JP2012144783A - Apparatus and method for producing thin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and method for producing a thin film, which is excellent in productivity, and can subject a surface of a substrate to oxidization treatment and also can form a thin-film on the surface thereof, continuously and stably in a single vacuum container without providing a differential pressure structure, while conveying a belt-like substrate.SOLUTION: The apparatus for producing the thin film on the surface of the belt-like substrate in vacuum includes: a conveying mechanism for conveying the substrate 4; a thin film-forming unit for forming the thin film in a first thin film-forming region 15a on the surface of the substrate held by the conveying mechanism, wherein the thin film-forming unit is arranged facing the first thin film-forming region and includes a vapor deposition source 3a for housing a raw vapor deposition material; a first gas nozzle 17a, arranged ahead of the first thin film-forming region 15a in a conveying path of the substrate, for supplying an ozone-containing gas to the surface of the substrate; and the vacuum container for housing the conveying mechanism, the thin film-forming unit, and the first gas nozzle.

Description

  The present invention relates to a thin film manufacturing apparatus and a thin film manufacturing method for forming a thin film on a strip-shaped substrate by evaporating a thin film raw material.

  Thin film formation techniques such as vacuum deposition, sputtering, and CVD contribute to a wide range of industrial fields including the semiconductor industry, and are widely used for high performance and miniaturization of devices. For example, in a lithium secondary battery, studies are being made to increase the battery capacity by forming a Si thin film as an electrode active material layer on a current collector made of a metal such as copper.

  However, when the Si thin film is directly formed on the current collector made of copper, there is a problem that the reaction and diffusion proceed at the interface between the active material layer and the current collector, and the charge / discharge characteristics of the active material layer deteriorate. .

  In Patent Document 1, in order to solve this problem, after forming an oxide film by oxidizing the surface of a current collector made of copper, an active material layer is formed on the oxide film using a thin film forming technique. A method is disclosed. This document describes that an ECR source is used in the presence of oxygen gas at a constant pressure for the oxidation treatment of the current collector surface.

Japanese Patent No. 3754374

  However, in the oxidation method using the ECR source, the oxygen gas pressure during the oxidation treatment is required to be higher than the gas pressure during the thin film formation. Therefore, Patent Document 1 describes that when performing oxidation treatment and thin film formation in the same chamber, after performing the oxidation treatment under high pressure, the thin film formation is performed after the gas pressure in the chamber is lowered. With such a method, the productivity of thin film formation is reduced, and it is impossible to continuously form a thin film while conveying a strip-shaped current collector.

  When a thin film made of a material having a high melting point is formed on the surface of the current collector, a heating means such as an electron beam is used as a means for evaporating the material. At this time, if the gas pressure is high, abnormal discharge occurs and the thin film is formed. The inconvenience that it cannot be formed occurs. Furthermore, when the gas pressure fluctuates during the formation of the thin film, there arises a problem that the composition of the formed thin film changes.

  Therefore, in the case of continuously forming a thin film while transporting the belt-shaped current collector, in the same vacuum vessel, a section for performing an oxidation treatment on the current collector surface to form an oxide film, By separating the compartment for forming a thin film on the current collector surface and providing a differential pressure structure between the two compartments, the gas pressure in both compartments can be maintained at a gas pressure suitable for each treatment. Conceivable.

  However, when the differential pressure structure is provided, there is a disadvantage that the configuration of the apparatus becomes complicated and the apparatus becomes large.

  The present invention has been made in view of the above circumstances, and in carrying out oxidation treatment and thin film formation of a substrate surface continuously while transporting a belt-like substrate, a single vacuum container is provided without providing a differential pressure structure. It is an object of the present invention to provide a thin film production apparatus and a thin film production method excellent in productivity that can stably carry out both treatments.

  The thin film manufacturing apparatus of the present invention is a thin film manufacturing apparatus for forming a thin film on a surface of a strip-shaped substrate having a front surface and a back surface in a vacuum, and includes a transport mechanism for transporting the substrate and the transport mechanism. A thin film forming means for forming a thin film in the first thin film forming region on the surface of the substrate being held, the vapor deposition accommodating the deposition raw material disposed facing the first thin film forming region A thin film forming means including a source, a first gas nozzle that is disposed in front of the first thin film forming region in the transport path of the substrate, and supplies an ozone-containing gas toward the surface of the substrate; and the transport mechanism; The thin film forming means and a vacuum container that houses the first gas nozzle.

  The thin film manufacturing apparatus of the present invention forms a thin film by evaporating a vapor deposition material from a vapor deposition source in a vacuum and adhering it to a substrate surface. Further, a thin film is continuously formed on the substrate while the belt-shaped substrate is conveyed, and the substrate surface is oxidized as a pretreatment for forming the thin film. Thereby, the oxidation process of the substrate surface and the thin film formation on the substrate oxidized thereby can be continuously performed in a single vacuum vessel.

  Ozone is used for the oxidation of the substrate surface. Oxidation with ozone has better reaction efficiency than oxidation with oxygen, so that the amount of gas to be introduced is small, and the substrate surface can be oxidized under a low gas pressure. Therefore, it is not necessary to oxidize the substrate surface under high gas pressure as in Patent Document 1, and it can be performed under the same low gas pressure as that for forming a thin film.

  Therefore, it is not necessary to provide a differential pressure structure in the thin film manufacturing apparatus of the present invention. That is, in the thin film manufacturing apparatus of the present invention, no differential pressure structure is provided between the first thin film forming region and the first gas nozzle, and the substrate oxidation by the ozone-containing gas and the thin film formation in the first thin film forming region are performed. Can be carried out under the same gas pressure.

  Moreover, it is not necessary to change the gas pressure in the vacuum vessel during the substrate oxidation and thin film formation, and the same gas pressure can be maintained, so that both processes can be carried out stably.

  The thin film formed in the present invention may be a non-oxide thin film or an oxide thin film.

  When forming a thin film made of oxide, oxygen gas or ozone-containing gas may be separately supplied in the vicinity of the first thin film forming region, or the ozone-containing gas used for the oxidation of the substrate surface may be used. . In the latter case, by supplying the ozone-containing gas from the first gas nozzle, both the oxidation of the substrate surface and the oxidation of the vapor deposition material can be achieved, so that the configuration of the apparatus can be simplified, which is preferable. Ozone is preferable because it has a high reaction efficiency with the vapor deposition material and can efficiently oxidize the vapor deposition material.

  The thin film manufacturing apparatus of the present invention includes a substrate oxidation promoting portion that is disposed in the vicinity of the surface of the substrate in a region to which an ozone-containing gas is supplied by the first gas nozzle and promotes oxidation of the surface by the ozone-containing gas. Furthermore, it is preferable to have. Thereby, the oxidation of the substrate surface by ozone can be promoted, and the desired oxidation can be achieved more reliably. The substrate oxidation accelerating portion is a light irradiation portion that irradiates light toward the substrate surface in a region to which ozone-containing gas is supplied from the first gas nozzle, or a region in which ozone-containing gas is supplied from the first gas nozzle. A heating unit that heats the substrate surface can be used.

  As a light irradiation part, the ultraviolet irradiation part which irradiates an ultraviolet-ray to the said surface of the said board | substrate in the area | region where ozone containing gas is supplied by said 1st gas nozzle is preferable. When the temperature of the substrate rises, the substrate may be thermally deformed. However, when the ultraviolet irradiation unit is used, the oxidation of the substrate surface by ozone can be promoted without increasing the temperature of the substrate so much.

  The thin film manufacturing apparatus of the present invention may be configured to form a thin film not only on the front surface of the substrate but also on the back surface of the substrate. In this case, the thin film manufacturing apparatus of the present invention is disposed behind the first thin film formation region in the substrate transport path, and has an inverted structure for turning the substrate upside down so that the back surface faces the vapor deposition source. A second gas nozzle that is disposed after the reversal structure in the transport path and supplies an ozone-containing gas toward the back surface of the substrate, and is set after the second gas nozzle in the transport path of the substrate A thin film is formed on the back surface of the substrate in the second thin film formation region. With the above configuration, the oxidation on both sides of the substrate and the formation of the thin film on both sides of the oxidized substrate can be continuously performed in a single vacuum vessel. The oxidation treatment and thin film formation on the back surface may be the same as the oxidation treatment and thin film formation described above. The vapor deposition source facing the back surface may be different from the vapor deposition source facing the front surface, or may share the same material.

  The thin film manufacturing method of the present invention is a thin film manufacturing method using the thin film manufacturing apparatus, supplying the ozone-containing gas from the first gas nozzle toward the surface of the substrate and irradiating ultraviolet rays. Then, the step of oxidizing the surface and the step of causing the evaporated deposition material to enter the oxidized surface and forming a thin film in the first thin film forming region are included. As described above, oxidation of the substrate surface and formation of a thin film on the oxidized substrate surface can be continuously performed in a single vacuum container without providing a differential pressure structure.

  According to the present invention, ozone is used for the oxidation of the substrate surface, so that the oxidation of the substrate surface and the thin film formation can be performed under the same low gas pressure. Therefore, oxidation of the substrate surface and thin film formation can be carried out continuously in the same vacuum vessel. In addition, it is not necessary to separate the compartment for performing the oxidation treatment by providing the differential pressure structure and the compartment for forming the thin film. Therefore, the number of exhaust pumps used can be reduced, and the vacuum vessel can be reduced in size. As described above, it is possible to improve the productivity of forming a thin film accompanied with the oxidation treatment of the substrate surface and reduce the manufacturing cost.

Sectional drawing which shows typically the thin film manufacturing apparatus which is 1st embodiment of this invention The principal part expansion perspective view which expands and shows the oxidizable area | region 14a vicinity shown in FIG. Sectional drawing which shows typically the thin film manufacturing apparatus 101 which is 2nd embodiment of this invention. Sectional drawing which shows typically the thin film manufacturing apparatus 102 which is 3rd embodiment of this invention. The principal part expansion perspective view which expands and shows the oxidizable area | region 14a vicinity in FIG. Sectional drawing which shows typically the thin film manufacturing apparatus 103 which is 4th embodiment of this invention.

  Hereinafter, embodiments of a thin film manufacturing apparatus and a thin film manufacturing method using the same according to the present invention will be described with reference to the drawings.

(First embodiment)
<Configuration of thin film manufacturing equipment>
FIG. 1 is a cross-sectional view schematically showing a thin film manufacturing apparatus according to the first embodiment of the present invention. The thin film manufacturing apparatus 100 includes a vacuum vessel 1, an exhaust pump 2 for exhausting the vacuum vessel 1, an ozone-containing gas, an oxygen gas, and the like from the outside of the vacuum vessel 1 to the vacuum vessel 1. And a gas introduction pipe (not shown) for introducing the gas.

  Inside the vacuum vessel 1, vapor deposition sources 3a and 3b for accommodating and evaporating vapor deposition materials, a conveyance unit for conveying the sheet-like substrate 4, and a cooling can roll 6a for cooling and supporting the substrate 4 are provided. , 6b, a shielding plate 10 that forms a shielding region where the vapor deposition material evaporated from the vapor deposition sources 3a and 3b does not reach, and a partial region of the cooling can roll 6 is shielded from the vapor deposition material to control the deposition amount of the vapor deposition film. Masks 11a and 11b and a movable shutter 13 for blocking the vapor deposition material evaporated from the vapor deposition sources 3a and 3b in a timely manner are provided.

  Further, connected to the gas introduction pipe, are connected to the gas introduction pipe, and raw material oxidation gas nozzles 12a and 12b for supplying gas (raw material oxidation gas) for oxidizing the vapor deposition raw material evaporated from the vapor deposition sources 3a and 3b. The substrate oxidation gas nozzles 17a and 17b for supplying a gas for oxidizing the substrate surface (ozone-containing gas which is a substrate oxidation gas), and the substrate oxidation gas supplied in the vicinity of the gas nozzles 17a and 17b Irradiating lamps 5a and 5b are provided. In the present embodiment, since the raw material oxidizing gas is supplied from the gas nozzles 12a and 12b, the deposited film is oxidized to form a thin film made of oxide. However, in the present invention, a thin film made of a non-oxide may be formed without installing the gas nozzles 12a and 12b, that is, without supplying the raw material oxidizing gas.

  The belt-shaped substrate 4 is supplied with a substrate oxidizing gas from the gas nozzle 17a, and is oxidizable region 14a where the substrate surface is oxidized by being irradiated with light from the lamp 5a, and the evaporation material evaporated from the evaporation source 3a is deposited. The deposition possible region 15a where the film is formed, the substrate oxidizing gas is supplied from the gas nozzle 17b, the light is emitted from the lamp 5b, the oxidizable region 14b where the back surface of the substrate is oxidized, and the deposition raw material evaporated from the deposition source 3b. It is hold | maintained and conveyed by a conveyance part and a cooling can roll so that it may pass through the vapor deposition possible area | region 15b in which it deposits and a vapor deposition film is formed in this order. The oxidizable region 14a including the lamp 5a and the gas nozzle 17a is provided in front of the deposition possible region 15a and the mask 11a in the substrate transfer path. The oxidizable region 14b including the lamp 5b and the gas nozzle 17b is provided after the deposition possible region 15a and the mask 11a and before the mask 11b and the deposition possible region 15b in the substrate transfer path.

  The lamps 5a and 5b irradiate the substrate surface with light, thereby decomposing ozone contained in the substrate oxidizing gas supplied from the gas nozzles 17a and 17b to promote the oxidation of the substrate surface. The lamps 5a and 5b may be halogen lamps or ultraviolet lamps, but are preferably ultraviolet lamps. In the halogen lamp, for example, a high output power of 400 W is applied to promote the oxidation reaction of the substrate by ozone, so that the substrate temperature rises. As a result, the substrate becomes soft and easily deformed. Since the ultraviolet lamp can promote the oxidation reaction with a low output power such as 40 W, the oxidation efficiency can be increased without increasing the substrate temperature, and damage to the substrate can be reduced.

  In the present invention, a heater can be used instead of the lamp. In this case, in order to avoid damage to the substrate, it is preferable to install the heater so as not to contact the substrate. At this time, in order to ensure the transfer of heat from the heater to the substrate, it is preferable to introduce a heat transfer gas into the space between the heater and the substrate.

  The temperature of the cooling can rolls 6a and 6b is controlled by passing a cooling / heating medium therethrough. The temperature is about -10-30 degreeC. Vapor deposition sources 3a and 3b are arranged below the cooling can rolls 6a and 6b, and a vapor deposition film is formed on the substrate 4 while the substrate 4 is transported along the cooling can rolls. Thereby, since the board | substrate 4 is cooled by a cooling can roll, it can reduce that the temperature of the board | substrate 4 raises by receiving the heat | fever of a vapor deposition raw material, and can suppress the thermal deformation of a board | substrate.

  In FIG. 1, the openings of the masks 11 a and 11 b are disposed at the lowermost portions of the cooling can rolls 6 a and 6 b, respectively, so that the vapor of the deposition material is incident on the surface of the substrate 4 as perpendicularly as possible. Since the growth direction of the vapor deposition particles on the substrate surface is governed by the incident direction of the vapor of the vapor deposition material, the vapor deposition particles grow vertically on the substrate in the above-described normal incidence, thereby forming a dense film. Can do. In addition, in normal incidence, since the distance between the vapor deposition sources 3a and 3b and the substrate is short, the film formation rate can be increased, and the productivity is improved.

  As another form, you may arrange | position the opening part of mask 11a, 11b diagonally with respect to a horizontal direction along cooling can roll 6a, 6b (for example, FIG. 6). In this case, the vapor of the vapor deposition material is incident obliquely with respect to the normal direction of the substrate 4. In this oblique incidence, since the vapor deposition particles grow obliquely on the substrate, a gap can be provided between adjacent vapor deposition particles.

  In any form, the film thickness of the deposited film to be formed can be controlled by changing the length of the opening defined by the mask 11a or the mask 11b and the transport speed of the substrate.

  In the present invention, the substrate 4 is linearly held between the two transport rolls 8 without providing the cooling can rolls 6a and 6b, and the vapor deposition film is formed on the substrate in the linear region (deposition possible region). It can also be formed. Although the linear deposition possible region can be set horizontally, it may be set obliquely.

  The vapor deposition sources 3a and 3b include a heat-resistant crucible (for example, a carbon crucible) that accommodates the vapor deposition material, and an electron beam heating device (not shown) for evaporating the vapor deposition material. The crucible is configured to be appropriately removable. When performing vapor deposition, the vapor deposition material accommodated in the crucible is heated by an electron beam heating device, evaporates from the upper surface of the crucible, and deposits on the surface of the substrate 4.

  The transport unit includes a first roll 7 and a second roll 9 that can wind and hold the substrate 4, and a plurality of transport rolls 8 that guide and transport the substrate 4. The substrate transport path is defined such that two oxidizable regions 14a and 14b and two vapor depositionable regions 15a and 15b are disposed between the first roll 7 and the second roll 9. The conveyance path is defined so that the substrate after facing the vapor deposition source 3a is turned over by the conveyance roll 8 so that the back surface of the substrate faces the vapor deposition source 3b. In this transport path, first, the surface of the substrate 4 is oxidized and the deposited film is formed in the oxidizable region 14a and the deposition possible region 15a. Then, after the substrate is turned over, the oxidizable region 14b and the deposition are formed. In the possible region 15 b, oxidation treatment and vapor deposition film formation are performed on the back surface of the substrate 4. No differential pressure structure is provided between the oxidizable region 14a and the vapor-depositable region 15a and between the oxidizable region 14b and the vapor-depositable region 15b.

  However, in the present invention, inversion of the substrate is not essential, and a thin film manufacturing apparatus that performs oxidation treatment and formation of a deposited film only on the surface of the substrate may be used.

  If the board | substrate 4 used by this invention is a strip | belt-shaped board | substrate, the material will not be specifically limited. When producing an electrode of a lithium secondary battery, a metal foil that can collect current (for example, an aluminum foil, a copper foil, a nickel foil, or the like) is used. As the copper foil, for example, a rolled copper foil or an electrolytic copper foil is used.

<Configuration of lamps 5a and 5b>
FIG. 2 is an enlarged perspective view of a main part showing the vicinity of the oxidizable region 14a including the lamp 5a shown in FIG.

  The oxidizable region 14a is disposed in front of the deposition possible region 15a in the substrate transfer path. Here, the lamp 5 a is installed so as to be parallel to the width direction of the substrate 4 and to irradiate light to the entire width of the substrate 4. An ozone-containing gas is supplied from the gas nozzle 17 a to the space between the lamp 5 a and the substrate 4. The gas nozzle 17 a has a plurality of holes for ejecting ozone-containing gas at equal intervals in the nozzle portion, and thereby the ozone-containing gas is uniformly ejected in the width direction of the substrate 4. Ozone is decomposed by the light emitted from the lamp 5a, whereby the surface of the substrate 4 is efficiently oxidized and an oxide film is formed.

<Operation of thin film manufacturing equipment>
Next, a procedure for performing oxidation of the substrate surface and formation of a deposited film using the thin film manufacturing apparatus described above will be described.

During the oxidation of the substrate surface and the formation of the vapor deposition film, the vacuum vessel 1 is evacuated by the exhaust pump 2. At the same time, an ozone-containing gas is introduced from the raw material oxidation gas nozzles 12a and 12b and the substrate oxidation gas nozzles 17a and 17b. Thereby, the inside of the vacuum vessel 1 is placed in an ozone-containing atmosphere having a pressure of about 10 ⁻² Pa, for example.

  Ozone is a highly active oxidizing agent. In order to achieve high oxidizing power, it is preferable that the ozone concentration in the ozone-containing gas is high, but from the viewpoint of safety, it is preferably about 15% or less, but is not particularly limited. As the ozone-containing gas, a mixed gas of ozone and oxygen can be used. Specific examples of the ozone-containing gas include a mixed gas having an ozone concentration of 15% and an oxygen concentration of 85%.

  The oxidation of the vapor deposition raw material may be achieved by introducing oxygen gas not containing ozone from the raw material oxidation gas nozzles 12a and 12b. Oxidation of the vapor deposition material can also be achieved by oxygen gas. However, since ozone is more active than oxygen and has good oxidation efficiency of the vapor deposition material, it is preferable to introduce ozone-containing gas also from the material oxidation gas nozzles 12a and 12b.

  In the case where the ozone-containing gas is introduced from the raw material oxidation gas nozzles 12a and 12b, the substrate receives heat from the vapor deposition raw material in the vapor deposition possible region, and the substrate temperature is high. It is not necessary to separately provide a substrate oxidation promoting part such as.

  Next, a specific processing process will be described. The substrate 4 is transported by unwinding the substrate 4 from the first roll 7 that winds and holds the substrate 4 and winding the substrate 4 on the second roll 9. The substrate 4 drawn out from the first roll 7 is first oxidized in the oxidizable region 14a by being sprayed with ozone-containing gas from the substrate oxidation gas nozzle 17a, and irradiated with light from the lamp 5a. By being decomposed, the surface of the substrate 4 is efficiently oxidized, and an oxide film is formed.

  The substrate 4 is further transported, and a vapor deposition film is formed on the oxide film on the substrate surface in the next reachable vapor deposition region 15a. Specifically, first, an electron beam generated by an electron beam heating device is deflected by a deflection yoke, irradiated to a vapor deposition material accommodated in a crucible, and heated. For example, Si can be used as the vapor deposition material, and specifically, Si scraps (scrap silicon: purity 99.9999%) generated when a semiconductor wafer is formed can be used. The heated deposition material is evaporated from the upper surface of the crucible toward the substrate surface. The deposition material reacts with the ozone-containing gas or oxygen gas introduced from the material oxidation gas nozzle 12a, whereby the deposition material is oxidized, and the deposition film made of the oxide of the deposition material is formed on the oxide film on the substrate surface. Is formed. When the deposition material is Si, the deposited film formed is made of SiOx (where 0 <x ≦ 2). Thus, in the vapor deposition possible region 15a, an oxide thin film is formed on the surface of the substrate 4 by a vapor phase method in an ozone-containing atmosphere.

  The substrate 4 having the oxide thin film formed on the front surface is further conveyed, passes through the inversion structure, and the back surface reaches the oxidizable region 14b. In the oxidizable region 14b, ozone-containing gas is blown from the substrate oxidation gas nozzle 17b, and light is irradiated by the lamp 5b, whereby the introduced ozone gas is decomposed, and the back surface of the substrate 4 is efficiently oxidized, and the oxidation is performed. A film is formed.

  The substrate 4 is further transported, and a vapor deposition film is formed on the oxide film on the back surface of the substrate in the vapor deposition possible region 15b reached next. Specifically, it is the same as the formation of the vapor deposition film in the vapor deposition possible region 15a, and the vapor deposition raw material reacts with the ozone-containing gas or oxygen gas introduced from the raw material oxidation gas nozzle 12b. Oxidized, and a vapor deposition film made of an oxide of the vapor deposition material is formed on the oxide film on the back surface of the substrate.

  Through the above process, the oxide film formation and the vapor deposition film formation on both sides of the belt-like substrate can be carried out continuously in a single vacuum vessel without changing the pressure in the vessel.

  Thereafter, the substrate transport direction is reversed, the substrate 4 is fed out from the second roll 9, and the substrate 4 is wound around the first roll 7, and the vapor deposition film is formed in the same manner as described above. A second vapor deposition film can be formed on the vapor deposition film. By forming the deposition film while reversing the substrate by reversing the substrate transport direction in this way, it is possible to form a deposition film with an arbitrary number of layers, thereby controlling the film thickness of the entire deposition film. can do.

  In this case, when forming the second and subsequent deposited films, the oxide film forming step can be omitted, but the oxide film forming step is performed to promote the oxidation of the already formed deposited film. You can also. According to this method, it is possible to form a vapor deposition film having a high degree of oxidation while reducing the amount of gas introduced from the raw material oxidation gas nozzles 12a and 12b. Further, by controlling the amount of gas introduced, the degree of oxidation in the deposited film of each layer can be controlled, and deposited films having different degrees of oxidation in the thickness direction can also be formed.

  As described above, in the thin film manufacturing apparatus 100, the oxidizable region 14a or 14b and the vapor depositable region 15a or 15b are arranged in the vacuum vessel 1 without being separated by pressure difference, and the substrate surface is oxidized under the same pressure. Thin film formation by vapor deposition is possible. As a result, the number of exhaust pumps used can be reduced and the vacuum vessel can be reduced in size, and productivity can be improved.

  Further, although the electron beam evaporation can deposit the evaporation material at a high film formation rate, there is an inconvenience that abnormal discharge occurs in the evaporation possible regions 15a and 15b when the pressure in the vacuum vessel increases. Therefore, it is necessary to reduce the gas introduction amount and lower the pressure in the vacuum vessel. In the thin film manufacturing apparatus 100, by utilizing ozone oxidation, the substrate surface can be oxidized with a small amount of gas introduction, so that stable film formation can be realized. Further, when forming a thin film made of an oxide, more stable film formation can be realized by using ozone for the oxidation of the deposition material.

(Second embodiment)
FIG. 3 is a cross-sectional view schematically showing a thin film manufacturing apparatus 101 according to the second embodiment of the present invention. Hereinafter, differences from the thin film manufacturing apparatus 100 will be described.

  The oxidizable region 14a is provided in front of the vapor deposition possible region 15a in the substrate transfer path, but is provided so as to be close to or partially overlap the vapor deposition possible region 15a. The lamp 5a and the substrate oxidizing gas nozzle 17a in the oxidizable region 14a are disposed between the mask 11a and the cooling can roll 6a. The oxidizable region 14b is provided in front of the vapor deposition possible region 15b in the substrate transport path, but is provided so as to be close to or partially overlap the vapor deposition possible region 15b. The lamp 5b and the substrate oxidizing gas nozzle 17b in the oxidizable region 14b are disposed between the mask 11b and the cooling can roll 6b.

  The thin film manufacturing apparatus 101 performs the same operation as the thin film manufacturing apparatus 100 to continuously form the oxide film and the vapor deposition film on both sides of the belt-shaped substrate, and fluctuate the pressure in the container in a single vacuum container. Can be implemented without any problem.

  The thin film manufacturing apparatus 101 has the same advantages as the thin film manufacturing apparatus 100, and also has the following advantages. The oxidizable regions 14a and 14b are provided so as to be close to or partially overlap with the deposition possible regions 15a and 15b, respectively. For this reason, since the vapor deposition film is formed immediately after the surface of the substrate is oxidized, when the substrate is transported between the oxidation treatment of the substrate and the vapor deposition film formation, an organic substance or the like is formed on the oxide film of the substrate. Can be avoided. Since there is no inclusion of impurities, the adhesion between the substrate and the deposited film can be improved.

  Furthermore, since the substrate oxidation gas nozzles 17a or 17b are disposed in the vicinity of the deposition possible region 15a or 15b, the gas introduced from the gas nozzles 17a and 17b can also contribute to the oxidation of the deposition material, and the total amount of gas is small. A vapor deposition film made of an oxide can be efficiently formed by the amount introduced. As a result, the pressure in the vacuum vessel can be lowered, and more stable film formation can be realized. Further, since the ozone-containing gas is introduced from the gas nozzles 17a and 17b, even if the gas introduced from the gas nozzles 12a and 12b is an oxygen gas that does not contain ozone, an efficient oxidation of the vapor deposition material by ozone is realized. Can do.

(Third embodiment)
FIG. 4 is a cross-sectional view schematically showing a thin film manufacturing apparatus 102 according to the third embodiment of the present invention. Hereinafter, differences from the thin film manufacturing apparatus 100 will be described.

  The oxidizable region 14a is provided in front of the deposition possible region 15a in the substrate transport path, but is provided so as to partially overlap the deposition possible region 15a. In the oxidizable region 14a, the organic substance decomposition lamp 30a, the substrate oxidation and raw material oxidation gas nozzle 31a, and the lamp 5a are arranged in this order in the substrate transfer path, and all are arranged between the mask 11a and the cooling can roll 6a. Has been. The oxidizable region 14b is provided before the deposition possible region 15b in the substrate transport path, but is provided so as to partially overlap the deposition possible region 15b. In the oxidizable region 14b, the organic substance decomposition lamp 30b, the substrate oxidation and raw material oxidation gas nozzle 31b, and the lamp 5b are arranged in this order in the substrate transport path, and all are arranged between the mask 11b and the cooling can roll 6b. Has been.

  The organic matter decomposition lamps 30a and 30b irradiate the substrate surface with light to decompose and remove the organic matter adhering to the substrate surface. For example, the 40 W ultraviolet lamp described above can be used as the organic matter decomposition lamp.

  The substrate oxidation and raw material oxidation gas nozzles 31a and 31b may be the same as the substrate oxidation gas nozzles 17a and 17b, but the ozone-containing gas introduced from here also oxidizes the deposition raw material in addition to the oxidation of the substrate surface. To contribute.

  FIG. 5 is an enlarged perspective view of an essential part showing the vicinity of the oxidizable region 14a in FIG. 4 together with the cooling can roll 6a. Here, the organic matter decomposition lamp 30 a and the lamp 5 a are installed so as to be parallel to the width direction of the substrate 4 and to irradiate light to the entire width of the substrate 4. An ozone-containing gas is supplied from the gas nozzle 31 a to the space between the lamp 5 a and the substrate 4. The gas nozzle 31 a has a plurality of holes for ejecting ozone-containing gas at equal intervals in the nozzle portion, and thereby the ozone-containing gas is uniformly ejected in the width direction of the substrate 4. Ozone is decomposed by the light emitted from the lamp 5a, whereby the surface of the substrate 4 is oxidized and an oxide film is formed.

  In the third embodiment, before the substrate surface is oxidized in the oxidizable region 14a or the oxidizable region 14b, the substrate surface is irradiated with light from the organic matter decomposition lamp 30a or 30b, thereby being attached to the substrate surface. Organic matter is decomposed and removed. Thereafter, an ozone-containing gas is introduced from the gas nozzle 31a or the gas nozzle 31b, and light is irradiated by the lamps 5a and 5b, whereby the introduced ozone is decomposed, and the surface of the substrate 4 is efficiently oxidized, and the width direction A uniform oxide film is formed. In the evaporable region 15a or the evaporable region 15b, which partially overlaps the oxidizable region 14a or the oxidizable region 14b, the evaporated deposition material reacts with the ozone-containing gas introduced from the gas nozzle 31a or the gas nozzle 31b. The deposition material is oxidized, and a deposition film made of the oxide of the deposition material is formed on the oxide film on the substrate surface.

  The thin film manufacturing apparatus 102 has the same advantages as the thin film manufacturing apparatus 100 and the thin film manufacturing apparatus 101, and also has the following advantages. By disposing the organic matter decomposition lamp 30a or 30b in front of the gas nozzle, the substrate surface is oxidized after removing the organic matter on the substrate surface, so that an oxide film can be formed on the substrate surface to which no organic matter is attached. It is possible to improve the adhesion between the oxide film and the vapor deposition film. Further, since the substrate oxidizing gas and the raw material oxidizing gas are ejected from one gas nozzle, the number of gas nozzles can be halved and the cost can be reduced. Further, since the amount of gas introduced can be small, the pressure in the vacuum vessel can be reduced, and more stable film formation can be realized.

(Fourth embodiment)
FIG. 6 is a cross-sectional view schematically showing a thin film manufacturing apparatus 103 according to the fourth embodiment of the present invention. Hereinafter, differences from the thin film manufacturing apparatus 100 will be described.

  In the thin film manufacturing apparatus 103, there is only one vapor deposition source, which is represented by reference numeral 3. The vapor deposition source 3 and the cooling can rolls 6a and 6b are arranged so that the vapor deposition raw material evaporated from the vapor deposition source 3 reaches the surfaces of the two cooling can rolls. The two cooling can rolls are arranged at a shorter interval, and the lamp 40 and the substrate oxidation and raw material oxidation gas nozzles 41 are arranged in this order in the substrate conveyance path. The gas nozzle 41 is the same as the substrate oxidation and raw material oxidation gas nozzles 31a and 31b except that the gas nozzle 41 is configured to eject gas to both of the two cooling can rolls. The lamp 40 is the same as the lamps 5a and 5b except that the lamp 40 is configured to irradiate light to both of the two cooling can rolls. A shielding plate 10 is disposed between the lamp 40 and the gas nozzle 41 and the vapor deposition source 3, and two openings are provided by the shielding plate 10 and the mask 11a or 11b. The vapor deposition material evaporated from the vapor deposition source 3 passes through the opening, and deposits on the surface of the substrate held by the cooling can roll to form a vapor deposition film. These openings are arranged obliquely with respect to the horizontal direction along the cooling can rolls 6a and 6b.

  In the fourth embodiment, as in the third embodiment, one gas nozzle supplies an ozone-containing gas that is used for both the oxidation of the substrate surface and the oxidation of the deposition material, but one gas nozzle is provided for two cooling can rolls. By supplying gas from the gas nozzle, substrate oxidation and oxidation of the deposited film are achieved on both surfaces of the substrate with one gas nozzle. In addition, since one lamp irradiates two cooling can rolls, substrate oxidation on both sides of the substrate is achieved with one lamp. Moreover, formation of a vapor deposition film is achieved on both surfaces of a substrate with one vapor deposition source. As described above, it is possible to reduce the size of the vacuum container and realize cost reduction.

  The thin film production apparatus of the present invention can be suitably used in a method of forming a thin film by evaporating a deposition material from a deposition source in a vacuum and attaching it to a substrate surface, such as a deposition method, a sputtering method, or a CVD method. . In particular, since the gas pressure in the vacuum container can be kept low, it can be suitably used in a thin film forming method using an electron beam. Thereby, various devices including a deposited film, for example, electrochemical devices such as batteries, optical devices such as photonic elements or optical circuit components, device elements such as sensors, and the like can be manufactured. According to the present invention, since the deposited film is formed after oxidizing the substrate surface, the reaction at the interface between the current collector and the Si thin film, particularly when the Si thin film is formed on the current collector made of copper, and It is possible to suppress diffusion and avoid a decrease in charge / discharge characteristics of the active material layer.

DESCRIPTION OF SYMBOLS 100, 101, 102, 103 Thin film manufacturing apparatus 1 Vacuum container 2 Exhaust pump 3a, 3b Deposition source 4 Substrate 5a, 5b Lamp 6a, 6b Cooling can roll 7, 9 roll 8 Conveyance roll 10 Shielding plate 11a, 11b Mask 12a, 12b Raw material oxidation gas nozzle 13 Shutter 14a, 14b Oxidizable region 15a, 15b Deposition possible region 17a, 17b Substrate oxidation gas nozzle 30a, 30b Organic substance decomposition lamps 31a, 31b, 41 Substrate oxidation and raw material oxidation gas nozzle 40 Lamp

Claims (6)

A thin film manufacturing apparatus for forming a thin film on a surface of a belt-like substrate having a front surface and a back surface in a vacuum,
A transport mechanism for transporting the substrate;
A thin film forming means for forming a thin film in the first thin film forming region on the surface of the substrate held by the transport mechanism, and is disposed opposite to the first thin film forming region. Thin film forming means including a vapor deposition source containing
A first gas nozzle that is disposed in front of the first thin film formation region in the transport path of the substrate and supplies an ozone-containing gas toward the surface of the substrate;
A thin film manufacturing apparatus comprising: the transport mechanism; the thin film forming means; and a vacuum container that houses the first gas nozzle.   The thin film manufacturing apparatus according to claim 1, wherein the thin film is a thin film made of an oxide.   The substrate oxidation promoting portion that is disposed in the vicinity of the surface of the substrate in a region to which the ozone-containing gas is supplied by the first gas nozzle and further promotes oxidation of the surface by the ozone-containing gas. The thin film manufacturing apparatus described.   The thin film manufacturing apparatus according to claim 3, wherein the substrate oxidation accelerating unit is an ultraviolet irradiation unit that irradiates the surface of the substrate with ultraviolet rays in a region to which an ozone-containing gas is supplied by the first gas nozzle. An inversion structure that is disposed after the first thin film formation region in the substrate transport path, and reverses the substrate so that the back surface faces the vapor deposition source.
A second gas nozzle that is disposed after the reversal structure in the transport path of the substrate and supplies an ozone-containing gas toward the back surface of the substrate;
The thin film manufacturing apparatus according to any one of claims 1 to 4, wherein a thin film is formed on the back surface of the substrate in a second thin film formation region set after the second gas nozzle in the transport path of the substrate. A thin film manufacturing method using a thin film manufacturing apparatus for forming a thin film on the surface of a belt-like substrate having a front surface and a back surface in a vacuum, wherein the thin film manufacturing apparatus includes:
A transport mechanism for transporting the substrate;
A thin film forming means for forming a thin film in the first thin film forming region on the surface of the substrate held by the transport mechanism, and is disposed opposite to the first thin film forming region. Thin film forming means including a vapor deposition source containing
A first gas nozzle that is disposed in front of the first thin film formation region in the transport path of the substrate and supplies an ozone-containing gas toward the surface of the substrate;
A vacuum vessel that houses the transport mechanism, the thin film forming means, and the first gas nozzle;
The method includes supplying the ozone-containing gas from the first gas nozzle toward the surface of the substrate and oxidizing the surface by irradiating ultraviolet rays.
Allowing the evaporated deposition material to enter the oxidized surface to form a thin film in the first thin film formation region; and
A method for producing a thin film.