WO2010067603A1 - 薄膜の形成方法 - Google Patents
薄膜の形成方法 Download PDFInfo
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- WO2010067603A1 WO2010067603A1 PCT/JP2009/006741 JP2009006741W WO2010067603A1 WO 2010067603 A1 WO2010067603 A1 WO 2010067603A1 JP 2009006741 W JP2009006741 W JP 2009006741W WO 2010067603 A1 WO2010067603 A1 WO 2010067603A1
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- thin film
- substrate
- cooling
- gas
- film forming
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/04—Coating on selected surface areas, e.g. using masks
- C23C14/042—Coating on selected surface areas, e.g. using masks using masks
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/243—Crucibles for source material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/541—Heating or cooling of the substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
Definitions
- the present invention relates to a method for forming a thin film.
- thin film technology has been widely deployed to improve the performance and miniaturization of devices.
- the thinning of devices is not only a direct merit for users, but also plays an important role in environmental aspects such as protecting earth resources and reducing power consumption.
- it is indispensable to meet industrial demands such as high efficiency, stabilization, high productivity, and low cost in thin film formation.
- high deposition rate film formation technology is essential for high productivity in thin film formation, and high deposition rates are achieved in film formation methods such as vacuum evaporation, sputtering, ion plating, and CVD. Is underway.
- a winding-type thin film forming method is used as a method for continuously forming a large amount of a thin film.
- the winding-type thin film forming method is a method in which a long substrate wound around a winding roll is unwound to a conveyance system, a thin film is formed on a substrate traveling in the conveyance process, and then wound on a winding roll. It is a method to take.
- a high deposition rate film formation method such as vacuum evaporation using an electron beam, a thin film can be continuously formed in large quantities with high productivity. Can do.
- the winding-type thin film forming method and the vacuum deposition method are combined, radiant heat from the evaporation source and thermal energy of the deposited particles are applied to the substrate. As a result, the temperature of the substrate rises, causing deformation or fusing of the substrate. Further, even when combined with other film forming methods having different heat sources, a thermal load is applied to the substrate during film forming. In order to prevent the substrate from being deformed or blown by such a thermal load, the winding-type thin film forming method requires cooling of the substrate.
- a method for cooling the substrate a method in which the substrate is thermally conducted along a cylindrical can arranged on the path of the transport system is widely used. According to this cooling method, it is possible to ensure thermal contact between the substrate and the cylindrical can, and to release the heat of the substrate to the cylindrical can having a large heat capacity. Thereby, the temperature rise of a board
- a gas cooling method in which a gas is introduced between a substrate and a cylindrical can (see, for example, Patent Document 1). According to this method, thermal contact via gas can be ensured between the substrate and the cylindrical can, and the temperature rise of the substrate can be suppressed.
- a cooling belt can be used as a means for cooling the substrate.
- a cooling belt is used as the substrate cooling means. It is valid.
- a cooling mechanism using a further cooling belt or a liquid cooling medium is provided inside the cooling belt, thereby improving the cooling efficiency and improving the efficiency of the substrate material. An increase in temperature can be suppressed (see, for example, Patent Document 2).
- the present invention solves the above-mentioned problems, and gas cooling required for film formation at a high film formation rate is simple and low-cost while suppressing deterioration in the degree of vacuum and resulting deterioration in thin film quality. It aims at providing the formation method of the thin film implement
- a thin film forming method of the present invention is a thin film forming method for forming a thin film by depositing a film forming material on a substrate having a front surface and a back surface in a vacuum, A first disposing step of disposing a first cooling surface so as to be close to the back surface in the first thin film forming region; and forming a first thin film on the surface of the substrate in the first thin film forming region.
- a cooling gas containing a gas that reacts with the film forming material hereinafter also referred to as a reactive gas
- the first thin film forming step can be performed once to form a single thin film on the surface.
- a multilayer thin film can also be formed in the said location by implementing a 1st thin film formation process in multiple times with respect to the predetermined location of the said surface.
- the amount of reactive gas introduced when forming the first layer thin film should be less than the amount of reactive gas introduced when forming the second layer thin film. Is preferred. As will be described below, the amount of reactive gas introduced when forming the first thin film may be zero. If it does in this way, at the time of thin film formation of the 1st layer, reaction with an exposed substrate and reactive gas before a thin film is formed can be controlled. Note that when the substrate reacts with the reactive gas, the substrate surface may be discolored or the strength of the substrate may be reduced.
- the first cooling step is performed. Preferably it is done. If it does in this way, at the time of thin film formation of the 1st layer, direct contact with an exposed substrate and reactive gas before forming a thin film can be avoided.
- the substrate has a property of reacting with a reactive gas (especially when the substrate is a metal foil), when the substrate and the reactive gas come into contact with each other, they react (if the reactive gas contains oxygen, the substrate is oxidized).
- the substrate deteriorates, but according to the above method, such substrate deterioration can be avoided.
- Reactive gas can be introduced.
- the cooling gas mainly composed of non-reactive gas is preferably composed only of non-reactive gas, but may be a mixture of non-reactive gas and reactive gas. In the latter case, the reactive gas may be contained in a small amount as much as an impure gas.
- the cooling gas mainly composed of non-reactive gas contains non-reactive gas in an amount of more than 95% by volume, preferably 99% by volume or more, more preferably 99.9% by volume, with the remainder being reacted. Occupied by sex gas.
- the method for forming a thin film of the present invention includes a second disposing step of disposing a second cooling surface so as to be close to the front surface in the second thin film forming region, and forming the second thin film on the back surface of the substrate.
- a cooling gas containing a gas that reacts with the film forming material between the second cooling surface and the surface during the second thin film forming step and the second thin film forming step for forming a thin film in the region A second cooling step of cooling the substrate by introducing a thin film, whereby a thin film can be formed on both surfaces of the substrate.
- a multilayer thin film can be formed on both sides of the substrate by performing the first thin film forming step and the second thin film forming step a plurality of times.
- the amount of reactive gas introduced when forming the first layer thin film is less than the amount of reactive gas introduced when forming the second layer thin film. preferable. If it does in this way, at the time of thin film formation of the 1st layer, reaction with an exposed substrate and reactive gas before a thin film is formed can be controlled. Note that when the substrate reacts with the reactive gas, the substrate surface may be discolored or the strength of the substrate may be reduced.
- the first thin film forming step of forming the first layer thin film on the surface no cooling gas is introduced between the first cooling surface and the back surface, or the composition is not performed.
- the second thin film forming step of introducing a cooling gas containing only a gas that does not react with the film material and forming a thin film of the first layer on the back surface between the second cooling surface and the surface No cooling gas is introduced, or a cooling gas mainly composed of a gas that does not react with the film forming material is introduced, and further, after the first thin film is formed on both surfaces of the substrate
- the first cooling process is performed during the first thin film forming process for forming the second and subsequent thin films on the surface, and the first thin film forming process is performed for forming the second and subsequent thin films on the back surface.
- the second cooling step is preferably performed inside. According to this method, when the reactive gas is introduced as the cooling gas, both sides of the substrate are covered with the first layer of the thin film, so that the deterioration of the substrate due to the contact with the reactive gas is ensured. It can be avoided.
- a metal foil can be used as the substrate. According to the present invention, even when a highly reactive material such as a metal foil is used, deterioration of the substrate due to introduction of the reactive gas as the cooling gas can be avoided.
- the reactive gas is not particularly limited as long as it is a gas that reacts with the film forming material.
- Specific examples include oxygen gas and nitrogen gas.
- hydrocarbon gas and hydrogen gas usually do not react with the film forming material, but can react with the film forming material under special conditions such as an atmosphere in which plasma is generated.
- a reactive gas containing oxygen is preferable. Since oxygen easily reacts with the film forming material and is easily removed by reacting with the vapor of the film forming material, deterioration of the degree of vacuum due to the introduction of the cooling gas can be most effectively suppressed.
- a reactive gas is introduced as the cooling gas, only the reactive gas may be introduced, or a reactive gas and a non-reactive gas may be mixed and introduced.
- the non-reactive gas is not particularly limited, and examples thereof include carbon dioxide gas, argon gas, helium gas, neon gas, xenon gas, and krypton gas in addition to the above-described hydrocarbon gas and hydrogen gas. .
- the total introduction amount of the cooling gas at the time of forming the first thin film is any layer after the second layer.
- the total amount of the cooling gas introduced during the formation of the thin film is preferably less. If only a non-reactive gas is introduced as a cooling gas when forming the thin film of the first layer, the vapor of the film forming material floating and the cooling gas will not react and the cooling gas will not be removed. The degree of vacuum tends to deteriorate. In order to avoid this, the total amount of cooling gas introduced during the formation of the first layer thin film is reduced, and the amount of cooling gas introduced is relatively increased during the formation of the second and subsequent thin films. The cooling ability can be secured while avoiding the deterioration of the above.
- the film deposition rate when forming the thin film of the first layer is such that the thin film formation of any layer after the second layer is performed. It is preferably slower than the film deposition rate of time. If the cooling gas is not introduced when the first layer thin film is formed, or if the total introduction amount of the cooling gas is reduced, the substrate may not be sufficiently cooled. By reducing the film deposition rate, the thermal load on the substrate is reduced. When an excessive thermal load is applied to the substrate, the physical properties of the substrate deteriorate. Therefore, when the cooling ability is lowered, it is preferable to reduce the thermal load on the substrate by slowing the film deposition rate.
- the thin film formed from the present invention may be composed of only a thin film material, or may include a thin film material and oxygen. In the latter case, it is preferable to introduce oxygen as a cooling gas because a change in the quality of the thin film is reduced.
- a gas that reacts with a film forming material is introduced as a cooling gas. Therefore, even if the cooling gas leaks from between the cooling body and the substrate, the leaked cooling gas All or a part of this reacts with vapor or the like of the film forming material in the vacuum chamber. As a result, the cooling gas is consumed and removed from the atmosphere, so that deterioration of the degree of vacuum due to the introduction of the cooling gas can be reduced.
- This makes it possible to cool the gas necessary for film formation at a high film formation rate, while maintaining sufficient cooling capacity, while suppressing deterioration of the degree of vacuum and deterioration of thin film quality resulting from it, and at low cost and simple facilities. It can be realized using. Further, according to the present invention, it is possible to prevent the deterioration of the substrate and the quality of the thin film due to the high reactivity of the introduced cooling gas.
- Configuration diagram of a film forming apparatus according to Embodiment 1 of the present invention Plane transparent view of the cooling body in FIG. 2 is a cross-sectional view of the cooling body taken along the line AA in FIG. (A) Another configuration diagram of the cooling body in FIG. 1 (b) Perspective view of the gas nozzle in FIG. Another configuration diagram of the cooling body in FIG. Configuration diagram of a film forming apparatus according to Embodiment 2 of the present invention Configuration diagram of film forming apparatus according to Embodiment 3 of the present invention Configuration diagram of film forming apparatus according to Embodiment 4 of the present invention
- FIG. 1 is a configuration diagram of a film forming apparatus 20 according to Embodiment 1 of the present invention.
- a film forming apparatus 20 according to Embodiment 1 of the present invention includes a cooling body 1, a substrate 21, and a first winding core in an internal space of a vacuum chamber 22 that is a pressure-resistant container-like member.
- a roller 23, a plurality of transport rollers 24, a metal mask 25, a second winding core roller 26, a film formation source 27, a shielding plate 29, and a film formation reaction gas introduction pipe 30 are accommodated.
- Exhaust means 37 is provided at the outer lower part of the vacuum chamber 22, and the inside of the vacuum chamber 22 is maintained in a reduced pressure state suitable for thin film formation.
- the exhaust means 37 is constituted by various vacuum exhaust systems using, for example, an oil diffusion pump, a cryopump, a turbo molecular pump or the like as a main pump.
- an oil diffusion pump a cryopump, a turbo molecular pump or the like as a main pump.
- two oil diffusion pumps with a diameter of 14 inches are provided as the exhaust means 37.
- separate exhaust means may be connected to each of the upper space and the lower space of the vacuum chamber 22 as in the third embodiment described later.
- the substrate 21 is a strip-like long substrate, and as the material thereof, various metal foils including aluminum foil, copper foil, nickel foil, titanium foil, stainless steel foil, polyethylene terephthalate, polyethylene naphthalate, polyamide, Various polymer films including polyimide, composites of polymer films and metal foils, and the like can be used.
- the material of the substrate 21 is not limited to the above, and may be a strip-like long substrate made of other materials.
- the substrate 21 preferably has a width of 50 to 1000 mm and a thickness of 3 to 150 ⁇ m. If the width of the substrate 21 is less than 50 mm, gas loss in the width direction of the substrate 21 during gas cooling is large, and if the thickness of the substrate 21 is less than 3 ⁇ m, the heat capacity of the substrate 21 is extremely small, and thermal deformation is likely to occur. However, this does not mean that the present invention is not applicable.
- the conveyance speed of the substrate 21 varies depending on the type of thin film to be formed and the film formation conditions, but is set to 0.1 to 500 m / min in the first embodiment.
- the tension applied in the traveling direction of the substrate 21 being transferred can be appropriately selected depending on the material and thickness of the substrate 21 or the process conditions such as the film formation rate (film deposition rate).
- the first winding roller 23, the second winding roller 26, and the plurality of transport rollers 24 are roller-like members that are rotatably provided around the axis disposed in the vacuum chamber 22.
- a substrate 21 before film formation is wound around the first core roller 23, and the substrate 21 is supplied toward the closest conveying roller 24.
- the plurality of transport rollers 24 sequentially guide the substrate 21 supplied from the winding core roller 23 to a region where film formation is performed, and guide the substrate 21 formed during the transport to the second winding roller 26.
- the second winding roller 26 can be rotated by a driving means (not shown), and winds and stores the substrate 21 after film formation.
- the conveyance roller 24 is arranged so as to go around the winding core roller 26 between the first opening 31a and the second opening 31b in the conveyance path of the substrate 21 (reverse structure). With this structure, the surface of the substrate 21 facing the film forming source 27 can be reversed. Therefore, when the substrate 21 passes through the first opening 31a, vapor deposition is performed on the surface of the substrate 21, and when the substrate 21 passes through the second opening 31b, vapor deposition is performed on the back surface of the substrate 21. It can be carried out. Therefore, when the vapor deposition apparatus 20 is used, it becomes possible to continuously form a vapor deposition film on both surfaces of the substrate 21 while keeping the vacuum state of the vacuum chamber 22.
- the metal mask 25 is formed in an inverted V shape at the center of the vacuum chamber 22, and is close to a surface (front surface or back surface) on the side of the substrate 21 on which the substrate 21 is traveling in parallel with the transport path of the substrate 21. Installed.
- a first opening 31a and a second opening 31b are formed in the center of the left and right wings of the metal mask 25, respectively.
- the surface of the substrate 21 refers to a surface that is formed while traveling through the opening 31a of the metal mask 25 but is not deposited while traveling through the opening 31b of the metal mask 25.
- the back surface of the film means a surface on the side where the film is not formed while traveling through the opening 31a but is formed while traveling through the opening 31b.
- a film forming source 27 is provided in a vertical lower space at the bottom of each of the openings 31 a and 31 b at a position facing the concave portion of the metal mask 25.
- a shielding plate 29 is joined to the lower ends of the left and right wings of the metal mask 25 and the inner wall of the vacuum chamber 22, and the internal space of the vacuum chamber 22 is divided into an upper space 22 a and a lower space 22 b.
- a thin film forming region is formed in the lower space 22b of the vacuum chamber 22, and the regions where the vapor deposition particles of the film forming material 18 flying from the film forming source 27 come into contact with the front surface or the back surface of the substrate 21 are respectively opened.
- It can be limited to 31a or 31b only. That is, the first opening 31a defines a first thin film formation region where a thin film is formed on the surface of the substrate, and the second opening 31b is a second thin film formation region where a thin film is formed on the back surface of the substrate. Is specified.
- the film forming source 27 includes a container-like member 19 whose upper part in the vertical direction is open, and a film forming material 18 placed therein.
- a heating means such as an electron gun is disposed in the vicinity of the film forming source 27 to heat and evaporate the film forming material 18 in the film forming source 27.
- an evaporation crucible is used as the container-like member 19.
- the film forming source 27 is not limited to the above, and various film forming sources can be used. For example, an evaporation source by resistance heating, induction heating, electron beam heating, an ion plating source, a sputtering source, a CVD source, or the like can be used. Further, as the film forming source 27, an ion source or a plasma source can be used in combination.
- a film formation reaction gas introduction pipe 30 which is a tubular member, is installed in parallel with the left and right wing parts of the metal mask 25.
- the upper end portion of the film formation reaction gas introduction pipe 30 is positioned below the lowermost portions of the openings 31 a and 31 b of the metal mask 25 in the upper space in the vertical direction of the evaporation crucible 19.
- a lower end portion of the film formation reaction gas introduction pipe 30 is connected to a film supply gas supply means (not shown) such as a gas cylinder or a gas generator provided outside through the side wall of the vacuum chamber 22. ing.
- a film forming reaction gas such as oxygen or nitrogen is appropriately supplied to the vapor of the film forming material 18 from the film forming reaction gas supply means through the film forming reaction gas introduction pipe 30.
- the vapor deposition particles of the film forming material 18 flying from the film forming source 27 react with the film forming reaction gas to become an oxide, nitride, or oxynitride, and the surface or back surface of the substrate 21. Stick on top.
- a thin film is formed on the front surface or the back surface of the substrate 21 by depositing the vapor deposition particles attached in this way.
- oxygen gas is used as the film formation reaction gas.
- the cooling body 1 is on the side on which the substrate 21 is not deposited between the auxiliary rollers 28 disposed above and below the openings 31 a and 31 b of the metal mask 25. Are installed close to each other.
- a pair of auxiliary rollers 28 are arranged before and after the cooling body 1 along the conveyance path of the substrate 21 and are in contact with the surface of the substrate 21 on which the film is not formed. Thereby, the conveyance path
- the material of the cooling body 1 is not particularly limited, and metals such as copper, aluminum, stainless steel and the like, carbon, various ceramics, engineering plastics, and the like that can easily secure the processed shape can be used.
- metals such as copper, aluminum, stainless steel and the like, carbon, various ceramics, engineering plastics, and the like that can easily secure the processed shape can be used.
- the cooling body 1 is cooled by the refrigerant.
- the refrigerant is usually a liquid or gaseous substance, typically water.
- a coolant channel (not shown) is installed in contact with or embedded in the cooling body 1, and the coolant 1 is cooled by passing the coolant through the channel.
- the material of the piping is not particularly limited, and pipes such as copper and stainless steel can be used.
- the pipe may be attached to the cooling body 1 by welding or the like.
- a coolant channel may be formed by directly opening a hole for allowing the coolant to pass through the cooling body 1.
- FIG. 2 is a plan transparent view of the cooling body 1 when the vicinity of the opening 31a or 31b is viewed from the film forming source 27 in FIG. 1
- FIG. 3 is a cross-sectional view of the cooling body 1 along the AA cross-sectional line in FIG. It is.
- the cooling body 1 has a manifold 32, a large number of pores 33 extending from the manifold 32 to the cooling surface 11, and a cooling gas inlet 35 connected to the manifold 32. ing.
- the cooling gas inlet 35 is connected to a cooling gas supply source (not shown) arranged outside.
- the large number of pores 33 connect the manifold 32 and the cooling surface (surface adjacent to the substrate 21) 11 of the cooling body 1.
- the surface area of the cooling surface 11 is larger than the openings 31 a and 31 b of the metal mask 25.
- the cooling body 1 is disposed so that the cooling surface 11 faces the surface of the substrate 21 on which the film is not formed and covers the entire openings 31a and 31b.
- the cooling body 1 (or the cooling surface 11) is supplied from the cooling surface 11 through a cooling gas inlet 35, a manifold 32, and a large number of pores 33 from a cooling gas supply source (not shown).
- a cooling gas is introduced between the substrate 21 and the substrate 21.
- the introduced gas transmits the cold heat of the cooling body 1 to the substrate 21 to cool the substrate 21.
- the cooling gas supply source include a gas cylinder and a gas generator.
- argon gas (non-reactive gas) and / or oxygen gas (reactive gas) that is the same as the film-forming reaction gas is used as the cooling gas.
- the substrate 21 By cooling the substrate 21 by gas cooling in this manner, the temperature rise of the substrate 21 due to the radiant heat from the film forming source 27 and the thermal energy of the vapor deposition particles can be suppressed, so that the thin film can be stably formed. It can be carried out.
- the configuration of the cooling body 1 is not limited to the above, and the configurations shown in FIGS. 4 and 5 may be used.
- FIG. 4 (a) is another configuration diagram of the cooling body 1 in FIG. 1
- FIG. 4 (b) is a perspective view of the gas nozzle 34 in FIG. 4 (a).
- a plurality of side flute gas nozzles 34 having a plurality of outlets 34a are embedded in the cooling body 1, and a plurality of cooling gas introductions are provided. Each is connected to the mouth 35.
- FIG. 5 is another configuration diagram of the cooling body 1 in FIG. 1.
- the gas flow rate introduced between the cooling body 1 and the substrate 21 can be increased at the same vacuum chamber pressure, and the cooling efficiency is further improved to suppress the temperature rise of the cooling gas.
- the gas introduction method is not limited to the above method, and other methods may be used as long as the cooling gas as the heat transfer medium can be introduced while being controlled between the cooling body 1 and the substrate 21. You can also.
- a single layer or multiple thin films can be formed on both surfaces of the substrate 21. That is, as described above, the substrate 21 is transported from the first core roller 23 toward the second core roller 26 to form a film, whereby a single-layer thin film is formed on both surfaces of the substrate 21. . Thereafter, when the film is formed again while reversing the transport direction of the substrate 21 and transporting from the second core roller 26 toward the first core roller 23, two layers of thin films are formed on both surfaces of the substrate 21. Can be formed. In this way, by repeating the film formation while reversing the transport direction of the substrate, it is possible to form a multilayer thin film with an arbitrary thickness on both surfaces of the substrate 21.
- FIG. 6 is a configuration diagram of a film forming apparatus 40 according to Embodiment 2 of the present invention.
- the film forming apparatus 40 according to the second embodiment of the present invention has the shape of the metal mask 45 and the locations of the openings 31 c, 31 d, 31 e and 31 f of the metal mask 45 and the cooling body 1.
- the same components as those in FIG. 1 are denoted by the same reference numerals, and description thereof is omitted.
- the metal mask 45 is formed in a substantially W shape in the central portion of the vacuum chamber 22 and is disposed in parallel with the substrate 21 and close to the surface of the traveling substrate 21 on the side where the film is formed.
- the concave portion at the center of the metal mask 45 has an acute angle shape, and the bottom thereof and the bottom of the wing provided on the left and right sides of the concave are joined by a shielding plate 29.
- Convex portions are formed on the left and right by the two wing portions.
- openings 31d and 31e are provided at the same positions as in FIG. 1, and openings 31c and 31f are also formed at the center of the left and right wings.
- the cooling bodies 1 are respectively disposed so as to face the surfaces of the substrate 21 on which the film is not formed, in accordance with the openings 31c, 31d, 31e, and 31f. As a result, the film thickness that can be formed on both surfaces of the substrate 21 in one reciprocating run can be approximately double that of the film forming apparatus 20 in FIG. be able to.
- FIG. 7 is a configuration diagram of a film forming apparatus 60 according to Embodiment 3 of the present invention.
- the endless belt 70 defines the transport path of the substrate 21 in the vicinity of the opening 31g.
- the exhaust means 37a and 37b are respectively connected to the upper space 22a and the lower space 22b of the vacuum chamber 22 (however, in the third embodiment, as in the first embodiment, only in the lower space 22b. Exhaust means may be connected). Details will be described below, but the same components as those in FIG.
- the endless belt 70 defines a part of the transport path of the substrate 21 along its outer peripheral surface, and is installed so as to pass between the cooling surface 11 and the substrate 21.
- a through hole is formed in the endless belt 70 in the thickness direction.
- the substrate 21 passes through the first winding roller 23, the upstream conveying roller 24, the upstream auxiliary roller 78, the endless belt 70, the downstream gap adjusting roller 77, the downstream auxiliary roller 78, and the second.
- the core roller 26 is guided.
- the pair of auxiliary rollers 78 are provided on each of the upstream side and the downstream side of the transport path of the substrate 21 when viewed from the endless belt 70, and is positioned at a position closest to the endless belt 70 on the transport path of the substrate 21. It is a roller. This makes it possible to apply tension to the substrate 21 so that the distance between the substrate 21 and the endless belt 70 does not open too much, and as a result, the substrate 21 comes into close contact with the endless belt 70 appropriately.
- the shielding plate 79 is disposed between the film forming source 27 and the endless belt 70.
- a thin film formation region on the surface of the substrate 21 is defined by the opening 31 g of the shielding plate 79.
- a region that is not shielded by the shielding plate 79 is a thin film formation region on the surface of the substrate 21 where the material particles from the film forming source 27 can reach.
- the exhaust means 37a is connected to the upper space 22a of the vacuum chamber 22, and the exhaust means 37b is connected to the lower space 22b of the vacuum chamber 22.
- the degree of vacuum of the upper space 22a and the lower space 22b can be changed, so that the degree of vacuum of the lower space 22b including the thin film formation region can be lowered so that excellent thin film quality can be achieved. it can.
- various vacuum pumps such as an oil diffusion pump, a cryopump, and a turbo molecular pump can be used. When helium gas is introduced as a cooling gas, an oil diffusion pump and a turbo molecular pump are preferable. .
- FIG. 7 illustrates a cryopump or a turbo molecular pump.
- the endless belt 70 will be described in more detail.
- the endless belt 70 is hung on two cans 71 and travels by driving the can 71 with a motor or the like.
- a conveyance path of the substrate 21 in the vicinity of the opening 31 g is defined along the outer peripheral surface of the endless belt 70.
- the travel speed of the endless belt 70 during film formation is equal to the transport speed of the substrate 21 by the substrate transport mechanism including the core roller and the transport roller. However, there may be some difference between the travel speed of the endless belt 70 and the transport speed of the substrate 21 as long as the substrate 21 is not damaged.
- the material of the endless belt 70 is not particularly limited, but metals such as stainless steel, titanium, molybdenum, copper, and titanium are excellent from the viewpoint of heat resistance.
- the thickness of the endless belt 70 is, for example, 0.1 to 1.0 mm.
- the endless belt 70 having such a thickness is not easily deformed by the radiant heat and the heat of the vapor flow at the time of film formation, and is flexible to the extent that a relatively small diameter can 71 can be used.
- the endless belt 70 may have a resin layer on the outer peripheral surface side in contact with the substrate 21. That is, a metal belt lined with resin can be used as the endless belt 70.
- a resin layer having excellent flexibility is provided on the surface, the adhesion between the endless belt 70 and the substrate 21 is increased in the section where the endless belt 70 is in contact with the can 71. Therefore, the cooling efficiency of the substrate 21 based on the direct contact between the endless belt 70 and the substrate 21 is improved. Further, since the substrate 21 is difficult to slide on the endless belt 70, it is possible to prevent the back surface of the substrate 21 from being scratched.
- the substrate 21 may be attached to the endless belt 70 using an electrostatic force.
- the endless belt 70 is in close contact with the can 71 and is cooled by the can 71. Thereby, the cooling effect of the board
- the endless belt 70 has a plurality of through holes formed at equal intervals along the longitudinal direction (circumferential direction). In this way, the substrate 21 can be uniformly cooled. Further, through holes are formed in the endless belt 70 at equal intervals along a plurality of rows in the width direction. In this way, the substrate 21 can be uniformly cooled in both the longitudinal direction and the width direction. Therefore, uneven cooling is less likely to occur within the surface of the substrate 21, and a sufficient cooling effect on the substrate 21 can be achieved.
- the arrangement of the through holes is not limited to the above, and can be changed as appropriate. In addition, various shapes such as a circle, a triangle, a rectangle, and an ellipse can be appropriately employed as the opening shape of the through hole.
- a groove-shaped through hole may be formed.
- the number of rows of the through holes is not limited to 2 rows or 3 rows, but may be 4 rows or more, and in some cases 20 rows or more.
- the gap adjusting roller 77 that adjusts the width of the gap between the endless belt 70 and the cooling body 1 is provided on the cooling surface 11 of the cooling body 1. , And so as to slightly protrude from the cooling surface 11.
- the gap adjusting roller 77 With the gap adjusting roller 77, the width of the gap between the cooling surface 11 and the endless belt 70 can be kept constant with high accuracy. As a result, the cooling surface 11 can be prevented from coming into contact with the endless belt 70 and being scratched. Further, if the gap between the cooling surface 11 and the endless belt 70 is made as narrow as possible and the pressure in the gap is maintained, the cooling gas is easily introduced into the through hole. In this case, a sufficient cooling effect can be obtained with a small amount of cooling gas, which is advantageous in suppressing an increase in pressure in the vacuum chamber 22.
- a roller made of metal such as stainless steel or aluminum can be used.
- the surface of the gap adjusting roller 17 may be formed of rubber or plastic.
- the diameter of the gap adjusting roller 17 is set, for example, within a range of 5 to 100 mm so as to ensure sufficient strength and not take up installation space.
- a single layer or multiple thin films can be formed on one side of the substrate 21. That is, as described above, film formation is performed while the substrate 21 is transported from the core roller 23 toward the core roller 26, thereby forming a single-layer thin film on one surface of the substrate 21. Thereafter, when the film is formed again while being transferred from the winding roller 26 toward the winding roller 23 by reversing the conveyance direction of the substrate 21, a two-layer thin film can be formed on one surface of the substrate 21. By repeating the film formation while reversing the substrate transport direction in this manner, a multilayer thin film can be arbitrarily formed on one surface of the substrate 21.
- FIG. 8 is a configuration diagram of a film forming apparatus 80 according to the fourth embodiment of the present invention.
- the film forming apparatus 80 according to the fourth embodiment of the present invention has only one opening, and forms a film on only one side of the substrate. 1 is different from FIG. 1 in that it does not have an inverted structure, a metal mask 25, a film formation reaction gas introduction pipe 30, and the like.
- the same components as those in FIG. 1 are denoted by the same reference numerals, and description thereof is omitted.
- the shielding plate 89 is disposed between the film forming source 27 and the substrate 21.
- a thin film formation region on the surface of the substrate 21 is defined by the opening 31 h of the shielding plate 89.
- a region that is not shielded by the shielding plate 89 is a thin film formation region on the surface of the substrate 21 where the material particles from the film forming source 27 can reach.
- the film-forming reaction gas introduction tube 30 since the film-forming reaction gas introduction tube 30 is not used, only the film-forming material 18 adheres to the surface of the substrate 21 to form a thin film. However, as in the first embodiment, by using the film formation reaction gas introduction tube 30, a thin film made of an oxide or the like of the film forming material 18 can be formed.
- a single-layer thin film can be formed only on one surface of the substrate 21. That is, by forming the film while transporting the substrate 21 from the first core roller 23 toward the second core roller 26, a single-layer thin film is formed on one surface of the substrate 21.
- the substrate 21 After forming a single-layer thin film, if the film is formed again while being transported from the second core roller 26 toward the first core roller 23 by reversing the transport direction of the substrate 21, the substrate 21. A two-layered thin film can be formed on one side. By repeating the film formation while reversing the substrate transport direction in this manner, a multilayer thin film having an arbitrary thickness can be formed on one surface of the substrate 21.
- Example 1 In Example 1, a silicon multilayer thin film having a thickness of about 8 ⁇ m was formed on both surfaces of the current collector by vacuum deposition using the film forming apparatus 20 shown in FIG. A roughened copper foil (thickness: 18 ⁇ m, width: 100 mm, manufactured by Furukawa Circuit Foil Co., Ltd.) was used as the current collector substrate 21, and silicon was used as the film forming material 18.
- the cooling body 1 was made of aluminum, and the length of the cooling surface 11 in the width direction of the substrate 21 was 90 mm.
- the substrate transport mechanism of the film forming apparatus 20 can reciprocate, and a silicon thin film having a film thickness of about 0.5 ⁇ m can be formed on both surfaces of the substrate 21 by one-way travel. Therefore, in Example 1, the silicon film having a thickness of about 8 ⁇ m was formed on both surfaces of the substrate 21 by repeating the film forming process by reciprocating traveling a total of 16 times for each one time.
- the cooling body 1 was arranged with a distance of about 1 mm from the substrate 21 and cooled with 10 ° C. cooling water.
- a metal mask 25 having a size of each opening 200 mm in the running direction ⁇ 85 mm in the width direction is arranged with a distance of about 2 mm from the substrate 21 so that the film forming width of the thin film in the width direction of the substrate 21 is 85 mm. did.
- no film formation reaction gas was introduced.
- silicon was melted by a 270 degree deflection electron beam evaporation source (manufactured by JEOL Ltd.) as a heating means.
- the molten silicon was irradiated with an electron beam having an acceleration voltage of ⁇ 10 kV and an emission current of 520 to 700 mA, and the generated vapor was directed to the copper foil substrate 21.
- the first layer thin film was formed on both surfaces of the substrate 21 at an emission current of 520 mA, a substrate transfer speed of 0.8 m / min, and a film deposition speed of 35 nm / sec without introducing a cooling gas.
- the thin film formation of the 2nd to 16th layers on both surfaces of the substrate 21 was performed at an average emission current of 700 mA, a substrate transport speed of 2.4 m / min, and a film deposition speed of 100 nm / sec. At this time, each 120 sccm of oxygen gas as a cooling gas was introduced into two gaps between the cooling surface 11 and the substrate 21.
- Example 1 high-temperature silicon vapor deposition particles adhere to the substrate 21 through the openings 31a and 31b of the metal mask 25. However, when forming the second to sixteenth layer thin films, 21 is cooled by the cooling gas from the non-film-forming surface side.
- the degree of vacuum in the vacuum chamber 22 is 0.003 Pa when the melting of silicon is completed and the molten metal surface is stabilized, according to a vacuum gauge provided in the piping path leading to the intake port of the oil diffusion pump as the exhaust means 37. It was about 0.004 Pa when the first layer of the silicon multilayer thin film was formed, and about 0.012 Pa when the second to sixteenth layers were formed.
- the degree of vacuum in the vacuum chamber 22 when oxygen gas of 120 sccm is introduced as a cooling gas under the same vacuum conditions without melting silicon, that is, without forming a thin film, is about 0.082 Pa. Met.
- the influence of the introduction of oxygen gas as a cooling gas on the substrate of the copper foil was examined by visual color change of the copper foil and stress-elongation characteristics.
- the stress-elongation characteristic was measured by pulling a copper foil test piece having a narrow portion having a width of 6 mm and a length of 40 mm at a speed of 50 mm / min.
- the strength before applying the heat load is about 10 N / mm, and it has been found that the strength of the copper foil substrate experienced at a temperature exceeding 400 ° C. is greatly reduced.
- the first layer formation received by the copper foil substrate 21 is The heat load at that time is 1 ⁇ 2 or less of the formation of the second to sixteenth layers. Therefore, at the time of forming the first layer, even if the cooling gas was not introduced, no significant deterioration due to the temperature rise of the copper foil substrate 21 did not occur.
- the introduction of oxygen gas as the cooling gas is only performed when the second to sixteenth layers are formed, the first layer has a stable film quality without being oxidized.
- film formation with a larger heat load was performed than when the first layer was formed.
- the cooling foil was introduced and the copper foil was sufficiently cooled, The remarkable deterioration of the copper foil substrate 21 did not occur.
- oxygen gas as a cooling gas is introduced only when the second to sixteenth layers are formed, so that deterioration due to oxidation of the exposed surface of the copper foil substrate 21 is prevented. I was able to.
- most of the cooling oxygen gas reacts with the silicon vapor and is removed from the space of the vacuum chamber 22 at the time of film formation, so that the reduction of the degree of vacuum in the vacuum chamber 22 due to the introduction of the cooling gas is suppressed. can do.
- the deterioration of the copper foil due to the temperature rise can be evaluated by, for example, a change in mechanical property value by a tensile test or the like as described above.
- the thermally deteriorated copper foil exhibits phenomena such as an increase in elongation with respect to a tensile load and a decrease in breaking strength. These characteristic deteriorations lead to deformation and breakage of the electrode plate because the silicon thin film used for the lithium secondary battery electrode plate expands when lithium is occluded.
- Example 2 In Example 2, a silicon oxide multilayer thin film having a thickness of about 15 ⁇ m was formed on both surfaces of the current collector by vacuum deposition using the film forming apparatus 40 shown in FIG. 6 based on Embodiment 2. .
- a roughened copper foil (thickness: 18 ⁇ m, width: 100 mm, manufactured by Furukawa Circuit Foil Co., Ltd.) was used as the current collector substrate 21, and silicon was used as the film forming material 18.
- the cooling body 1 was made of aluminum whose surface was black anodized, and the length of the cooling surface 11 in the width direction of the substrate 21 was 90 mm.
- the substrate transport mechanism of the film forming apparatus 40 can reciprocate, and a silicon oxide thin film having a film thickness of about 1 ⁇ m can be formed on both surfaces of the substrate 21 by one-way travel. Therefore, in Example 2, the film forming process by reciprocating traveling is repeated 15 times in total, one way, so that a silicon oxide multilayer thin film having a thickness of about 15 ⁇ m is laminated on both surfaces of the substrate 21. did.
- the cooling body 1 was placed in a vacuum chamber 22 having a volume of 0.4 m 3 with an interval of about 0.5 mm from the substrate 21 and cooled with cooling water at 10 ° C.
- a metal mask 45 having a size of each opening of 150 mm in length in the running direction and 85 mm in the width direction is arranged with a distance of about 2 mm from the substrate 21 so that the film forming width of the thin film in the width direction of the substrate 21 is 85 mm. did.
- oxygen gas is introduced toward each opening 31 of the metal mask 45 from the film introduction reaction gas introduction pipe 30 installed on the film formation surface side of the substrate 21, thereby providing a copper foil.
- the silicon vapor deposition particles before being deposited on the substrate 21 were oxidized. Thereby, a thin film made of silicon oxide was formed.
- silicon was melted by a 270 degree deflection electron beam evaporation source (manufactured by JEOL Ltd.) as a heating means.
- the molten silicon was irradiated with an electron beam having an acceleration voltage of ⁇ 10 kV and an emission current of 700 to 950 mA, and the generated vapor was directed to the copper foil substrate 21.
- the first layer thin film was formed on both surfaces of the substrate 21 at an emission current of 700 mA and a substrate transfer speed of 1.8 m / min.
- 30 sccm of oxygen gas as the film formation reaction gas is supplied from the film formation reaction gas introduction pipe 30 (not shown) to the opening 31c of the metal mask 45,
- the films were introduced toward 31d, 31e, and 31f, respectively, and a first layer thin film was formed at a film deposition rate of 100 nm / second.
- 9 sccm of each argon gas as a cooling gas was introduced into four gaps between the cooling surface 11 and the substrate 21.
- the thin film formation of the second to fifteenth layers on both surfaces of the substrate 21 was performed at an average emission current of 950 mA, a substrate transfer speed of 3.6 m / min, and a film deposition speed of 200 nm / sec.
- 30 sccm of oxygen gas as a film formation reaction gas was introduced from the film formation reaction gas introduction pipe 30 toward the openings 31 c, 31 d, 31 e, and 31 f of the metal mask 25.
- 60 sccm of oxygen gas and 9 sccm of argon gas as cooling gases were respectively introduced into four gaps between the cooling surface 11 and the substrate 21.
- high-temperature silicon vapor-deposited particles oxidized by oxygen gas as a film-forming reaction gas pass through the openings 31c, 31d, 31e, and 31f of the metal mask 45 and are on the substrate 21. Adhere to.
- the substrate 21 is cooled by argon gas from the non-film-forming surface side, and when the second to fifteenth layer thin films are formed, it is cooled by argon gas and oxygen gas.
- the degree of vacuum in the vacuum chamber 22 is 0.003 Pa when the melting of silicon is completed and the molten metal surface is stabilized, according to a vacuum gauge provided in the piping path leading to the intake port of the oil diffusion pump as the exhaust means 37. It was about 0.020 Pa when the first layer of the silicon oxide multilayer thin film was formed, and about 0.028 Pa when the second to fifteenth layers were formed.
- the degree of vacuum in the vacuum chamber 22 when oxygen gas of 60 sccm and argon gas of 9 sccm are introduced as cooling gases under the same vacuum conditions without melting silicon, that is, without forming a thin film, is as follows. , About 0.094 Pa.
- the rate of increase in the degree of oxidation x due to the introduction of oxygen gas, which is a cooling gas, is only about 1/10 of the rate of increase in the degree of oxidation x due to the introduction of oxygen gas, which is a film forming reaction gas. It can be said that the introduction of oxygen gas, which is a gas, has a very small effect on thin film quality.
- the formed thin film was heated (annealed) in an oxygen atmosphere with a pressure of 0.1 Pa or less and then the degree of oxidation x was measured, the thin film obtained when oxygen gas was introduced as the cooling gas was introduced. The almost same oxidation degree x was obtained with the thin film obtained in the absence. From this, it can be said that the quality of the thin film is not deteriorated by introduction of oxygen gas which is a cooling gas.
- the cooling gas leaked from between the cooling surface 11 and the substrate 21 remains only to slightly increase the degree of oxidation of the silicon oxide multilayer thin film. It is possible to form a stable thin film without drastically changing the film thickness. The reason is not sufficiently clear, but it seems that the effect is larger when the distance between the metal mask 45 and the substrate 21 is narrower. That is, when the distance between the metal mask 45 and the substrate 21 is narrow, most of the cooling gas leaked from between the cooling surface 11 and the substrate 21 does not enter the lower space 22 b of the vacuum chamber 22 and does not enter the vacuum chamber 22. Diffuses in the upper space 22a.
- the degree of oxidation of the silicon oxide multilayer thin film is substantially determined by the oxygen gas introduced as the film forming reaction gas.
- the film deposition rate at the time of forming the first layer is 1 ⁇ 2 of the film deposition rate at the time of forming the second to fifteenth layers
- the first layer received by the copper foil substrate 21 is used.
- the heat load during formation is considerably smaller than that during formation of the second to fifteenth layers. Therefore, at the time of forming the first layer, only a small amount of argon gas as a cooling gas was introduced, and the copper foil substrate 21 did not significantly deteriorate.
- the introduction of oxygen gas as a cooling gas is only performed when the second to fifteenth layers are formed, the first layer has a stable film quality with a low degree of oxidation.
- Example 2 since oxygen gas is introduced as a cooling gas only when the second to sixteenth layers are formed, deterioration due to oxidation of the exposed surface of the copper foil substrate 21 is prevented. I was able to.
- most of the cooling oxygen gas reacts with the silicon vapor and is removed from the space of the vacuum chamber 22 at the time of film formation, so that a reduction in the degree of vacuum in the vacuum chamber 22 due to the introduction of the cooling gas is suppressed. can do.
- the oxygen gas same as the film forming reaction gas is used as the cooling gas only when forming the second and subsequent thin films. Even if the amount of cooling gas introduced is increased, the deterioration of the degree of vacuum and the deterioration of the substrate can be suppressed. Thereby, a stable thin film can be formed with high efficiency using simple equipment at low cost.
- the thin film forming method of the present invention has been exemplified.
- the thin film forming method of the present invention is not limited to the above. The same effect can be obtained.
- film formation on the substrate 21 can be performed while the substrate 21 is traveling along a cylindrical cooling can which is the cooling body 1. At that time, the cooling gas can be supplied from a hole or groove provided on the surface of the cylindrical cooling can.
- argon gas and oxygen gas are used as the cooling gas, they are not limited to the above.
- an inert gas such as helium gas, neon gas, xenon gas, or krypton gas, or hydrogen gas may be used as a cooling gas after the first layer is formed.
- various hydrocarbon gases and nitrogen gases may be appropriately selected and used as a cooling gas for forming the first layer or a cooling gas for forming the second layer or later depending on the substrate material and the film forming material. Can do.
- the method for forming a negative electrode for a lithium ion secondary battery is taken as an example, but the present invention is not limited to this.
- an electrode plate for an electrochemical capacitor can be formed with a similar configuration.
- it is applied to various applications that require high-speed stable film formation, including transparent electrode films, capacitors, decorative films, solar cells, magnetic tapes, gas barrier films, various sensors, various optical films, hard protective films, etc. be able to.
- the thin film formation method of the present invention even if the amount of cooling gas introduced in the gas cooling is increased, after the cooling gas leaks from between the cooling body and the substrate, most of the amount is, for example, vapor of the film forming material. Since it reacts, it does not exist as floating gas, and deterioration of the vacuum degree can be prevented. This makes it possible to cool the gas necessary for film formation at a high film formation rate, while maintaining sufficient cooling capacity, while suppressing deterioration of the degree of vacuum and deterioration of thin film quality resulting from it, and at low cost and simple facilities. It can be realized using. In addition, it is possible to prevent deterioration of the substrate due to the introduced cooling gas and deterioration of the quality of the thin film.
- Cooling body 18 Film-forming material 19 Evaporation crucible 20, 40, 60 Film-forming apparatus 21 Substrate 22 Vacuum tank 22a Upper space 22b Lower space 23 Core roller A 24 Conveying roller 25, 45 Metal mask 26 Core roller B 27 Deposition source 29 Shielding plate 30 Deposition reaction gas introduction pipe 31a, 31b, 31c, 31d, 31e, 31f, 31g Opening 32 Manifold 33 Pore 34 Gas nozzle 34a Outlet 35 Cooling gas inlet 36 Exhaust port 37 , 37a, 37b Exhaust means 70 Endless belt 71 Can 77 Gap adjusting roller 78 Auxiliary roller 79 Shield plate
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Abstract
Description
図1は、本発明の実施の形態1に係る成膜装置20の構成図である。図1に示すように、本発明の実施の形態1に係る成膜装置20は、耐圧性の容器状部材である真空槽22の内部空間に、冷却体1、基板21、第一の巻き芯ローラ23、複数の搬送ローラ24、メタルマスク25、第二の巻き芯ローラ26、成膜源27、遮蔽板29、および、成膜反応用ガス導入管30を収容することで構成されている。
以下、冷却体1の構成について、図2、図3を用いて詳細に説明する。
図6は、本発明の実施の形態2に係る成膜装置40の構成図である。図6に示すように、本発明の実施の形態2に係る成膜装置40は、メタルマスク45の形状と、メタルマスク45の開口部31c、31d、31e、31fおよび冷却体1の配置箇所が、図1と異なる。図1と同一構成要素については同一符号を付し、説明を省略する。
図7は、本発明の実施の形態3に係る成膜装置60の構成図である。図7に示すように、本発明の実施の形態3に係る成膜装置60では、エンドレスベルト70によって、開口部31g近傍での基板21の搬送経路を規定している。また、排気手段37a、37bは、真空槽22の上側空間22aと下側空間22bにそれぞれ接続されている(ただし、本実施の形態3でも、実施の形態1と同様、下側空間22bのみに排気手段を接続してもよい)。以下に詳細を説明するが、図1と同一構成要素については同一符号を付し、説明を省略する。
基板21は、第一の巻き芯ローラ23から、上流側の搬送ローラ24、上流側の補助ローラ78、エンドレスベルト70、下流側のギャップ調整ローラ77、下流側の補助ローラ78を経て、第二の巻き芯ローラ26に導かれている。一対の補助ローラ78は、エンドレスベルト70から見て、基板21の搬送経路の上流側と下流側とのそれぞれに設けられており、基板21の搬送経路上でエンドレスベルト70に最も近い場所に位置しているローラである。これにより、基板21とエンドレスベルト70の距離が開きすぎないよう基板21に張力をかけることが可能になり、その結果、基板21がエンドレスベルト70に適度に密着するようになる。
遮蔽板79は、成膜源27とエンドレスベルト70との間に配置されている。遮蔽板79の開口部31gによって、基板21の表面における薄膜形成領域が規定されている。遮蔽板79によって遮蔽されていない領域が、成膜源27からの材料粒子が到達できる基板21の表面の薄膜形成領域である。
エンドレスベルト70についてさらに詳しく説明する。
(実施の形態4)
図8は、本発明の実施の形態4に係る成膜装置80の構成図である。図8に示すように、本発明の実施の形態4に係る成膜装置80は、開口部を1つのみ有しており、基板の片面のみに成膜をする装置であり、搬送ローラ24により構成される反転構造や、メタルマスク25、および、成膜反応用ガス導入管30等を有しない点で図1と異なる。図1と同一構成要素については同一符号を付し、説明を省略する。
本実施例1では、実施の形態1に基づき、図1に示す成膜装置20を用いて、集電体の両面上にそれぞれ厚さ約8μmのシリコン多層薄膜を真空蒸着法により形成した。集電体の基板21としては、粗面化銅箔(厚さ18μm、幅100mm 古河サーキットフォイル(株)製)を用い、成膜材料18としては、シリコンを用いた。冷却体1には、アルミニウムで構成されたものを使用し、基板21の幅方向における冷却面11の長さは90mmとした。
真空槽22内の真空度は、排気手段37としての油拡散ポンプの吸気口に至る配管経路に設けた真空計によると、シリコンの溶融が終了し、溶湯面が安定した時点で0.003Pa、シリコン多層薄膜の第1層形成時で約0.004Pa、第2~第16層形成時で約0.012Paであった。
(基板への影響)
冷却用ガスとして酸素ガス導入による銅箔の基板に対する影響を、目視による銅箔の色変化と、応力-伸び特性によって調べた。応力-伸び特性(S-S曲線)は、幅6mm、長さ40mmの幅狭部を持った銅箔試験片を50mm/minの速度で引っ張って測定した。使用した基板では、熱負荷印加前の強度は約10N/mmであり、400℃を越える温度を経験した銅箔基板の強度が大幅に低下することが分かっている。
(評価)
本実施例1では、第1層形成時の膜堆積速度を、第2~第16層形成時の膜堆積速度の約1/3としているために、銅箔の基板21が受ける第1層形成時の熱負荷は、第2~第16層形成時の1/2以下となる。そのため、第1層形成時には、冷却用ガスが導入されなくても、銅箔の基板21の温度上昇による顕著な劣化は発生しなかった。また、冷却用ガスとしての酸素ガスの導入は、第2~第16層の形成時のみとしているため、第1層は酸化されず安定した膜質となった。さらに、第2~第16層形成時に、第1層形成時に比して熱負荷の大きい成膜を行ったが、冷却用ガスが導入され銅箔が十分に冷却されていたので、温度上昇による銅箔の基板21の顕著な劣化は発生しなかった。
本実施例2では、実施の形態2に基づき、図6に示す成膜装置40を用いて、集電体の両面上にそれぞれ厚さ約15μmのシリコン酸化物多層薄膜を真空蒸着法により形成した。集電体の基板21としては、粗面化銅箔(厚さ18μm、幅100mm 古河サーキットフォイル(株)製)を用い、成膜材料18としては、シリコンを用いた。冷却体1には、表面を黒色アルマイト処理したアルミニウムで構成されたものを使用し、基板21の幅方向における冷却面11の長さは90mmとした。
真空槽22内の真空度は、排気手段37としての油拡散ポンプの吸気口に至る配管経路に設けた真空計によると、シリコンの溶融が終了し、溶湯面が安定した時点で0.003Pa、シリコン酸化物多層薄膜の第1層形成時で約0.020Pa、第2~第15層形成時で約0.028Paであった。
(酸化度xへの影響)
成膜を平均膜堆積速度約100nm/sにて行った際に、酸素導入による薄膜構成材料SiOxの酸化度xの変化を確認した。成膜反応用ノズルから酸素ガスを導入しない場合(導入量0sccm)、酸化度xは0.22であったが、成膜反応用ノズルから1600sccmで酸素ガスを導入した場合、酸化度xは0.75であった。これより、成膜反応用ガスである酸素ガス導入による酸化度xの上昇率は、成膜反応用ガス100scmあたり0.0331であることが分かる。
(評価)
このように、本実施例2によれば、冷却面11と基板21との間から漏れ出した冷却用ガスは、シリコン酸化物多層薄膜の酸化度を僅かに増加させる程度に留まり、薄膜の性質に劇的な変化を与えることなく、安定した薄膜を形成することができる。その理由は充分明らかではないが、メタルマスク45と基板21との間隔が狭い方が、効果が大きいと思われる。すなわち、メタルマスク45と基板21との間隔が狭いと、冷却面11と基板21との間から漏れ出した冷却用ガスの大半は、真空槽22の下側空間22bに回り込まずに真空槽22の上側空間22aで拡散する。このため、基板21の成膜面に至るまでに、その大半が基板21の成膜面付近以外で浮遊しているシリコン蒸気に捕獲されるものと考えられる。その結果、基板21上に形成されるシリコン酸化物多層薄膜の酸化度の増加が抑制されるものと考えられる。したがって、本実施例2では、シリコン酸化物多層薄膜の酸化度は、成膜反応用ガスとして導入された酸素ガスによりほぼ決定される。
18 成膜材料
19 蒸発用坩堝
20、40、60 成膜装置
21 基板
22 真空槽
22a 上側空間
22b 下側空間
23 巻き芯ローラA
24 搬送ローラ
25、45 メタルマスク
26 巻き芯ローラB
27 成膜源
29 遮蔽板
30 成膜反応用ガス導入管
31a、31b、31c、31d、31e、31f、31g 開口部
32 マニホールド
33 細孔
34 ガスノズル
34a 吹出口
35 冷却用ガス導入口
36 排気ポート
37、37a、37b 排気手段
70 エンドレスベルト
71 キャン
77 ギャップ調節ローラ
78 補助ローラ
79 遮蔽板
Claims (9)
- 真空中で、表面と裏面を有する基板上に成膜材料を堆積させることで薄膜を形成する薄膜形成方法であって、
第一薄膜形成領域において前記裏面に近接するように第一冷却面を配置する第一配置工程と、
前記基板の前記表面上に、前記第一薄膜形成領域内で薄膜を形成する第一薄膜形成工程と、
第一薄膜形成工程の実施中に、前記第一冷却面と前記裏面との間に、前記成膜材料と反応するガスを含む冷却用ガスを導入することで前記基板を冷却する第一冷却工程と、を含む、薄膜形成方法。 - 第一薄膜形成工程を前記表面の所定箇所に対して複数回実施することにより当該箇所に多層薄膜を形成し、
第一層目の薄膜を形成する際に導入する前記成膜材料と反応するガスの量が、第二層目の薄膜を形成する際に導入する前記成膜材料と反応するガスの量よりも少ない、請求項1記載の薄膜形成方法。 - 第一薄膜形成工程を前記表面の所定箇所に対して複数回実施することにより当該箇所に多層薄膜を形成し、その際、
第一層目の薄膜を形成する第一薄膜形成工程の実施中に、前記第一冷却面と前記裏面との間に、冷却用ガスを導入しないか、又は、前記成膜材料と反応しないガスを主体とする冷却用ガス、を導入し、
第二層目以降の薄膜を形成する第一薄膜形成工程の実施中に、第一冷却工程を行う、請求項2記載の薄膜形成方法。 - 第二薄膜形成領域において前記表面に近接するように第二冷却面を配置する第二配置工程と、
前記基板の前記裏面上に、前記第二薄膜形成領域内で薄膜を形成する第二薄膜形成工程と、
第二薄膜形成工程の実施中に、前記第二冷却面と前記表面との間に、前記成膜材料と反応するガスを含む冷却用ガスを導入することで前記基板を冷却する第二冷却工程と、を含み、
前記基板の両面に薄膜を形成する、請求項1記載の薄膜形成方法。 - 前記基板が金属箔である、請求項1記載の薄膜形成方法。
- 前記成膜材料と反応するガスは、酸素を含む、請求項1記載の薄膜形成方法。
- 前記第一層目の薄膜形成時の膜堆積速度が、第二層目以降のいずれかの層の薄膜形成時の膜堆積速度より遅い、請求項2記載の薄膜形成方法。
- 前記第一層目の薄膜形成時の前記冷却用ガスの総導入量が、第二層目以降のいずれかの層の薄膜形成時の前記冷却用ガスの総導入量より少ない、請求項2記載の薄膜形成方法。
- 前記薄膜が、前記成膜材料及び酸素を含む、請求項1記載の薄膜形成方法。
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