that the internal pressure can be made lower than the external pressure. The metal film may be formed under vacuum (below atmospheric pressure), and the chamber 11 is configured to withstand a desired vacuum level (e.g., approximately 50 Pa (absolute pressure)). The chamber 11 is typically formed in a rectangular parallelepiped shape for ease of manufacture, but the outer peripheral wall may be curved for pressure resistance.

[0031] The heating unit 21 and the heating unit 24 are capable of applying heat to the copper formate S and the substrate W, respectively. The heating unit 21 includes a plate 22 on which the copper formate S is placed and a lamp 23 for heating the plate 22. In this embodiment, the plate 22 is formed in a plate shape and is disposed at the bottom within the chamber 11. The plate 22 has a mounting surface 22t on which the copper formate S is placed, which is formed flat from the viewpoint of mounting stability. Typically, the back surface of the mounting surface 22t is also formed flat. The plate 22 is typically disposed within the chamber 11 so that the mounting surface 22t is horizontal. The lamp 23 is configured to be able to heat the copper formate S placed on the plate 22 via the plate 22. In this embodiment, the lamp 23 is disposed below the plate 22 and in close proximity to the plate 22. In this embodiment, the lamp 23 is configured by a plurality of infrared lamps arranged along the back surface of the plate 22 at appropriate intervals. The plate 22 is formed of a material capable of transferring heat generated by the lamps 23 to the copper formate S. Typically, the plate 22 is formed of graphite, but may also be formed of a metal with high thermal conductivity. The amount of heat transferred from the lamps 23 to the copper formate S via the plate 22 is sufficient to raise the temperature of the copper formate S to the temperature at which the copper formate S vaporizes (sublimes). The plate 22 is typically configured to raise the temperature above the temperature at which the copper formate S vaporizes. The plate 22 is provided with a temperature sensor 41 that detects the temperature of the plate 22. The heating unit 24 includes a plate 25 on which the substrate W is placed and which incorporates a heater. The plate 25 may be, for example, a hot plate. In this embodiment, the plate 25 is formed in a plate shape and is disposed above the plate 22. The placement surface 25t of the plate 25 typically faces the placement surface 22t of the plate 22 within the chamber 11, and the two are disposed parallel to each other.

[0032] A vacuum feed-through (particularly a motion field-through) may be attached to the top lid 12 so that the plate 25 can be moved even when the chamber is in a vacuum state. For example, as shown in FIG. 1 , a bellows-type linear feed-through 42 may be attached to the top lid 12 so that the plate 25 can be moved up and down. The linear feed-through 42 moves the plate 25 up and down while maintaining the vacuum state in the chamber, thereby allowing the distance between the plate 25 and the plate 22, i.e., the distance between the substrate W and the copper formate S, to be adjusted as desired. The motion field-through may be attached to a vacuum component according to the purpose, such as moving or rotating the plate 25 in a vacuum.

[0033] The gas supply unit 35 includes a gas supply source (not shown), a gas supply nozzle 36, a gas supply pipe 37 that guides the supply gas C from the gas supply source (not shown) to the gas supply nozzle 36, and a gas supply control valve 38 disposed on the gas supply pipe 37. In this embodiment, the gas supply unit 35 is provided with a plurality of gas supply nozzles 36, and the gas supply pipe 37 branches into a plurality of pipes downstream of the gas supply control valve 38 as viewed in the flow direction of the supply gas C, and the branched gas supply pipes 37 are connected to each gas supply nozzle 36. The gas supply unit 35 is configured such that when the gas supply control valve 38 is opened, the supply of the supply gas C into the chamber 11 is supplied, and when the gas supply control valve 38 is closed, the supply of the supply gas C into the chamber 11 is interrupted. A gas is typically used as the supply gas C, and the type of the supply gas C may be an inert gas, or, for cooling purposes, air may be used from the viewpoint of reducing costs.

[0034] The exhaust unit 39 has an exhaust pipe 39j, a vacuum pump 39p disposed in the exhaust pipe 39j, and an exhaust control valve 39v also disposed in the exhaust pipe 39j. One end of the exhaust pipe 39j is connected to an exhaust port 39h provided in the chamber 11. The exhaust unit 39 is configured such that, with the vacuum pump 39p operating, when the exhaust control valve 39v is opened, the fluid in the chamber 11 is exhausted to the outside of the chamber 11, and when the exhaust control valve 39v is closed, the exhaust of the fluid to the outside of the chamber 11 is stopped.

[0035] The chamber 11 may further be provided with a formic acid supply unit 31. The formic acid supply unit 31 has a formic acid source (not shown), a formic acid nozzle 32, a formic acid pipe 33 that introduces formic acid F from the formic acid source (not shown) to the formic acid nozzle 32, and a formic acid control valve 34 disposed in the formic acid pipe 33. The formic acid source (not shown) has a vaporizer that vaporizes formic acid and is configured to be able to supply vaporized formic acid F into the chamber 11. The formic acid supply unit 31 is configured so that when the formic acid control valve 34 is opened, vaporized formic acid F is supplied into the chamber 11, and when the formic acid control valve 34 is closed, the supply of formic acid F into the chamber 11 is interrupted.

[0036] The control device 50 controls the operation of the metal film manufacturing apparatus 1. The control device 50 is connected to the heating units 21 and 24 by wire or wirelessly and is configured to send control signals to the heating units 21 and 24 to control the amount of heat generated (including no heat generation) from the lamps 23 and the plate 25. The control device 50 is also connected to the gas supply control valve 38 by wire or wirelessly and is configured to send control signals to the gas supply control valve 38 to control the supply of the supply gas C to the chamber 11 through the opening and closing operation of the gas supply control valve 38. The control device 50 is also connected to the vacuum pump 39p and the exhaust control valve 39v by wire or wirelessly and is configured to send control signals to the vacuum pump 39p and the exhaust control valve 39v to control the start and stop of the vacuum pump 39p and the opening and closing operation of the exhaust control valve 39v to control the discharge of the fluid from the chamber 11. The control device 50 is also connected to the temperature sensor 41 by wire or wirelessly and is configured to receive a signal related to the temperature detected by the temperature sensor 41. The control device 50 is also connected by wire or wirelessly to an opening / closing mechanism (not shown) that moves the top lid 12 of the chamber 11, and is configured to be able to control the opening and closing of the chamber 11 by sending a control signal to the opening / closing mechanism (not shown). When the formic acid supply unit 31 is provided, the control device 50 is also connected by wire or wirelessly to the formic acid control valve 34, and is configured to be able to control the supply of formic acid F to the chamber 11 through the opening and closing operation of the formic acid control valve 34 by sending a control signal to the formic acid control valve 34.

[0037] In the above description, the heating unit 21 includes the plate 22 and the lamps 23. However, instead of the lamps 23, a heater may be built into the plate 22. Similarly to the heating unit 21, the heating unit 24 may be configured with a plate and heat sources (lamps) arranged on its back surface. The plates 22 and 25 may be arranged so that their installation surfaces face each other. They may be arranged horizontally within the chamber 11, one above the other, or vertically, one to the left and one to the right. Furthermore, a showerhead (not shown) may be installed between the heating units 21 and 24 within the chamber 11 to uniformly distribute the vaporized copper formate S to the substrate W. The showerhead may have any suitable shape, such as a shape that covers the copper formate S before vaporization or a shape that collects the vaporized copper formate S. The showerhead may have any suitable number and arrangement of ports for distributing the vaporized copper formate S to the substrate W. The showerhead may be configured to be at the ambient temperature within the chamber 11, or may be configured to be temperature-controllable by the control device 50.

[0038] Continuing with reference to Fig. 2, a method for manufacturing an article having a metal film according to a second embodiment of the present disclosure will be described. In the second embodiment, copper formate S is heated and vaporized, and copper is deposited on the substrate W by decomposition of the vaporized copper formate S, thereby forming a metal film. Fig. 2 is a flowchart illustrating the procedure for forming a metal film using the metal film manufacturing apparatus 1.

[0039] 1 will be referred to as appropriate when referring to the configuration of the metal film manufacturing apparatus 1. The following description of the film formation procedure using the metal film manufacturing apparatus 1 also includes a description of the operation of the metal film manufacturing apparatus 1. In the initial state before operation, the metal film manufacturing apparatus 1 has the formic acid control valve 34, gas supply control valve 38, and exhaust control valve 39v closed, and the lamp 23, plate 25, and vacuum pump 39p stopped.

[0040] When the metal film manufacturing apparatus 1 is activated, the control device 50 opens the top lid 12 of the chamber 11 via an opening / closing mechanism (not shown), and copper formate S is placed on the plate 22 (placement step: S1-1). Here, "placing copper formate S on the plate 22" refers to placing the copper formate S in a state in which it receives heat from the plate 22, typically placing copper formate S on the placement surface 22t of the plate 22. Copper formate S may be placed directly on the plate 22, or, in the case of powder, may be placed in a container with excellent thermal conductivity, such as an aluminum petri dish. Similarly, a substrate W is placed on the plate 25 (placement step: S1-1). Here, "placing the substrate W on the plate 25" refers to placing the substrate W in a state in which it receives heat from the plate 25, typically placing the substrate W on the placement surface 25t of the plate 25. The top lid 12 is then closed via an opening / closing mechanism (not shown), and the chamber 11 is sealed.

[0041] Once the copper formate S and the substrate W have been placed and the chamber 11 is sealed, the control device 50 turns on the lamp 23 to start heating the heating unit 21, and opens the exhaust control valve 39v to exhaust the gas from the chamber 11 (vacuum exhaust step: S2). At this time, it is preferable to increase the degree of vacuum from the viewpoint of favorable gas diffusion when nitrogen gas is supplied, as will be described later, and in this embodiment, the pressure inside the chamber 11 is set to about 50 Pa (absolute pressure). Once the chamber 11 has reached a predetermined degree of vacuum, the control device 50 closes the exhaust control valve 39v. Next, the control device 50 opens the gas supply control valve 38 to supply nitrogen gas (N ２) is supplied (nitrogen supply step: S3). The nitrogen gas then spreads throughout the chamber 11, and the pressure inside the chamber 11 becomes approximately ambient (atmospheric) pressure. Once the pressure inside the chamber 11 reaches ambient pressure, the control device 50 increases the output of the lamp 23 to raise the plate 22 to a first predetermined temperature, which is maintained for a predetermined time (heating and maintaining step: S4). Here, the first predetermined temperature is any temperature that can vaporize impurities such as water (hydrated water) contained in the copper formate S. In this embodiment, the first predetermined temperature is set to 120°C, but it can be changed as appropriate depending on the conditions, and it may not be limited to a single point but may have a range. The temperature of the plate 22 may be estimated based on actual measurement data from the temperature detected by the temperature sensor 41. If the temperature change of the plate 22 and the temperature change of the copper formate S can be considered to be the same, the temperature detected by the temperature sensor 41 may be treated as the temperature of the copper formate S. When copper formate S reaches the first predetermined temperature, typically, all of the water becomes gas, so that copper formate S becomes anhydrous even if it is a hydrate.

[0042] Thereafter, the control device 50 opens the exhaust control valve 39v to exhaust the gas from the chamber 11 (evacuation step: S5), similar to the evacuation step (S2). Once the chamber 11 has reached a predetermined vacuum level, the control device 50 closes the exhaust control valve 39v and increases the output of the lamp 23 to raise the plate 22 to a second predetermined temperature (heating and maintaining step: S7). Once the plate 22 has reached the second predetermined temperature, the plate 22 is maintained at the second predetermined temperature for a predetermined time (heating and maintaining step: S7). The second predetermined temperature is any set value that can vaporize copper formate S, and is preferably as high as possible within the allowable range. In this embodiment, the second predetermined temperature is set to 270°C, but it can be changed as appropriate depending on the conditions and may be set to a range of values. The "predetermined time" may be an empirically estimated time required for film formation, or a time determined based on the actual measured thickness of the formed film.

[0043] While the plate 22 is maintained at the second predetermined temperature, the degree of vacuum in the chamber 11 may be the same as that in the evacuation step (S2), or may be on the order of several tens to several hundreds of Pa. Considering ease of manufacturing the device, a range of 5 Pa to 100 Pa is preferable. Even if the degree of vacuum in the chamber 11 is set to, for example, 50 Pa, the pressure in the chamber 11 will rise to approximately 500 Pa to 10,000 Pa due to the subsequent evaporation of copper formate S. The metal film may be formed under atmospheric pressure without evacuating the chamber 11 (reduced pressure).

[0044] Optionally, while maintaining the plate 22 at the second predetermined temperature, the control device 50 may control the plate 25 to maintain a third predetermined temperature in order to heat the substrate W to be coated. For example, if it takes a long time to heat the temperature, the temperature of the plate 25 may be raised at an early stage (such as by the time of the evacuation step (S2)). Alternatively, the plate 25 may be controlled to reach the third predetermined temperature (e.g., 280°C) by the time the temperature raising and maintaining step (S7) begins (by t2 in FIG. 4 described below). By heating the substrate W with the plate 25 and maintaining it at a predetermined temperature, deposition of non-metallic substances generated by the decomposition of copper formate S can be suppressed, allowing for the formation of a copper film with higher purity.

[0045] After the copper film has been formed, the control device 50 opens the exhaust control valve 39v to exhaust the gas from the chamber 11 (evacuation step: S8). The control device 50 then opens the gas supply control valve 38 to supply nitrogen gas into the chamber 11 through the gas supply nozzle 36, thereby restoring the pressure inside the chamber 11 to atmospheric pressure (nitrogen supply step: S9). Furthermore, the control device 50 turns off the lamp 23 (and the plate 25) and forcibly cools the heating unit 21, the heating unit 24, and the substrate by, for example, opening the gas supply control valve 38 to supply supply gas C into the chamber 11 through the gas supply nozzle 36 (cooling step: S10). Note that the exhaust unit 39 may also be used in the cooling step to favorably diffuse the supply gas C. The control device 50 then opens the chamber 11 and removes the substrate from the heating unit 24 (removal step: S11). This completes the production of a substrate having a copper film. After the substrate is removed from the heating unit 24, the control device 50 determines whether or not a command to terminate the manufacture of the substrate having the copper film has been received (determination step: S12). If no command has been received, the process returns to the placing step (S1-1) to process the next substrate W, and the above-described flow is repeated thereafter. On the other hand, if a command has been received in the step of determining whether or not a command to terminate the manufacture of the substrate having the copper film has been received (determination step: S12), the manufacture is terminated.

[0046] As described above, in the temperature increasing and maintaining step (S7), as shown in FIG. 3 , powdered copper formate S is heated to generate copper formate S gas, and the substrate W is exposed to the vaporized copper formate S, whereby copper (Cu) contained in the copper formate S is deposited on the substrate W, forming a copper film. Note that FIG. 3 is a schematic representation of the manner in which copper formate S is vaporized and the copper contained in the copper formate is deposited on the substrate W. In FIG. 3 , copper formate S is conveniently depicted as a bond between copper and a carboxyl group (Cu-COOH). Note that the substrate W may or may not be heated.

[0047] Referring now to FIG. 4 , the temperature profile of the plate 22 in the above-described manufacturing method, i.e., the temperature profile during heating of copper formate S, will be described. The graph in FIG. 4 has temperature on the vertical axis and time on the horizontal axis. At time t0, copper formate S is placed in the heating unit 21, and the temperature of the plate 22 begins to rise. The temperature is then increased to a first predetermined temperature (120°C in this embodiment). At time t1, the plate 22 reaches the first predetermined temperature, and the predetermined temperature is maintained until time t2, thereby vaporizing the hydrated water contained in the copper formate. The temperature is then further increased to a second predetermined temperature (270°C in this embodiment). At time t3, the plate 22 reaches the second predetermined temperature, and the predetermined temperature is maintained until time t4, thereby depositing the copper contained in the vaporized copper formate S on the substrate W. When the copper film formation is completed at time t4, cooling of the substrate begins. After the temperature of the substrate has decreased, the substrate with the copper film is removed from the chamber 11. Since the plate 22 and the copper formate S are in direct contact or in contact via a container, the temperature change of the plate 22 can be considered to be the same as the temperature change of the copper formate S. Similarly, the temperature change of the plate 25 can be considered to be the same as the temperature change of the substrate W.

[0048] Here, the first predetermined temperature will be described in more detail. The first predetermined temperature can be referred to as the temperature at which hydration water is removed from copper formate S, i.e., the dehydration temperature. In the graph of FIG. 4, the first predetermined temperature (dehydration temperature) is described as 120°C. However, the first predetermined temperature (dehydration temperature) is not limited to 120°C, and may be any temperature at which the hydration water in the hydrate (the hydration water in copper formate S in the second embodiment) can be vaporized. The temperature at which the hydration water can be vaporized may be, for example, 10°C to 120°C, 15°C to 80°C, or 20°C to 60°C, regardless of whether or not copper formate S is heated to the first predetermined temperature. Preferably, it is 20°C to 50°C.

[0049] When copper formate S is heated to a first predetermined temperature (e.g., 50°C), as shown in FIG. 4 , copper formate S is placed in the heating unit 21, and then the temperature of the plate 22 is started to increase, and the temperature of the plate 22 is raised to the first predetermined temperature (50°C). At time t1, the plate 22 reaches the first predetermined temperature (50°C), and the first predetermined temperature of the plate 22 is maintained until time t2. Alternatively, the first predetermined temperature (dehydration temperature) may be room temperature. "Room temperature" refers to a state in which neither heating nor cooling is performed externally. When copper formate S is heated to room temperature, the temperature of the plate 22 is not started to increase after copper formate S is placed in the heating unit 21, and the plate 22 is maintained at room temperature until time t2. At this time, the hydration water contained in the copper formate S naturally evaporates at room temperature.

[0050] At temperatures of 100° C. or less, whether or not the water of hydration contained in copper formate S has evaporated can be determined by measuring the mass of copper formate S. Therefore, the plate 22 may have a mass meter function.

[0051] Furthermore, in order to promote the vaporization of the hydrated water contained in copper formate S, the pressure inside the chamber may be reduced, regardless of whether copper formate S is heated or not. The pressure inside the chamber when reduced may be 1000 Pa or less, or may be 50 Pa or less, and is preferably 10 Pa or less. A lower pressure inside the chamber is preferable because a lower pressure can promote the vaporization of the hydrated water.

[0052] FIG. 10 is a graph showing the copper film formation rate when the first predetermined temperature (dehydration temperature) is changed. The film formation rate was calculated using the following formula (1): Film formation rate (%) = 100 × (mass of copper attached (deposited) on the substrate) / (mass of copper in the loaded copper formate tetrahydrate) (1). Under a reduced pressure of 10 Pa, the film formation rates were 21.2% at 25°C (room temperature), 20.9% at 60°C, 17.9% at 80°C, 9.0% at 100°C, and 8.8% at 120°C. Under atmospheric pressure, the rate was 17.9% at 25°C (room temperature). Thus, it can be seen that the temperature at which hydration water is dehydrated, i.e., the first predetermined temperature, is preferably closer to room temperature.

[0053] FIG. 11 is a graph showing the copper film formation rate during the process of mass loss of 1 g of copper formate S due to dehydration. When copper (II) formate tetrahydrate becomes anhydrous, its mass decreases by approximately 32%. The graph in FIG. 11 also shows that after 20 minutes, the mass of copper formate S stops changing and becomes anhydrous, and the copper film formation rate stabilizes. The measurements in FIG. 11 were performed at room temperature (i.e., without heating) and under reduced pressure (2 Pa). The mass loss rate was calculated using the following formula (2): Mass Loss Rate (%) = 100 × {1 - (mass of copper formate after dehydration) / (mass of copper formate tetrahydrate loaded)} (2) The graphs in FIGS. 10 and 11 reveal that dehydration at 60°C or below until the mass of copper formate S decreases by 30% or more can significantly improve the copper film formation rate.

[0054] Continuing with reference to Fig. 5, a method for manufacturing an article having a metal film according to a third embodiment of the present disclosure will be described. In the third embodiment, copper formate S is generated from a copper plate and formic acid, the generated copper formate S is heated and vaporized, and copper is deposited on the substrate W by decomposition of the vaporized copper formate S, thereby forming a metal film. Fig. 5 is a flowchart illustrating the procedure for forming a metal film using the metal film manufacturing apparatus 1. Only steps different from those in Fig. 2 will be described.

[0055] In FIG. 2 , copper formate S is placed on the plate 22 in the placing step (S1-1). However, in FIG. 5 , a copper plate is placed on the plate 22 instead of copper formate S (placement step: S1-2). Alternatively, a copper plate may be placed instead of the plate 22 so that the lamp 23 heats the copper plate directly without using the plate 22. That is, the heating unit 21 may be composed of only the lamp 23. The presence or absence of the plate 22 is appropriately selected depending on the shape of the metal. The evacuation step (S2), nitrogen supply step (S3), temperature increase and maintenance step (S4), and evacuation step (S5) are the same as those in FIG. 2 . However, in FIG. 5 , formic acid is supplied into the chamber after the evacuation step (S5) (formic acid supply step: S6). By supplying formic acid gas, the copper plate in the chamber is exposed to the formic acid gas. As a result, copper formate S is generated on the surface of the copper plate from formic acid and copper. The produced copper formate S is heated and vaporized in the temperature increase and maintenance step (S7), and the vaporized copper formate S forms a copper film on the substrate W. The subsequent vacuum evacuation step (S8), nitrogen supply step (S9), cooling step (S10), removal step (S11), and judgment step (S12) are the same as the vacuum evacuation step (S8), nitrogen supply step (S9), cooling step (S10), removal step (S11), and judgment step (S12) in FIG.

[0056] Continuing with reference to FIG. 2 , a method for manufacturing an article having a metal film according to a fourth embodiment of the present disclosure will be described. In the fourth embodiment, copper formate S is placed on a substrate W, and copper is deposited on the substrate W by decomposition of the copper formate S to form a metal film. Therefore, in the placement step (S1-1) of FIG. 2 , the substrate W is first placed on the plate 22, and then copper formate S is placed on the substrate W. The subsequent steps (S2 to S12) are the same as those in the second embodiment. Thus, since the fourth embodiment of the present disclosure uses only one heating unit, the metal film manufacturing apparatus 1 does not need to be equipped with the heating unit 24. As an example, in the fourth embodiment, copper formate S paste can be used to print copper formate S on the substrate W. Therefore, wiring or the like is printed on the substrate W to be coated with the copper formate S paste, and the substrate W is heated to form a copper film, thereby forming copper wiring exactly as printed.

[0057] As another embodiment, in the metal film manufacturing apparatus 1 of the first embodiment, the heating unit 21 may be provided separately as a vaporizer, independent of the chamber. An example of this configuration will be described as a metal film manufacturing apparatus 2 according to a fifth embodiment of the present disclosure, with reference to FIG. 6 . FIG. 6 is a schematic diagram of the metal film manufacturing apparatus 2. To avoid redundant description, the configuration different from the metal film manufacturing apparatus 1 of FIG. 1 will be mainly described. The metal film manufacturing apparatus 2 includes a chamber 111 and a heating unit 161 serving as a vaporizer independent of the chamber 111. The heating unit 161 includes a heating unit 121 serving as a first heating unit. The chamber 111 includes a heating unit 124 serving as a second heating unit. The chamber 111 is in fluid communication with the heating unit 161 via a gas guide pipe 162.

[0058] The heating device 161 is configured to be able to be sealed like the chamber 111, and the internal pressure can be made lower than the external pressure. The chamber 111 has, like the chamber 11 of the metal film manufacturing apparatus 1, for example, a vacuum pump 139p and a discharge control valve 139v.

[0059] The gas guide pipe 162 may include a pipe heating unit 164 surrounding it, and the pipe heating unit 164 may be configured to enable temperature control by the control device 50. The pipe heating unit 164 maintains or adjusts the temperature of the gas (e.g., vaporized copper formate S) passing through the gas guide pipe 162, thereby preventing thermal decomposition of the gas and condensation. The gas guide pipe 162 may also be configured to have an on-off valve 163 in its passage so that the pressure inside the pipe can be adjusted. Furthermore, the gas guide pipe 162 may be configured to be movable within at least the film formation area (e.g., the area of ​​the substrate W) within the chamber 111. Alternatively, a shower head (not shown) may be provided on the gas outlet side of the gas guide pipe 162 so that the gas can be uniformly distributed throughout the film formation area.

[0060] In the metal film manufacturing apparatus 2, copper formate S as an organic compound containing metal is placed in a heating section 121 in a heating device 161, and a substrate W as a coating target is placed in a heating section 124 in a chamber 111. Copper formate S may be in a solid state (for example, a powder) or in a liquid state dissolved in a solvent.

[0061] Copper formate S is heated and vaporized by the heating unit 121, passes through the gas guide pipe 162, and reaches the chamber 111. The copper formate S discharged from the gas guide pipe 162 is sprayed onto the substrate W, and the copper contained in the copper formate S deposits on the substrate W to form a copper film. In the metal film manufacturing apparatus 2, the device for vaporizing copper formate S is independent, which improves controllability and operability during vaporization. Furthermore, the gas guide pipe 162 improves controllability of the film formation range. The temperatures of the heating units 121 and 124 can be controlled in the same way as the heating units 21 and 24 of the metal film manufacturing apparatus 1 shown in FIG. 1, respectively.

[0062] In another embodiment, copper formate S may be vaporized using a bubbling device 171 as a vaporizer shown in FIG. 7 instead of the heating device 161 shown in FIG. 6 . An example including the bubbling device 171 will be described as a metal film manufacturing apparatus 3 according to a sixth embodiment of the present disclosure with reference to FIG. 7 . FIG. 7 is a schematic configuration diagram of the metal film manufacturing apparatus 3. The metal film manufacturing apparatus 3 includes a chamber 111 and a bubbling device 171 independent of the chamber 111, and vaporizes copper formate S by a bubbling method. The bubbling device 171 and the chamber 111 are fluidly connected via a gas guide pipe 162. The chamber 111 and the gas guide pipe 162 may be the same as those in the metal film manufacturing apparatus 2 shown in FIG. 6 , and a repeated description will be omitted.

[0063] The bubbling device 171 includes a carrier gas guide pipe 172. In the bubbling device 171, a carrier gas G is blown into the copper formate S solution through the carrier gas guide pipe 172 and passes through in the form of bubbles. The copper formate S vaporized together with the carrier gas G is transported into the chamber 111 through the gas guide pipe 162. As with the metal film manufacturing apparatus 2 of FIG. 6 , the copper formate S discharged from the gas guide pipe 162 is sprayed onto the substrate W, and the copper contained in the copper formate S deposits on the substrate W to form a copper film. A showerhead (not shown) may be provided on the gas outlet side of the gas guide pipe 162. The carrier gas G may be any inert gas capable of transporting the vaporized copper formate S, such as helium, nitrogen, hydrogen, or argon.

[0064] Furthermore, in the metal film production apparatus 2 and the metal film production apparatus 3, an electric field (or plasma) may be generated between the gas guide tube 162 and the heating unit 124. For example, the electric field (or plasma) may be generated in the area surrounded by the dotted line in FIG. 8 . Specifically, as shown in FIG. 9A , a voltage may be applied to the gas outlet of the gas guide tube 162 (or the shower head, if one is provided) and a plate of the heating unit 124, using these electrodes. Alternatively, as shown in FIG. 9B , a separate electrode (e.g., a plate electrode 165) may be disposed between the gas outlet side of the gas guide tube 162 and the substrate W, and a voltage may be applied to the separate electrode. Alternatively, the electric field (or plasma) may be generated inside the gas guide tube 162. For example, as shown in FIG. 9C , a central electrode 166 may be provided in the center of the gas guide tube 162, and a voltage may be applied between the central electrode 166 and the gas guide tube 162. The application of a voltage can promote the thermal decomposition of copper formate S, which is an organic compound containing a metal. As a result, the heating temperature of the coating target (for example, the substrate W) can be lowered, and the range of materials that can be coated can be expanded compared to methods of forming a film by heating.

[0065] As described above, the first to sixth embodiments of the present disclosure have been described. In the present disclosure, the term "metal-containing organic compound" is not particularly limited as long as it can form a metal film using the method according to the present disclosure. For example, if the organic compound is a solid metal at room temperature (20°C), it is preferable that it vaporizes at a temperature higher than room temperature under atmospheric pressure due to its ease of vaporization. For example, it is preferable that the vaporization temperature is in the range of 500°C or less. "Atmospheric pressure" means 1 atmosphere, i.e., 101,325 Pa. Alternatively, instead of an organic compound containing a metal that is solid at room temperature, an organic compound containing a metal that is liquid or gaseous at room temperature may be used. Using an organic compound containing a metal that is gaseous at room temperature allows the object to be easily exposed to the gas of the organic compound containing a metal.

[0066] In the present disclosure, the shape of the metal-containing organic compound is not particularly limited. It may be powder, granules, paste, or pellet-like. Similarly, the shape of the metal used in the third embodiment is not particularly limited. It may be powder, granules, or plate-like. The paste can be prepared by appropriately selecting a solvent (water, organic solvent, etc.) and a resin for viscosity adjustment, and preparing it using a well-known method. Furthermore, instead of a solid metal-containing organic compound, a liquid metal-containing organic compound dissolved in a solvent may be used. The solvent may be any solvent that can dissolve the metal-containing organic compound, and the solution containing the metal-containing organic compound may be placed in a container with excellent thermal conductivity.

[0067] In the present disclosure, the metal-containing organic compound is not particularly limited as long as it can form a metal film using the method for producing an article having a metal film of the present disclosure. Examples of metals contained in the metal-containing organic compound include at least one selected from the group consisting of copper, tin, cobalt, nickel, cadmium, lead, zinc, manganese, and magnesium. Examples of metal-containing organic compounds composed of these metals and organic compounds include metal carboxylates formed from carboxylic acids and metals. Examples of carboxylic acids constituting the metal carboxylates include at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, and capric acid. Examples include copper formate, tin formate, cobalt formate, nickel formate, cadmium formate, lead formate, zinc formate, manganese formate, magnesium formate, and copper acetate. The metal carboxylates may be hydrated or anhydrous.

[0068] The organic compounds containing metals may further include metal alkoxides, metal alkylamides, metal amidinates, metal β-diketonates, and organometallic compounds such as metallocenes or metal carbonyls. Examples of organometallic compounds include trimethylgallium (55.7°C), triethylgallium (142.6°C), trimethylaluminum (127°C), triethylaluminum (187°C), dimethylaluminum hydride (154°C), triisobutylaluminum (130°C), trimethylindium (136°C), triethylindium (184°C), dimethylzinc (44°C), diethylzinc (118°C), trimethylarsenic (51°C), triethylarsenic (140°C), tertiarybutylarsine (69°C), triethylphosphorus (127.5°C), diethylphosphine (85°C), tertiarybutylphosphine (56.1°C), trimethylboron (-20.2°C), triethylboron (95°C), trimethylborate (68.7°C), tetraethoxysilane (165.8°C), and tetrakisdimethylaminotitanium. The boiling point or vaporization temperature is shown in parentheses.

[0069] In the present disclosure, when the purpose is to remove water, the first predetermined temperature may be a temperature at which water (hydrated water) can be vaporized that is equal to or lower than the vaporization temperature of the metal-containing organic compound. Thus, the first predetermined temperature may be appropriately adjusted to match the vaporization temperature of the substance to be removed. Alternatively, the film may be formed by directly raising the temperature to the second predetermined temperature without first raising the temperature to the first predetermined temperature and then maintaining the temperature. For example, if the metal-containing organic compound is not a hydrate, the temperature may be raised directly to the second predetermined temperature. The second predetermined temperature may be a temperature at which the metal-containing organic compound used vaporizes. For example, the second predetermined temperature may be determined based on measurement data obtained by simultaneous thermogravimetry and differential thermal analysis (TG-DTA) of the metal-containing organic compound. The third predetermined temperature when heating the coating target may be higher, lower, or the same as the second predetermined temperature. Alternatively, the third predetermined temperature may be higher, lower, or the same as the ambient temperature in the chamber. For example, the third predetermined temperature may be the second predetermined temperature ±50°C, the second predetermined temperature ±20°C, or the second predetermined temperature ±10°C.

[0070] In the present disclosure, as a method for vaporizing a metal-containing organic compound, a method such as plasma treatment or voltage application may be used instead of the above-mentioned heating or bubbling.

[0071] In the present disclosure, the object to be coated may be anything that requires a metal film, and is not particularly limited. For example, the metal film may be a seed layer for a semiconductor device, a coating film for a heat diffusion / heat dissipation component, or may be used in the manufacture of a metal electrode film or a metal reflective film, or may be used for antibacterial metal surface treatment. Examples of the object to be coated include substrates made of glass, ceramic, metal, or resins such as Teflon (registered trademark) or polyimide. In this specification, the term "article" refers to an object consisting of a metal film formed on the object to be coated, or an object including a metal film formed on the object to be coated. Examples include low-loss substrates for 5G and 6G, glass substrates for solar cells, glass and resin substrates used in semiconductors and electronic components, heat diffusion and heat dissipation components and surface metal films, optical thin films on displays and cameras, electromagnetic wave shielding plates for automobiles and aircraft, and metal electrode films on other electronic devices.

[0072] In the present disclosure, the distance between the metal-containing organic compound and the coating target may be any distance that allows the coating target to be exposed to a gas of the metal-containing organic compound. The distance may be determined appropriately taking into consideration the size of the apparatus, the amount and shape of the metal-containing organic compound, the shape of the coating target, and the like. The distance between the first heating unit and the second heating unit may be adjusted using a motion field through or the like so that an appropriate distance is maintained between the metal-containing organic compound and the coating target.

[0073] In the above explanation, the metal film manufacturing apparatus and the method for manufacturing an article having a metal film according to the embodiment of the present invention have been described as examples mainly using Figures 1 to 9. However, the configuration, structure, number, arrangement, shape, material, etc. of each part are not limited to the above specific examples, and any suitable selections adopted by a person skilled in the art are also included within the scope of the present invention as long as they include the gist of the present invention.

[0074] All references, including publications, patent applications, and patents, cited in this specification are herein incorporated by reference to the same extent as if each individual reference were specifically and individually indicated to be incorporated by reference in its entirety.

[0075] The use of nouns and similar referents in connection with the description of the present invention (particularly in connection with the claims that follow) shall be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The words "comprises," "has," "includes," and "comprises" shall be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise noted. The recitation of numerical ranges herein is merely intended to serve as a shorthand method for individually referring to each value falling within the range, unless otherwise indicated herein, and each value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. Any example or exemplary language used herein (e.g., "etc.") is intended merely to better describe the invention and does not pose a limitation on the scope of the invention, unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0076] Preferred embodiments of the invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of these preferred embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor anticipates that skilled artisans will apply such variations as appropriate, and intends to practice the invention otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, this invention includes any combination of the above-described elements in all variations thereof unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims

1. A step of vaporizing an organic compound containing a metal, The method comprises the steps of: depositing the metal contained in the vaporized organic compound onto the object to be coated to form a metal film; A method for manufacturing an article having a metal film.

2. To produce a metal-containing organic compound composed of a metal and an organic compound, the steps include exposing the metal to a gas of the organic compound, A step of vaporizing the generated organic compound containing the metal, The method comprises the steps of: depositing the metal contained in the vaporized organic compound onto the object to be coated to form a metal film; A method for manufacturing an article having a metal film.

3. The steps include: placing an organic compound containing a metal on the object to be coated, The method comprises the steps of depositing the metal contained in the organic compound containing the aforementioned metal onto the object to be coated to form a metal film. A method for manufacturing an article having a metal film.

4. Within the chamber, the organic compound containing the metal and the object to be coated are arranged to face each other. A method for manufacturing an article according to claim 1 or claim 2.

5. The organic compound containing the aforementioned metal is in the form of a paste or pellets. A method for manufacturing an article according to claim 1 or claim 3.

6. The aforementioned metal-containing organic compound is a hydrate, The method further comprises the step of removing water of hydration from the hydrate of the metal-containing organic compound at a temperature of 10°C to 120°C. A method for manufacturing an article according to any one of claims 1 to 3.

7. The aforementioned metal-containing organic compound is a hydrate, The method further comprises the step of removing the water of hydration from the hydrate of the metal-containing organic compound at room temperature. A method for manufacturing an article according to any one of claims 1 to 3.

8. The step of removing the hydrated water is carried out under reduced pressure. A method for manufacturing an article according to claim 6.

9. The method further comprises the step of heating the object to be coated. A method for manufacturing an article according to any one of claims 1 to 3.

10. The metal contained in the aforementioned organic compound is at least one selected from the group consisting of copper, tin, cobalt, nickel, cadmium, lead, zinc, manganese, and magnesium. A method for manufacturing an article according to any one of claims 1 to 3.

11. Chamber and, The first heating section within the chamber is for heating an organic compound containing a metal in order to generate a gas of the organic compound containing the metal, The device comprises a second heating section within the chamber, which is opposite to the first heating section, and is used to heat an object to be covered. Metal film manufacturing equipment.

12. Chamber and, The first heating section within the chamber, the first heating section for heating metal, A second heating section in the chamber, facing the first heating section, wherein the second heating section is for heating an object to be covered, The system includes an organic compound supply unit for supplying an organic compound gas into the chamber. Metal film manufacturing equipment.

13. Chamber and, The chamber comprises a first heating section for heating an object to be coated and an organic compound containing metal on the object to be coated, Metal film manufacturing equipment.

14. Chamber and, A vaporizer for producing gases of metal-containing organic compounds, A gas guide pipe that fluidly connects the chamber and the vaporizer, The first heating section within the vaporizer is for heating an organic compound containing a metal in order to generate a gas of the organic compound containing the metal, The chamber comprises a second heating section for placing and heating an object to be covered, Metal film manufacturing equipment.

15. Chamber and, A vaporizer for producing gases of metal-containing organic compounds, A gas guide pipe that fluidly connects the chamber and the vaporizer, The chamber comprises a second heating section for placing and heating an object to be covered, The vaporization apparatus includes a bubbling device for generating a gas of an organic compound containing the metal using a carrier gas. Metal film manufacturing equipment.

16. Within the chamber, there is a control unit that controls the pressure and the temperature of the heating section, The system further comprises a plurality of control valves that operate to control the temperature and pressure within the chamber in response to the control of the control unit. A metal film manufacturing apparatus according to any one of claims 11 to 15.