JPWO2017014092A1 - Atomic layer deposition winding film forming apparatus and atomic layer deposition method - Google Patents

Abstract

The atomic layer deposition winding film forming apparatus unwinds the base material and the transport auxiliary material, respectively, and forms a film forming member in which the transport auxiliary material is detachably stacked on one surface of the base material. An unwinding device configured to deliver a film forming member; a first vacuum chamber into which a first precursor gas is introduced; a second vacuum chamber into which a second precursor gas is introduced; A third vacuum chamber provided between the one vacuum chamber and the second vacuum chamber, into which purge gas is introduced, and a holding unit that holds both ends in the width direction of the film forming member; A transport mechanism for transporting the film forming member to the first vacuum chamber, the second vacuum chamber, and the third vacuum chamber, and the base material of the film forming member sent out from the transport mechanism A take-up device that winds up the film-forming member by means of the transport mechanism. A plurality of times by passing alternately the second vacuum air chamber, wherein forming the other surface is deposited atomic layer by atomic layer deposition film of the substrate in the deposition target member.

Description

The present invention relates to an atomic layer deposition winding film forming apparatus and atomic layer deposition method using an atomic layer deposition method in which an atomic layer is continuously deposited on the surface of a flexible base material that can be wound. About.
This application claims priority based on Japanese Patent Application No. 2015-143154 filed in Japan on July 17, 2015 and Japanese Patent Application No. 2015-252575 filed in Japan on December 24, 2015. Is hereby incorporated by reference.

There is a technique of rewinding a long rollable base material such as paper or plastic film in a vacuum and continuously forming a metal or metal oxide film by a film forming method such as vapor deposition or sputtering. This technique is used as a method for producing an optical film such as a metallic luster film used for gold and silver thread, a gas barrier film for food packaging, an electrode of a film capacitor, and antireflection. In recent years, a gas barrier with a water vapor transmission rate of 10 ⁻⁶ [g / (m ² · day)] has been developed for the development of flexible organic EL displays, organic EL lighting, and organic solar cells using organic semiconductors. There is a growing demand for commercialization of transparent gas barrier films having a thickness of about 10 μm including the substrate film.

In order to meet this demand, a winding device using an atomic layer deposition method has been studied.
The atomic layer deposition method is known as a method for forming a dense thin film. From the viewpoint of the superiority of the characteristics of the atomic layer deposition method, the atomic layer deposition method is used when forming an insulating film in a DRAM or a TFT.
Conventionally, the thin film deposition process is performed by batch processing. In order to improve productivity, an apparatus and technology developed for simultaneously processing a plurality of Si wafers are used. However, its productivity is limited. Moreover, in these batch processing apparatuses, it is not possible to continuously form a film on a rollable substrate.
In order to solve this problem, devices disclosed in Patent Documents 1 and 2 have been proposed.

Patent Documents 1 and 2 disclose techniques for continuously forming a thin film by an atomic layer deposition method.
In the step of depositing the atomic layer, the first precursor is adsorbed on the surface of the substrate, the excess first precursor is purged, and the first precursor is exposed to the second precursor. The cycle of the atomic layer deposition step including the step of reacting the body with the second precursor and the step of purging excess second precursor is repeated a plurality of times. Thereby, a thin film with a desired film thickness can be obtained.
In addition, as a precursor, the material of a nonpatent literature 1 can be used, for example.

In general, in one cycle of atomic layer deposition, a layer having a thickness of about 0.01 nm to 0.2 nm, and on average, about 0.1 nm is formed.
The desired film thickness varies depending on the application. In order to obtain a water vapor permeable high barrier film of 10 ⁻⁶ [g / (m ² · day)] or less, it is generally known that aluminum oxide requires 10 nm or more.
Therefore, in order to obtain an aluminum oxide layer having a thickness of 10 nm, it is necessary to perform 100 general atomic layer deposition cycles.

On the other hand, Patent Document 3 discloses a take-up atomic layer deposition apparatus using a rotating drum. In this apparatus, an atomic layer is deposited on a substrate while the substrate is positioned on a rotating drum.
Patent Document 4 discloses a take-up atomic layer deposition apparatus using a spray manifold. In this apparatus, an atomic layer is deposited on a substrate as the substrate passes in the vicinity of the spray manifold.

  Furthermore, an apparatus described in Patent Document 5 has been proposed. In this apparatus, the portions other than the holding portions at both ends of the base material are not in contact with the base material, and a stable atomic layer volume film can be continuously processed on the rollable base material.

  Moreover, as described in Patent Document 6, there is known an apparatus that is adapted to reduce the buckling of a base material.

International Publication No. 07/112370 Japan Special Table 2009-540122 Japan Special Table 2007-522344 Japan Special Table 2009-53548 Japanese Patent No. 5206908 International Publication No. 13/180005

M. Ritara (M. Ritala et al., “Atomic Layer Deposition”, Handbook of Tin Film Materials, United States, Academic Press, 2002, 1st) Volume, Chapter 2, pages 103-159

However, in the apparatuses described in Patent Documents 1 and 2, in order to obtain an atomic layer deposition film having a thickness of 10 nm, the substrate must pass through 100 sets of guide rollers. That is, the atomic layer deposition film contacts the guide roller 100 times. There is a risk of damage to the atomic layer deposition film or generation of particles due to rubbing or slipping due to contact between the atomic layer deposition film and the guide roller.
In addition, damage or particles may adhere to the atomic layer deposition film, which may degrade the performance of the atomic layer deposition film.

The performance required for conventional gas barrier films for food packaging is about 10 ⁻¹ [g / (m ² · day)] in terms of water vapor transmission rate, and small defects (scratches, pinholes, particle adhesion, etc.) are problematic. Must not.
However, high performance, for example, water vapor transmission rate of 10 ⁻⁶ [g / (m ² · day)] or less is required for organic EL displays and polymer solar cells, and for organic semiconductors. Yes. Therefore, even if a small defect occurs in the device, there is a risk of unacceptable performance degradation.

Paragraph 0007 of Patent Document 1 describes a transport mechanism. However, it is only disclosed that a guide that uses a roller and can support the base material at least when the conveyance direction of the base material is changed (turned) is desirable.
Paragraph 0030 also discloses a transport mechanism, but the use of a roller is only disclosed as the transport mechanism.

On the other hand, in Patent Document 2, regarding the conveyance method, “the contact between the roller 22 and the base material 20 should be kept to a minimum. It can be achieved by placing it on the diameter portion "(paragraph 0013).
However, when the thickness of the base material is thin and the rigidity is low, the base material may contact not only the portion having a large diameter but also the entire spool shape.
When the atomic layer deposition film touches the guide roller, defects such as minute pinholes are generated in the atomic layer deposition film and the intended performance cannot be obtained.
In particular, in the case of using a low-rigidity substrate such as a thin plastic film substrate or cloth, contact between the roller and the substrate cannot be prevented.

  In addition to the above disclosure, Patent Document 2 also discloses that “a gripping tool for holding the base material 20 as the base material 20 is wound around each roller 22 may be provided at the edge of the roller 22. (Paragraph 0013). However, there is no detailed disclosure regarding a gripping tool, a method of attaching to a roller edge, and a transport mechanism.

  Moreover, in the apparatus disclosed in Patent Document 3, an atomic layer is not deposited on the surface of the base material in contact with the rotating drum. Moreover, in the apparatus disclosed in Patent Document 4, an atomic layer is not deposited on the surface of the base material that is not exposed to the spray manifold. For this reason, Patent Documents 3 and 4 include damage to the atomic layer deposition film caused by the contact between the guide roller and the base material during the processing process, and a gas barrier caused by the damage, which is caused by using the apparatus described in Patent Documents 1 and 2. There is no suggestion about issues such as performance degradation.

  And the apparatus disclosed by patent document 5 is not contacting with respect to a base material except the holding part of both ends of a base material, and performs the continuous process of the stable atomic layer volume film | membrane to the base material which can be wound up. Is possible. In this apparatus, when the conveyance base material tension is increased in order to perform stable running of the base material, a wrinkle is formed in the central portion of the base material (a non-contact portion with a roller or the like) in the folded portion (end holding portion) of the base material. Buckling occurs. These generated tensions depend on the thickness of the substrate or the length in the width direction. That is, it is likely to occur on the low tension side when the substrate is thin or the width dimension is long. Due to the occurrence of buckling such as wrinkles and breakage, the gas barrier property of the substrate may be lowered.

  Furthermore, Patent Document 6 discloses that measures to reduce the buckling of the base material are achieved. However, when the substrate is thin, specifically, when the thickness of the plastic film is less than about 50 μm, the countermeasure is insufficient and buckling may occur.

The present invention has been made in view of the above problems, and performs a process of continuously forming an atomic layer deposited film on a rollable substrate without contact between the guide roller and the substrate. It is an object of the present invention to provide an atomic layer deposition winding film forming apparatus capable of performing the above.
In the present invention, the guide roller and the base material are not in contact with each other except for the both end portions of the base material that are held, and the base material slip at the both end portions of the base material is prevented by the suction type transport mechanism. . Accordingly, an object of the present invention is to provide an atomic layer deposition winding film forming apparatus capable of performing a process of continuously forming an atomic layer deposition film stably on a rollable substrate.
The suction type described above refers to a method in which a plurality of holes are formed on the roller surface, and the film substrate is adsorbed on the roller surface by sucking the substrate through the holes.

  In addition, the present invention can perform a process of continuously forming an atomic layer deposition film on a substrate without contacting the guide roller except for holding portions at both ends in the width direction of the substrate. Another object of the present invention is to provide an atomic layer deposition method winding film forming apparatus and an atomic layer deposition method winding film forming method capable of preventing the atomic layer deposition film from being damaged. In addition, the present invention provides an atomic layer deposition film laminate structure that can suppress buckling such as wrinkling and folding at the center of the base of the guide roller, which occurs remarkably on a thin base or a wide base. It is an object of the present invention to provide a film apparatus and an atomic layer deposition film laminate film forming method.

  In order to solve the above problems, in the present invention, in order to prevent the dense atomic layer deposition film from being damaged by the transport of the substrate, the film formation surface is not in contact with the guide roller, and the transport auxiliary material And the substrate is transported to form a film in a stable state in which no buckling such as wrinkles or creases occur in the substrate during transportation as compared with the conventional case.

  In order to solve the above problems, in the present invention, guides other than the holding portions at both ends in the width direction of the base material are used so that the dense atomic layer deposition film is not damaged by the transport of the base material. By transporting the substrate with the film forming surface not in contact with the roller and pasting it with the conveyance auxiliary material, stable conveyance that does not cause buckling such as wrinkling or bending of the substrate at the time of conveyance is achieved. To do. Furthermore, in the present invention, by using a slightly adhesive film for the conveyance auxiliary material for bonding the base material and the conveyance auxiliary material, it is possible to easily peel the conveyance auxiliary material from the substrate, and Enable reuse.

The atomic layer deposition winding film forming apparatus according to the first aspect of the present invention unwinds a base material and a transport auxiliary material, and the transport auxiliary material is peelably laminated on one surface of the base material. An unwinding device configured to form a film forming member and deliver the film forming member; a first vacuum chamber into which the first precursor gas is introduced; and a first vacuum gas into which the second precursor gas is introduced. Two vacuum chambers, a third vacuum chamber provided between the first vacuum chamber and the second vacuum chamber, into which purge gas is introduced, and both widthwise ends of the film forming member are held. A holding mechanism that transfers the film-forming member to the first vacuum chamber, the second vacuum chamber, and the third vacuum chamber; A winding device that winds up the substrate of the film forming member, and the film forming member is formed by the transport mechanism. By passing a plurality of times alternately said first vacuum air chamber and the second vacuum air chamber, wherein forming the other surface is deposited atomic layer by atomic layer deposition film of the substrate in the film forming member.
In the first aspect, the holding unit includes a roller that sandwiches both end portions in the width direction of the film forming member from the front surface and the back surface of the film forming member, and the roller includes a guide roller; The film forming member may include a nip roller that nips the film forming member with the guide roller.
Said 1st aspect WHEREIN: The said winding apparatus may be comprised so that the said base material may be wound up after peeling the said conveyance auxiliary material from the said film-forming member.
Said 1st aspect WHEREIN: Even if the said conveyance auxiliary material laminated | stacked on the said base material so that peeling is possible, it has the adhesive force of the range of 0.001N / 25mm-5N / 25mm in the surface laminated | stacked with the said base material. Good.
In the first aspect, the take-up device peels off the conveyance auxiliary material, and the unwinding device again laminates the peeled conveyance auxiliary material on one surface of the base material before film formation. It may be reused as a conveyance auxiliary material.
In the first aspect, the winding device may be configured to wind up the film forming member.
In the first aspect, the guide roller and the nip roller may be independently arranged in any one of the first vacuum chamber, the second vacuum chamber, and the third vacuum chamber. .
The atomic layer deposition method according to the second aspect of the present invention is an atomic layer deposition method in which an elongated base material is conveyed and an atomic layer deposition film is continuously formed on the base material. A conveyance auxiliary material is peelably laminated on one surface of the substrate to form a film forming member with respect to the material conveying direction, and the film forming member is conveyed, and on the other surface of the substrate An atomic layer is deposited to form an atomic layer deposited film, the transport auxiliary material is peeled off from the deposition target member after the atomic layer volume film is deposited, and the atomic layer deposited film stack is taken out.
In the second aspect, the peeled conveyance auxiliary material may be reused for forming the film forming member that is laminated on one surface of the base material.
Said 2nd aspect WHEREIN: Even if the said conveyance auxiliary material laminated | stacked on the said base material so that peeling is possible, it has the adhesive force of the range of 0.001N / 25mm-5N / 25mm in the surface laminated | stacked with the said base material. Good.
In the second aspect, an atomic layer deposition film may be formed on the base material that is thinner than the transport auxiliary material before lamination.

The atomic layer deposition winding film forming apparatus according to the above aspect of the present invention has no contact between the substrate and the guide roller except for the holding portions at both ends of the substrate. Therefore, there is no fear of damage due to contact with the guide roller in the atomic layer deposition film formed on the substrate surface. Further, the guide roller and the base material do not come into contact with each other except for the both end portions of the base material, which are held portions. Therefore, there is no fear of damage to the atomic layer deposition film formed on the substrate surface.
Therefore, by using the winding film forming apparatus according to the above aspect of the present invention, an atomic layer deposited film without mechanical damage can be continuously formed.

In addition, it is possible to suppress wrinkles and breakage at the center position in the width direction of the film forming member in the guide roller by transporting the base material while being bonded to the transport auxiliary material.
Therefore, by using the atomic layer deposition winding film forming apparatus according to the above aspect of the present invention, it is possible to continuously form an atomic layer deposition film without mechanical damage and by stable and clean conveyance. .

  Moreover, according to the said aspect of this invention, since it is not in contact with a guide roller except the holding | maintenance part of the both ends of the width direction of a base material, there is no possibility of damage to the atomic layer deposited film formed on the base-material surface. In addition, according to the above aspect of the present invention, it is possible to suppress buckling such as wrinkling and bending at the center side of the guide roller (non-contacting portion of the guide roller) that occurs remarkably on a thin base or a wide base. Therefore, when the substrate and the conveyance auxiliary material are bonded and conveyed, the atomic layer deposition film can be continuously formed by stable conveyance without mechanical damage.

1 is a schematic plan view showing an atomic layer deposition winding film forming apparatus according to a first embodiment of the present invention. 1 is a perspective view of a nip roller type nipping and conveying mechanism in an atomic layer deposition winding film forming apparatus according to a first embodiment of the present invention. 1 is a plan view in the axial direction of a nip roller type nipping and conveying mechanism in an atomic layer deposition winding film forming apparatus according to a first embodiment of the present invention. It is a front view of the nip roller type nipping / conveying mechanism in the atomic layer deposition winding film forming apparatus according to the first embodiment of the present invention. It is a side view of the nip roller type nipping and conveying mechanism in the atomic layer deposition winding film forming apparatus according to the first embodiment of the present invention. It is a perspective view of the guide rail in the atomic layer deposition winding film-forming apparatus concerning 1st Embodiment of this invention. It is sectional drawing of the guide rail in the atomic layer deposition winding film-forming apparatus which concerns on 1st Embodiment of this invention. It is a schematic plan view which shows the atomic layer deposition winding film-forming apparatus which concerns on 2nd Embodiment of this invention.

  An atomic layer deposition winding film forming apparatus according to an embodiment of the present invention unwinds a substrate and a conveyance auxiliary material (sheet), and the conveyance auxiliary material is detachably laminated on one surface of the substrate. An unwinding device configured to form a film forming member and to deliver the film forming member, a first vacuum chamber into which the first precursor gas is introduced, and a second precursor gas are introduced. A second vacuum chamber, a third vacuum chamber provided between the first vacuum chamber and the second vacuum chamber, into which purge gas is introduced, and both end portions in the width direction of the film forming member A transfer mechanism for transferring the film-forming member to the first vacuum chamber, the second vacuum chamber, and the third vacuum chamber; And a winding device for winding the base material of the film-forming member, and the transport mechanism An atomic layer deposition film is formed by allowing a film forming member to pass through the first vacuum chamber and the second vacuum chamber alternately a plurality of times, and depositing an atomic layer on the other surface of the substrate in the film forming member. Form. Thus, by attaching the conveyance auxiliary material, it is possible to stably convey the substrate surface, which is a film formation surface, without causing buckling such as wrinkles or bending. Furthermore, an atomic layer deposition film having a required characteristic can be formed uniformly and an atomic layer deposition film having a necessary barrier characteristic without a pinhole or the like can be stably formed on a substrate.

  The atomic layer deposition winding film forming apparatus according to this embodiment includes at least a first vacuum chamber into which a first precursor is introduced, a second vacuum chamber into which a second precursor is introduced, and an excess first A third vacuum chamber into which a purge gas used for discharging the precursor and the second precursor is introduced; and a transport mechanism for transporting the substrate through each vacuum chamber. Specifically, this transport mechanism includes a mechanism for unwinding a long (web) substrate, a mechanism for bonding the unwound substrate and a transport auxiliary material serving as a carrier, and a substrate winding A take-off mechanism and a mechanism that peels off the conveyance auxiliary material immediately before the take-up mechanism. In this manner, by attaching the conveyance auxiliary material to the base material, it is possible to stably convey the base material surface, which is a film formation surface, without causing buckling such as wrinkles or bending. Thereby, an atomic layer deposition film having uniform and necessary characteristics can be formed, and an atomic layer deposition film having necessary barrier characteristics without a pinhole or the like can be stably formed on a substrate.

  Specifically, this transport mechanism is a transport mechanism that can pinch or support both ends in the width direction of a rollable substrate. By using this transport mechanism, the surface of the rollable substrate that is coated in the film formation process can pass through each of the vacuum chambers in sequence without touching the mechanical parts arranged in the apparatus. it can. Therefore, it is possible to form a film in a stable state in which no buckling such as wrinkles or bending occurs on the base material during transportation, and an atomic layer deposition film without mechanical damage is formed.

  By using this transport mechanism, the base material can be prevented from being wrinkled or broken due to buckling of the base material to be coated in the course of film formation. In addition, the surface of the base material can sequentially pass through each of the vacuum chambers without touching the mechanical parts arranged in the apparatus, preventing mechanical damage and preventing unstable conveyance, A high-quality atomic layer deposition film is formed.

  In the atomic layer deposition winding film forming apparatus according to an embodiment of the present invention, the holding unit includes a roller that holds both ends in the width direction of the film forming member from the front surface and the back surface of the film forming member. And the roller includes a guide roller and a nip roller for nipping the film forming member between the guide roller and the guide roller. Thus, both end portions in the width direction of the base material can be clamped and transported while being pulled outward in the width direction. Thereby, it becomes possible to convey the substrate in a stable state in which no buckling such as wrinkling or bending occurs. Thereby, stable film formation can be performed.

  In the atomic layer deposition winding film forming apparatus according to an embodiment of the present invention, the winding apparatus is configured to wind up the base material after peeling the transport auxiliary material from the film forming member. This makes it possible to transport a base material that does not buckle, such as wrinkles or folds, in a stable state without causing any buckling, such as wrinkles or folds, in the base material without a conveyance auxiliary material. Become. Thereby, stable film formation can be performed.

  In the atomic layer deposition winding film forming apparatus according to the embodiment of the present invention, the winding apparatus is configured to wind up the film forming member. Thereby, an atomic layer deposition film can be stably formed on a substrate.

  An atomic layer deposition method according to an embodiment of the present invention forms an atomic layer deposition film on the substrate using an atomic layer deposition winding film forming apparatus according to an embodiment of the present invention.

  In the atomic layer deposition method according to an embodiment of the present invention, an atomic layer deposition film is formed on the base material that is thinner than the transport auxiliary material before lamination. Thereby, even if it is a thin base material, it becomes possible to stably form an atomic layer deposition film having necessary characteristics in a stable state in which no buckling such as wrinkles or bending occurs.

Hereinafter, an atomic layer deposition winding film forming apparatus according to a first embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a perspective view showing an atomic layer deposition winding film forming apparatus according to this embodiment. In the figure, reference numeral 100 denotes an atomic layer deposition winding film forming apparatus.
The embodiments of the present invention are not limited to the embodiments described below, and modifications such as design changes can be added based on the knowledge of those skilled in the art. The described embodiments are also included in the scope of the embodiments of the present invention.

  As shown in FIG. 1, the atomic layer deposition winding film forming apparatus 100 according to this embodiment includes a first zone 201, a second zone 202, a third zone 203, and an unwinding chamber (unwinding apparatus) 103. And a winding chamber (winding device) 104. The first zone 201 is a first vacuum chamber into which the first precursor gas is introduced. The second zone 202 is a second vacuum chamber into which the second precursor gas is introduced. The third zone 203 is a third vacuum chamber into which purge gas is introduced.

  The atomic layer deposition winding film forming apparatus 100 includes an unwinding roller 101, a winding roller 102, and guide rollers (holding units) 401a, 401b, and 401c. The unwinding roller 101 unwinds a long (web) -shaped base material 105 that is installed in the unwinding chamber 103. The take-up roller 102 takes up the take-up base material 105 installed in the take-up chamber 104. The guide rollers (holding units) 401 a, 401 b, and 401 c convey the laminated and rollable base material (laminate base material) 115 between the unwinding roller 101 and the winding roller 102.

  Further, a laminating base roller 111 and a laminating roller 503 are provided in the unwind chamber 103. The laminating substrate roller 111 unwinds a carrier laminating substrate (conveying auxiliary material) 113 to be bonded to the rewoundable substrate 105 unwound from the unwinding roller 101 in the conveying direction of the substrate 105. . The laminating roller 503 bonds the rollable base material 105 and the carrier laminating base material (conveying auxiliary material) 113 to form a laminated rollable base material (film forming member) 115.

  In the winding chamber 104, a delaminating roller 504 and a delaminating substrate roller 112 are provided. The delaminating roller 504 peels the carrier laminating base material 113 from the laminated base material 115 that can be taken up immediately before the winding roller 102. The delaminating substrate roller 112 winds up the carrier laminating substrate (conveying auxiliary material) 113 peeled from the laminated and rollable substrate 115.

The guide rollers (holding portions) 401a, 401b, 401c are provided with nip rollers (holding portions) 502a, 502b, 502c that nip the base material 105 together with the guide rollers 401a, 401b, 401c.
Note that the nip rollers 502a, 502b, and 502c can be appropriately removed depending on the state of conveyance of the laminated and rollable substrate 115.

  The nip rollers 502a, 502b, and 502c in the present embodiment are nip roller type configured to convey the both ends of the laminated rollable substrate 115 in the width direction together with the guide rollers 401a, 401b, and 401c while nipping. It is a clamping conveyance mechanism.

The atomic layer deposition winding film forming apparatus 100 according to the present embodiment uses a nip roller type nipping / conveying mechanism (conveying mechanism) 401a, 401b, 401c, 502a, 502b, 502c to apply a third substrate 115 that can be rolled up to a third state. The zone 203, the first zone 201, the third zone 203, the second zone 022 and the third zone 203 are passed in this order. Thereby, one atomic layer is deposited on the substrate. The nip roller type nipping / conveying mechanisms (conveying mechanisms) 401a and 502a are disposed only in the first zone. The nip roller type nipping / conveying mechanisms (conveying mechanisms) 401b and 502b are disposed only in the second zone. The nip roller type nipping / conveying mechanisms (conveying mechanisms) 401c and 502c are disposed only in the third zone.
The atomic layer deposition winding film forming apparatus 100 continuously deposits an atomic layer on the surface of the laminated rollable substrate 115. For this reason, the transport mechanisms 401a, 401b, 401c, 502a, 502b, and 502c are provided so that the atomic layers can be deposited on the surface of the substrate 115 laminated with the number of cycles necessary to obtain a desired film thickness. The film forming apparatus is designed so that the number of times the substrate passes through the above-described zone is a predetermined number.

  The rollable substrate 105 used in the present embodiment is selected from flexible materials such as a plastic film, a plastic sheet, a metal foil, a metal sheet, paper, and a nonwoven fabric. Although the thickness of the base material 105 which can be wound up is not specifically limited, the base material which has a thickness of 10 micrometers or more and 1000 micrometers or less can be used.

  Although it does not specifically limit as a material of a plastic film or a plastic sheet, For example, a polyethylene terephthalate (PET) etc. are mentioned.

A carrier laminate base material (conveyance auxiliary material) 113 used in the present embodiment is formed of a flexible material such as a plastic film or a plastic sheet, and can be bonded to a rollable base material 105. If it is a material, it will not specifically limit.
The thickness of the carrier laminate substrate (conveying auxiliary material) 113 is not particularly limited, but a substrate having a thickness of 10 μm or more and 1000 μm or less can be used.
Moreover, the thickness of the base material 105 which can be wound may be smaller than the thickness of the laminate base material 113 for carriers.

  The conveyance auxiliary material 113 used in the present embodiment is not particularly limited as long as it is a flexible base material such as a plastic film or a plastic sheet and can be bonded to the base material 105. As the conveyance auxiliary material 113, for example, the flexible base material is formed on the one surface (the surface to be bonded to the base material 105) and has an adhesive having an adhesive force that can be bonded to the base material 105. What has an adhesion layer is used. Alternatively, as the conveyance assisting material 113, for example, a base material having flexibility and an adhesive force that can be bonded to the base material 105 is used.

  The adhesive force of the conveyance auxiliary material 113 to the base material 105, that is, the adhesive force on the surface of the conveyance auxiliary material 113 laminated with the base material 105 is preferably 0.001 N / 25 mm to 5 N / 25 mm, and 0.05 N / More preferably, it is 25 mm to 0.50 N / 25 mm. For example, when the base material 105 is a base material made of polyethylene terephthalate (PET), the adhesive strength of the conveyance auxiliary material 113 to the base material 105 is preferably 0.001 N / 25 mm to 5 N / 25 mm. More preferably, it is 005 N / 25 mm to 3 N / 25 mm.

The rollable base material 105 unwound from the unwinding roller 101 and the carrier laminating base material (conveying auxiliary material) 113 unwound from the laminating substrate roller 111 are laminated in the unwinding chamber 103. 503 is bonded together. Thereafter, the laminated rollable substrate 115 is conveyed to the third zone 203.
A partition plate 103 a is installed between the unwind chamber 103 where the laminating roller 503 is installed and the third zone 203. The partition plate 103a is provided with an opening 106 necessary for the laminated rollable substrate 115 to pass therethrough.
The laminated base material 115 that can be wound up is conveyed from the unwind chamber 103 to the third zone 203 through the opening 106.

  The transport mechanisms 401 a, 401 b, 401 c, 502 a, 502 b, and 502 c have a predetermined tension applied to the laminated roll-up base material 115 so that the laminated roll-up base material 115 does not contact the opening 106. (Tension) is set to convey.

  An inert gas is introduced into the third zone 203 as a purge gas (see reference numeral 303, the flow of purge gas). As the inert gas, a gas appropriately selected from nitrogen, helium, argon and the like is used.

  In the third zone 203, the laminated rollable substrate 115 is sandwiched (nip) and guided by the guide roller 401 c and the nip roller 502 c in order to hold only both ends in the width direction. Even in 203, stable conveyance is maintained.

  Here, the nip roller type nipping and conveying mechanism in the present embodiment will be described.

2 to 5 show configuration examples of the nip roller type nipping and conveying mechanism 501 in the atomic layer deposition winding film forming apparatus 100 of the present embodiment. FIG. 2 is a perspective view of the nip roller type nipping / conveying mechanism 501. 3 and 4 are cross-sectional views of the nip roller type nipping and conveying mechanism. FIG. 5 is a plan view of the nip roller type nipping and conveying mechanism 501.
The nip roller type nipping and conveying mechanism 501 according to the present embodiment applies tension to the laminated base material 115 that can be wound. That is, the laminate base material 115 is pulled along the transport direction. Thereby, the slack of the laminate base material 115 is corrected, or the meandering is corrected. By using a nip roller type nipping and conveying mechanism 501 as shown in FIGS. 2 to 4, a greater effect can be obtained.

As shown in FIG. 4, the nip roller type nipping / conveying mechanism 501 includes two rollers 401 and 502 that sandwich the front and back surfaces of both end portions in the width direction of the laminate base material 115.
In the nip roller type nipping / conveying mechanism 501, the front and back surfaces of both ends in the width direction of the laminate base material 115 are sandwiched by two different rollers, and the laminate base material 115 is held by driving one or both rollers. Then, the laminate base material 115 is conveyed.

  The laminate base material (substrate film forming member) 115 is held by being nipped by the guide roller 401 and the nip roller 502. The held laminate base material 115 is stretched in the width direction with an appropriate tension by changing the rotation axis of the guide roller 401 or the nip roller 502, and is not loosened during conveyance but is substantially held in a flat shape.

  The nip roller type nipping and conveying mechanism 501 has a structure in which a nip roller 502 for the purpose of a nip is provided on a guide roller 401. Using this nip roller type nipping / conveying mechanism 501, the front and back surfaces of both ends in the width direction of the laminate base material 115 are sandwiched, and power is transmitted to the laminate base material 115 at the same time.

In other words, the nip roller type nipping / conveying mechanism 501 sandwiches the substrate with a plurality of rollers installed on the front and back surfaces of the substrate, and at least one of the rollers installed on the front and back surfaces (for example, the guide roller 401). Is configured to have a drive mechanism.
Specifically, the rotation axis direction of the nip roller 502 (first roller) is arranged to be inclined with respect to the rotation axis direction of the guide roller 401 (second roller).
In such a nip roller type nipping / conveying mechanism 501, the diameter of the nip roller 502 is preferably smaller than the diameter of the guide roller 402 as shown in FIG. 4.

  The correction of the slackness of the laminate substrate 115 or the correction of the meandering is controlled by adjusting the pressure with which the nip roller 502 presses the guide roller 401, the direction of the nip roller 502, and the direction of the guide roller 402. Thereby, the stable driving | running | working (conveyance of a base material) in the lamination base material 115 is realizable.

  The material of the guide roller 401 and the nip roller 502 is a material that can hold both ends in the width direction of the laminate base material 115 and can be conveyed while maintaining an appropriate frictional force necessary for the conveyance with the laminate base material 115. If it is, it will not be specifically limited.

  The laminate winding base material 115 held by the guide roller 401 and the nip roller 502 is conveyed to the first zone 201 through the opening 107 a provided in the partition wall between the third zone 203 and the first zone 201. The

Since the first precursor is introduced into the first zone 201 (see reference numeral 301), the first precursor is applied to both surfaces of the laminate base 115 when the laminate base 115 passes through the first zone 201. Adsorb.
During this time, only the both ends in the width direction of the laminate base material 115 are held by the guide roller 401a and the nip roller 502a. Therefore, both surfaces (film formation surfaces) of the laminate base material 115 on which the first precursor is adsorbed do not touch the mechanical parts arranged in the apparatus.

The material constituting the first precursor is appropriately selected according to the target deposition material.
For example, when the material deposited on the substrate 105 (target deposition material) is aluminum oxide, trimethylaluminum is used.
In addition, as a material of the 1st precursor used, the material shown by the nonpatent literature 1 can be used, for example.

The conveyance speed of the laminate base material 115 in the first zone 201 is calculated from the saturation adsorption time and the passage distance so that the time for the laminate base material 115 to pass through the first zone 201 is longer than the saturation adsorption time. The saturated adsorption time is a time until the amount of the first precursor adsorbed on the film forming surface of the laminate base 115 is saturated.
In addition, the tension during the conveyance of the laminate base material 115 is appropriately set so that the laminate base material 115 does not come into contact with the openings 106, 107a, and 107b.

The laminate base material 115 in which the first precursor is saturated and adsorbed in the first zone 201 is passed through another opening 107a provided in the partition wall disposed between the first zone 201 and the third zone 203. It is conveyed again to the third zone 203.
The gas in the first zone 201 is exhausted by an exhaust mechanism (reference numeral 304a) connected to the first zone. By using this exhaust mechanism, the pressure in the first zone 201 is maintained. The pressure in the third zone 203 is kept higher than the pressure in the first zone 201.
Therefore, the first precursor introduced into the first zone 201 is maintained under conditions that make it difficult to diffuse into the third zone 203.
At this time, the pressure difference between the first zone 201 and the third zone 203 is preferably about 0.01 Pa to 1 Pa. In FIG. 1, reference numeral 301 indicates the flow of the first precursor to the third zone 203.

Next, the laminate base material 115 is conveyed to the second zone 202 through the opening 107 b provided in the partition wall disposed between the third zone 203 and the second zone 202.
While the laminate substrate 115 passes through the third zone 203, the excess first precursor adsorbed on the laminate substrate 115 is vaporized and purged. At this time, in order to stabilize the conveyance state of the laminate base material 115, it is also possible to install guide rollers 401c and nip rollers 502c as guide rollers at both ends in the width direction of the laminate base material 115 in the third zone 203. is there.

  The conveyance speed of the laminate base material 115 in the third zone 203 is calculated from the passing distance so that a sufficient purge time can be obtained.

A second precursor is introduced into the second zone 202 (see reference numeral 302). While the laminate base material 115 passes through the second zone 202, the first precursor adsorbate adsorbed on both surfaces of the laminate base material 115 reacts with the second precursor to produce a target material.
During this time, only the both ends in the width direction of the laminate base material 115 are held by the guide roller 401b and the nip roller 502b. Therefore, when the first precursor adsorbate and the second precursor react, both surfaces of the laminate base 115 do not touch the mechanical parts arranged in the apparatus. In FIG. 1, reference numeral 302 indicates the flow of the second precursor to the second zone 202.

The material constituting the second precursor is appropriately selected according to the target deposition material.
For example, when the target deposition material is aluminum oxide, water, ozone, and atomic oxygen are used.
In addition, as a material of the 2nd precursor used, the material shown by the nonpatent literature 1 can be used, for example.

  The conveyance speed of the laminate base material 115 in the second zone 202 is calculated from the reaction time and the passage distance so that the time for the base material 105 to pass through the second zone 202 is longer than the reaction time.

  At this time, the conveyance tension of the laminate base material 115 can be set as appropriate so that the laminate base material 115 does not contact the opening 107b.

After the first precursor adsorbate and the second precursor reacted in the second zone 202, the laminate base material 115 was provided on a partition wall disposed between the second zone 202 and the third zone 203. It is again conveyed to the third zone 203 through another opening 107b.
The gas in the second zone 202 is exhausted by an exhaust mechanism (reference numeral 304b) such as a vacuum pump connected to the second zone. By using this exhaust mechanism, the pressure in the third zone 203 is kept higher than the pressure in the second zone 202. Therefore, the second precursor introduced into the second zone 202 is maintained under conditions that make it difficult to diffuse into the third zone 203.
At this time, the pressure difference between the second zone 202 and the third zone 203 is preferably about 0.01 Pa to 1 Pa. In FIG. 1, reference numeral 304 b indicates the flow of exhaust from the second zone 202 by the second zone exhaust mechanism.

The above process is one cycle of atomic layer deposition, and one atomic layer is deposited by this process. By repeating this one cycle a plurality of times, an atomic layer deposition film having a desired film thickness can be formed on the surface of the laminate substrate 115.
When the above-mentioned one cycle is repeated a plurality of times, the conveying speed of the laminate base material 115 depends on the time required for exposing the base material 105 to the first zone 201, the second zone 202, and the third zone 203, and the laminate base. It is set to the lowest speed among the conveying speeds calculated from the passing distance through which the material 115 passes through the zones 201, 202, and 203.

  The above cycle is repeated a plurality of times, and after an atomic layer deposition film having a desired film thickness is formed on the surface of the laminated base material 115, the laminated base material 115 is taken up in a take-up chamber.

A partition plate 104a is installed between the third zone 203 and the winding chamber 104 in which the winding roller 102 is installed. The partition plate 104a is provided with an opening 106 necessary for the laminate base material 115 to pass through.
The laminated base material 115 is transported from the third zone 203 to the winding chamber 104 through the opening 106 after film formation.

  At this time, the conveyance tension of the laminate base material 115 can be appropriately set so that the laminate base material 115 does not contact the opening 106.

In the winding chamber 104, the carrier laminating substrate 113 is peeled from the laminating substrate 115 via the delaminating roller 504 immediately before the winding roller 102. The peeled carrier laminate substrate 113 is wound up by the delaminate substrate roller 112.
Further, the rollable base material 105 from which the carrier laminate base material 113 is peeled off via the delaminating roller 504 is wound by the windup roller 102 immediately before the windup roller 102. That is, the base material (atomic layer deposited film laminate) 105 on which the atomic layer is deposited is taken up by the take-up roller 102.

  At this time, the laminate base material 113 on which the atomic layer deposition film is formed is wound up by the winding roll 102 without peeling off the carrier base material 113 from the laminate base material 115 on which the atomic layer deposition film is formed. Also good.

  The carrier laminate base material (conveyance auxiliary material) 113 can be repeatedly used as a conveyance auxiliary material by removing it from the delaminating roll 112 and installing it again on the laminating roll 111.

[Modification]
The following modifications may be added to the above embodiment.

(Nip roller rotation axis variable)
A configuration example of the nip roller type nipping / conveying mechanism 501 in the atomic layer deposition winding film forming apparatus 100 is shown in FIGS. 3 and 4 are schematic sectional views of the nip roller type nipping and conveying mechanism 501. FIG.

As shown in FIG. 4, the nip roller type nipping / conveying mechanism 501 includes two rollers 401 and 502 that sandwich the front and back surfaces of both ends in the width direction of the laminate base 115 and transmit power. Furthermore, at least one of the nip roller 502 (first roller) and the guide roller 401 (second roller) has a mechanism capable of changing the rotation axis.
That is, one of the rollers (for example, the nip roller 502) installed on the front surface and the back surface includes a mechanism for changing the rotation axis.

    It is possible to adjust the slackness of the laminate base material 115 by changing the rotation axis in a direction spreading with respect to the traveling direction of the laminate base material 115.

  When such a rotating shaft variable mechanism is provided only in the nip roller 502 of the nip roller type nipping and conveying mechanism 501, the diameter of the nip roller 502 whose rotating shaft is variable is set to the diameter of the other guide roller 401 as shown in FIG. It is preferable to make it smaller. However, this is not the case when the rotation axis of the guide roller 401 is variable or the rotation axes of both the guide roller 401 and the nip roller 502 arranged so as to face each other are variable.

Specifically, the nip roller type nipping / conveying mechanism 501 uses the rotation axis of the nip roller 502 so that the rotation axis direction of the nip roller 502 (first roller) is inclined with respect to the rotation axis direction of the guide roller 401 (second roller). Can be variable.
Further, the guide roller 401 may have a mechanism capable of changing the rotation axis, like the nip roller 502.
The nip roller type nipping / conveying mechanism 501 changes the rotational axis of at least one of the nip roller 502 and the guide roller 401 so that the width of the laminate base material 115 increases in the traveling direction of the laminate base material 115.

  For example, the rotation axis of the nip roller 502 is varied so that the rotation axis direction of the nip roller 502 is inclined with respect to the rotation axis direction of the guide roller 401. The rotation axis of the guide roller 401 is varied so that the rotation axis direction of the nip roller 502 is inclined with respect to the rotation axis direction of the guide roller 401. Alternatively, the rotation axis direction of one of the nip rollers 502 arranged to face each other is inclined with respect to the rotation axis direction of the other roller. The rotation axis directions of both the nip rollers 502 arranged so as to face each other are inclined with respect to the rotation axis direction of the guide roller 401. By these, it is possible to adjust the slackness of the laminate base material 115.

  The correction of the slackness of the laminate substrate 115 or the correction of the meandering is controlled by adjusting the pressure with which the nip roller 502 presses the guide roller 401, the direction of the nip roller 502, and the direction of the guide roller 402. Thereby, the stable driving | running | working (conveyance of a base material) in the lamination base material 115 is realizable.

(About guide rail)
6 and 7 are diagrams showing the configuration of the guide rail when the atomic layer deposition winding film forming apparatus 100 is used. FIG. 6 is a perspective view showing a position close to the opening when a guide rail is used. FIG. 7 is a sectional view of the guide rail.

  As shown in FIG. 6, the atomic layer deposition roll-up film forming apparatus 100 has a laminate base at a position close to the opening 107 provided in the partition wall disposed between the first zone 201 and the third zone 203. You may provide the guide rail 601 used when the material 115 passes. Further, a guide rail 601 used when the laminate base material 115 passes may be provided at a position close to the opening 107 provided in the partition wall disposed between the third zone 203 and the second zone 202. .

The guide rail 601 is an auxiliary tool used to increase the accuracy of the position of the laminate base material 115 passing through the opening 107 of the partition wall 108 arranged between the zones.
By using the guide rail 601, the laminate base material 115 can be accurately conveyed to the opening 107. Therefore, the width (X) of the opening 107 can be designed to be smaller. Further, the guide roller 401 and the nip roller 502 disposed in the third zone 203 can be omitted. Therefore, contamination generated by the precursor in the first zone 201 or the third zone 203 and the purge gas in the third zone 203 can be kept low.

For example, when there is a guide rail 601, the width (X) of the opening can be set to about 1 mm.
On the other hand, when the guide rail 601 is not provided, it is necessary to set the width (X) of the opening to about 5 mm in view of the stability of the position of the laminate base material 115 being conveyed.
The guide rail 601 is preferably installed at a position close to the opening 107 so as to sandwich both end portions of the laminate base 115 as shown in FIG.
The position where the guide rail 601 is installed is appropriately determined depending on the thickness of the laminate base material 115, the conveyance speed of the laminate base material 115, and the like.

  When the conveyance tension of the laminate base material 115 is low, there is a concern that the laminate base material 115 travels extremely unstable. In this case, there is a concern that particles are generated due to contact with the guide rail 601. For this reason, it is necessary to set the conveyance tension as high as possible. When the transport tension is increased, there is a high possibility that buckling such as wrinkles or folds will occur. On the other hand, in the present embodiment, a laminate base material 115 in which a rollable base material 105 for film formation is bonded to a carrier laminate base material 113 is conveyed. Therefore, even when the conveyance tension is increased, occurrence of buckling can be prevented.

  In the present embodiment, the case where the holding portion that holds both end portions in the width direction of the laminate base material 115 is configured by a pair of guide rollers 401 and nip rollers 502, but the present invention is not limited to this. . In the present invention, the holding unit may be configured by the guide roller 401 and at least one nip roller 502 that sandwiches both end portions in the width direction of the laminate base material 115 together with the guide roller 401. That is, the nip roller 502 may not be provided so as to face all the guide rollers 401.

  In the atomic layer deposition winding film forming apparatus 100 according to the present embodiment, the carrier laminate substrate 113 on the back side is peeled after the atomic layer deposition film formation. Therefore, it is possible to manufacture a base material in which atomic layer deposition is performed only on one side and no atomic layer is deposited on the back side.

  In the atomic layer deposition winding film forming apparatus 100 of the present embodiment, a winding tension is applied to the rollable base material 105 on which an ALD (Atomic Layer Deposition) film is formed, and the carrier laminate Similarly, a winding tension is applied to the base material 113. While the rollable base material 105 and the carrier laminate base material 113 are in close contact with each other, they are moved at the same speed and are peeled off at the same speed because they are not peeled off during conveyance. The adhesive strength (peel strength) has an influence on the ALD film. Therefore, the adhesive strength can be set so that it does not become so strong even at the time of conveyance by setting it to substantially the same speed.

  In the atomic layer deposition winding film forming apparatus 100 of the present embodiment, increasing the length of the transport distance and increasing the transport speed increase the tension applied to the substrate 105 that can be wound. Therefore, it has almost the same effect. When the tension increases, a tension is applied to the ALD film on the substrate 105 in the transport direction. However, the effect of the tension can be reduced by laminating and processing the carrier laminate substrate 115.

  Further, when the carrier laminate base 113 is peeled off, if the ALD film is subjected to a strong stress (peeling off), the barrier property may be deteriorated. Therefore, it is preferable not to increase the above-mentioned adhesive strength (peel strength) more than necessary. That is, it is preferable that the carrier laminate base material 113 and the base material 105 are in a state in which contact is maintained (sticking) over the entire surface, and the carrier 105 is not so strongly adhered that the base material 105 is deformed at the time of peeling.

Hereinafter, an atomic layer deposition winding film forming apparatus 100 according to a second embodiment of the present invention will be described with reference to the drawings.
FIG. 8 is a schematic view showing an atomic layer deposition winding film forming apparatus 100 in the present embodiment.
The present embodiment is different from the first embodiment described above in that the peeling in the winding chamber 104 is not performed. Other corresponding components are designated by the same reference numerals and description thereof is omitted.

In this embodiment, after the film formation, the laminate base material 113 is not peeled off from the base material 115 laminated in the take-up chamber 104, and the laminate base material 115 is taken up as it is by the take-up roller 102. .
Thereby, the base material 10 in a state of being bonded to the carrier base material 113 can be manufactured.

  Examples according to the present invention will be described below.

<Example 1>
A polyester film having a thickness of 25 μm was used as the substrate 105 that can be wound using the atomic layer deposition winding film forming apparatus 100 shown in FIG. In addition, a polyester film having a thickness of 75 μm was used as the carrier laminate substrate 113.

  The polyester film as the rollable substrate 105 was attached to the position of the unwinding roller 101. The polyester film as the carrier laminate base material (conveyance auxiliary material) 113 was pulled out from the laminate base material roller 111. They were then bonded together and conveyed as a laminated rollable substrate 115.

The laminated rollable base material 115 was conveyed to the third zone 203 and conveyed to the first zone 201 via the guide roller 401c and the nip roller 502c of the third zone 203.
The conveyance was performed in a state in which the conveyance tension of the laminated and rollable base material 115 when entering the first zone 201 was set to 50 N / width.

In the first zone 201, nitrogen gas used as a carrier gas and trimethylaluminum used as a first precursor were introduced.
The flow rate 301 of the gas supplied to the first zone 201 and the exhaust (decompression) amount 304a by the dry pump were adjusted so that the pressure in the first zone 201 was approximately 50 Pa.
While moving in the first zone 201 by the guide roller 401a and the nip roller 502a, saturated adsorption of trimethylaluminum was performed on both surfaces of the polyester film.

  The polyester film saturated with trimethylaluminum on both sides was conveyed again to the third zone 203. Nitrogen gas was introduced into the third zone 203 as an inert gas. The gas flow rate 303 was adjusted so that the pressure in the third zone 203 was approximately 50.5 Pa. While traveling through the third zone 203, excess trimethylaluminum was purged. After sufficient purging, the sheet was conveyed to the second zone 202 by the guide roller 401c and the nip roller 502c in the third zone 203.

Nitrogen gas used as the carrier gas and ion-exchanged water used as the second precursor were introduced into the second zone 202. The flow rate 302 of the gas supplied to the second zone 202 and the exhaust (decompression) amount 304b by the dry pump were adjusted so that the pressure in the second zone 22 was approximately 50 Pa.
While moving in the second zone 202 by the guide roller 401b and the nip roller 502b, trimethylaluminum on both sides of the polyester film reacted with ion-exchanged water, and one atomic layer was deposited on the substrate.

In addition, the conveyance speed of the polyester film was determined by the required purge time in the third zone 203.
The temperatures of the first zone 201, the second zone 202, and the third zone 203 were all maintained at 90 ° C.

  In addition, as the atomic layer deposition roll-up film forming apparatus 100 shown in FIG. 1, an apparatus that performs three cycles of atomic layer deposition by one transport is shown. However, in practice, an apparatus capable of 100 cycles was prepared, and 100 cycles of atomic layer deposition were performed.

As a result, the thickness of the aluminum oxide film formed on the polyester film was 10 nm.
Neither buckling nor rubbing with the opening 107 was confirmed on the laminated and rollable substrate 115 being conveyed.
Moreover, as a result of observing the damage of the surface using an electron microscope, the damage of the surface of the aluminum oxide film was not recognized.
Further, the water vapor permeability of the aluminum oxide film was measured.

<Comparative Example 1>
A polyester film having a thickness of 50 μm was used as the substrate 105 that can be wound using the atomic layer deposition winding film forming apparatus 100 shown in FIG.

The polyester film as the rollable substrate 105 was attached to the position of the unwinding roller 101. Then, it was transported to the third zone 203 and transported to the first zone 201 through the guide roller 401c and the nip roller 502c of the third zone 203.
The conveyance was performed in a state where the conveyance tension of the rollable base material 105 was set to 50 N / width.

In the first zone 201, nitrogen gas used as a carrier gas and trimethylaluminum used as a first precursor were introduced.
The flow rate 301 of the gas supplied to the first zone 201 and the exhaust (decompression) amount 304a by the dry pump were adjusted so that the pressure in the first zone 201 was approximately 50 Pa.
While moving in the first zone 201 by the guide roller 401a and the nip roller 502a, saturated adsorption of trimethylaluminum was performed on both surfaces of the polyester film.

  The polyester film saturated with trimethylaluminum on both sides was conveyed again to the third zone 203. Nitrogen gas was introduced into the third zone 203 as an inert gas. The gas flow rate 303 was adjusted so that the pressure in the third zone 203 was approximately 50.5 Pa. While traveling through the third zone 203, excess trimethylaluminum was purged. After sufficient purging, the sheet was conveyed to the second zone 202 by the guide roller 401c and the nip roller 502c in the third zone 203.

Nitrogen gas used as the carrier gas and ion-exchanged water used as the second precursor were introduced into the second zone 202. The flow rate 302 of the gas supplied to the second zone 202 and the exhaust (decompression) amount 304b by the dry pump were adjusted so that the pressure in the second zone 22 was approximately 50 Pa.
While moving in the second zone 202 by the guide roller 401b and the nip roller 502b, trimethylaluminum on both sides of the polyester film reacted with ion-exchanged water, and one atomic layer was deposited on the substrate.

In addition, the conveyance speed of the polyester film was determined by the required purge time in the third zone 203.
The temperatures of the first zone 201, the second zone 202, and the third zone 203 were all maintained at 90 ° C.

  In addition, as the atomic layer deposition roll-up film forming apparatus 100 shown in FIG. 1, an apparatus that performs three cycles of atomic layer deposition by one transport is shown. However, in practice, an apparatus capable of 100 cycles was prepared, and 100 cycles of atomic layer deposition were performed.

As a result, the thickness of the aluminum oxide film formed on the polyester film was 10 nm.
Although buckling was confirmed in the rollable base material 105 during conveyance, rubbing with the opening 107 was not confirmed.
Further, the water vapor permeability of the aluminum oxide film was measured.

<Comparative example 2>
A polyester film having a thickness of 25 μm was used as the substrate 105 that can be wound using the atomic layer deposition winding film forming apparatus 100 shown in FIG.

The polyester film as the rollable substrate 105 was attached to the position of the unwinding roller 101. Then, it was transported to the third zone 203 and transported to the first zone 201 through the guide roller 401c and the nip roller 502c of the third zone 203.
The conveyance was performed in a state where the conveyance tension of the rollable base material 105 was set to 10 N / width.

In the first zone 201, nitrogen gas used as a carrier gas and trimethylaluminum used as a first precursor were introduced.
The flow rate 301 of the gas supplied to the first zone 201 and the exhaust (decompression) amount 304a by the dry pump were adjusted so that the pressure in the first zone 201 was approximately 50 Pa.
While moving in the first zone 201 by the guide roller 401a and the nip roller 502a, saturated adsorption of trimethylaluminum was performed on both surfaces of the polyester film.

  The polyester film saturated with trimethylaluminum on both sides was conveyed again to the third zone 203. Nitrogen gas was introduced into the third zone 203 as an inert gas. The gas flow rate 303 was adjusted so that the pressure in the third zone 203 was approximately 50.5 Pa. While traveling through the third zone 203, excess trimethylaluminum was purged. After sufficient purging, the sheet was conveyed to the second zone 202 by the guide roller 401c and the nip roller 502c in the third zone 203.

Nitrogen gas used as the carrier gas and ion-exchanged water used as the second precursor were introduced into the second zone 202. The flow rate 302 of the gas supplied to the second zone 202 and the exhaust (decompression) amount 304b by the dry pump were adjusted so that the pressure in the second zone 22 was approximately 50 Pa.
While moving in the second zone 202 by the guide roller 401b and the nip roller 502b, trimethylaluminum on both sides of the polyester film reacted with ion-exchanged water, and one atomic layer was deposited on the substrate.

In addition, the conveyance speed of the polyester film was determined by the required purge time in the third zone 203.
The temperatures of the first zone 201, the second zone 202, and the third zone 203 were all maintained at 90 ° C.

  In addition, as the atomic layer deposition roll-up film forming apparatus 100 shown in FIG. 1, an apparatus that performs three cycles of atomic layer deposition by one transport is shown. However, in practice, an apparatus capable of 100 cycles was prepared, and 100 cycles of atomic layer deposition were performed.

As a result, the thickness of the aluminum oxide film formed on the polyester film was 10 nm.
Buckling and rubbing with the opening 107 were confirmed on the rollable base material 115 during conveyance.
Further, the water vapor permeability of the aluminum oxide film was measured.

  The water vapor permeability of the aluminum oxide film in Example 1 and Comparative Examples 1 and 2 was measured by the following method.

<Evaluation method>
The water vapor permeability was measured by the MOCON method (same pressure method). The measuring instrument used was measured at 40 ° C. and 90% Rh by MOCON AQUATRAN model 1 (an ultra-sensitive water vapor permeability measuring device AQUATRAN manufactured by MOCON).
Table 1 shows the water vapor permeability of the aluminum oxide films in Example 1, Comparative Example 1, and Comparative Example 2, and the occurrence of scratches.

  Thereby, in Example 1 which bonded together, it turns out that there is no flaw and water vapor permeability is low.

<Example 2>
A polyester film having a thickness of 25 μm was used as the substrate 105 by using the atomic layer deposition winding film forming apparatus 100 shown in FIG. Further, as the conveyance auxiliary material 113, a polyester film with an adhesive having a thickness of 50 μm and an adhesive force of 0.2 N / 25 mm with respect to polyethylene terephthalate (PET) was used.
In addition, the conveyance auxiliary material 113 is a conveyance auxiliary material that has already been peeled off and wound after being bonded to another base material twice.

  The polyester film as the base material 105 attached at the position of the unwinding roll 101 is bonded to the polyester film as the transport auxiliary material 113 drawn from the laminating roll 111 and transported as a laminated rollable base material 115. It was done.

The laminated rollable base material 115 was conveyed to the third zone 203 and conveyed to the first zone 201 through the guide roller 401c and the nip roller 502c of the third zone 203.
The laminated rollable base material 115 when entering the first zone 201 was conveyed with the conveyance tension set to 50 N / width.

In the first zone 201, nitrogen gas used as a carrier gas and trimethylaluminum used as a first precursor were introduced.
The displacement of the first zone 201 and the flow rate of the first precursor were adjusted so that the pressure in the first zone 201 was approximately 50 Pa.
Saturated adsorption of trimethylaluminum was performed on both sides of the polyester film while moving in the first zone 201 by the guide roller 401a and the nip roller 502a.

  The polyester film in which trimethylaluminum was saturated and adsorbed on both sides was conveyed again to the third zone 203. Nitrogen gas was introduced into the third zone 203 as an inert gas. The flow rate of the inert gas in the third zone 203 was adjusted so that the pressure in the third zone 203 was approximately 50.5 Pa. While traveling through the third zone 203, excess trimethylaluminum was purged. After sufficient purging, the polyester film was conveyed to the second zone 202 by the guide roller 401 c and the nip roller 502 c in the third zone 203.

Nitrogen gas used as the carrier gas and ion-exchanged water used as the second precursor were introduced into the second zone 202. The flow rate of the gas supplied to the second zone 202 and the amount of exhaust (decompression) in the second zone 202 by the dry pump were adjusted so that the pressure in the second zone 202 was approximately 50 Pa.
While moving in the second zone 202 by the guide roller 401b and the nip roller 502b, trimethylaluminum on both sides of the polyester film reacted with ion-exchanged water, and one atomic layer was deposited on the polyester film.

The conveyance speed of the polyester film was determined by the required purge time in the third zone 203.
The temperatures of the first zone 201, the second zone 202, and the third zone 203 were all maintained at 90 ° C.

  Further, as the atomic layer deposition winding film forming apparatus 100 shown in FIG. 1, an apparatus that performs three cycles of atomic layer deposition by one transport is shown, but in reality, an apparatus capable of 100 cycles is shown. 100 cycles of atomic layer deposition were performed.

As a result, the thickness of the aluminum oxide film formed on the polyester film was 10 nm.
Neither buckling nor rubbing with the opening 107 was confirmed on the laminated and rollable substrate 115 being conveyed.
Further, the water vapor permeability of the formed aluminum oxide film was measured.

<Comparative Example 3>
A polyester film having a thickness of 25 μm was used as the substrate 105 by using the atomic layer deposition winding film forming apparatus 100 shown in FIG. Further, as the conveyance auxiliary material 113, a polyester film with an adhesive having a thickness of 38 μm and an adhesive force of 0.5 N / 25 mm with respect to polyethylene terephthalate (PET) was used.
In addition, the conveyance auxiliary material 113 is a conveyance auxiliary material that has already been peeled off and wound after being bonded to another base material twice.

  The polyester film as the base material 105 attached at the position of the unwinding roll 101 is bonded to the polyester film as the transport auxiliary material 113 drawn from the laminating roll 111 and transported as a laminated rollable base material 115. Is done.

The laminated rollable base material 115 was conveyed to the third zone 203 and conveyed to the first zone 201 through the guide roller 401c and the nip roller 502c of the third zone 203.
The laminated rollable base material 115 when entering the first zone 201 was conveyed in a state where the conveyance tension was set to 20 N / width.

In the first zone 201, nitrogen gas used as a carrier gas and trimethylaluminum used as a first precursor were introduced.
The displacement of the first zone 201 and the flow rate of the first precursor were adjusted so that the pressure in the first zone 201 was approximately 50 Pa.
Saturated adsorption of trimethylaluminum was performed on both sides of the polyester film while moving in the first zone 201 by the guide roller 401a and the nip roller 502a.

  The polyester film saturated with trimethylaluminum on both sides was conveyed again to the third zone 203. Nitrogen gas was introduced into the third zone 203 as an inert gas. The flow rate of the inert gas in the third zone 203 was adjusted so that the pressure in the third zone 203 was approximately 50.5 Pa. While traveling through the third zone 203, excess trimethylaluminum was purged. After sufficient purging, the polyester film was conveyed to the second zone 202 by the guide roller 401 c and the nip roller 502 c in the third zone 203.

Nitrogen gas used as the carrier gas and ion-exchanged water used as the second precursor were introduced into the second zone 202. The flow rate of the gas supplied to the second zone 202 and the amount of exhaust (decompression) in the second zone 202 by the dry pump were adjusted so that the pressure in the second zone 202 was approximately 50 Pa.
While moving in the second zone 202 by the guide roller 401b and the nip roller 502b, trimethylaluminum on both sides of the polyester film reacted with ion-exchanged water, and one atomic layer was deposited on the polyester film.

In addition, the conveyance speed of the polyester film was determined by the required purge time in the third zone 203.
The temperatures of the first zone 201, the second zone 202, and the third zone 203 were all maintained at 90 ° C.

  Further, as the atomic layer deposition winding film forming apparatus 100 shown in FIG. 1, an apparatus that performs three cycles of atomic layer deposition by one transport is shown, but in reality, an apparatus capable of 100 cycles is shown. 100 cycles of atomic layer deposition were performed.

As a result, the thickness of the aluminum oxide film formed on the polyester film was 10 nm.
Neither buckling nor rubbing with the opening 107 was confirmed on the laminated and rollable substrate 115 being conveyed.
Further, the water vapor permeability of the formed aluminum oxide film was measured.

<Comparative Example 4>
A polyester film having a thickness of 50 μm was used as the substrate 105 using the atomic layer deposition winding film forming apparatus 100 shown in FIG.

The polyester film as the base material 105 attached to the position of the unwinding roll 101 was conveyed to the third zone 203 and conveyed to the first zone 201 through the guide roller 401c and the nip roller 502c of the third zone 203.
It conveyed in the state which set the conveyance tension of the base material 105 at the time of approaching to the 1st zone 201 as 50 N / width.

In the first zone 201, nitrogen gas used as a carrier gas and trimethylaluminum used as a first precursor were introduced.
The displacement of the first zone 201 and the flow rate of the first precursor were adjusted so that the pressure in the first zone 201 was approximately 50 Pa.
Saturated adsorption of trimethylaluminum was performed on both sides of the polyester film while moving in the first zone 201 by the guide roller 401a and the nip roller 502a.

  The polyester film saturated with trimethylaluminum on both sides was conveyed again to the third zone 203. Nitrogen gas was introduced into the third zone 203 as an inert gas. The gas flow rate in the third zone 203 was adjusted so that the pressure in the third zone 203 was approximately 50.5 Pa. While traveling through the third zone 203, excess trimethylaluminum was purged. After sufficient purging, the polyester film was conveyed to the second zone 202 by the guide roller 401 c and the nip roller 502 c in the third zone 203.

Nitrogen gas used as the carrier gas and ion-exchanged water used as the second precursor were introduced into the second zone 202. The flow rate of the gas supplied to the second zone 202 and the amount of exhaust (decompression) in the second zone 202 by the dry pump were adjusted so that the pressure in the second zone 202 was approximately 50 Pa.
While moving in the second zone 202 by the guide roller 401b and the nip roller 502b, trimethylaluminum on both sides of the polyester film reacted with ion-exchanged water, and one atomic layer was deposited on the polyester film.

In addition, the conveyance speed of the polyester film was determined by the required purge time in the third zone 203.
The temperatures of the first zone 201, the second zone 202, and the third zone 203 were all maintained at 90 ° C.

  Further, as the atomic layer deposition method roll-up film forming apparatus 100 shown in FIG. 1, there is shown an apparatus in which three cycles of atomic layer deposition are performed by one transport, but in reality, an apparatus capable of 100 cycles. Were prepared and 100 cycles of atomic layer deposition were performed.

As a result, the thickness of the aluminum oxide film formed on the polyester film was 10 nm.
Although buckling was confirmed in the base material 105 during conveyance, rubbing with the opening 107 was not confirmed.
Further, the water vapor permeability of the aluminum oxide film was measured.

<Comparative Example 5>
A polyester film having a thickness of 25 μm was used as the substrate 105 using the atomic layer deposition method roll-up film forming apparatus 100 shown in FIG.

The polyester film as the base material 105 attached to the position of the unwinding roll 101 was conveyed to the third zone 203 and conveyed to the first zone 201 through the guide roller 401c and the nip roller 502c of the third zone 203.
It conveyed in the state which set the conveyance tension of the base material 105 at the time of approaching to the 1st zone 201 as 10 N / width.

In the first zone 201, nitrogen gas used as a carrier gas and trimethylaluminum used as a first precursor were introduced.
The displacement of the first zone 201 and the flow rate of the first precursor were adjusted so that the pressure in the first zone 201 was approximately 50 Pa.
Saturated adsorption of trimethylaluminum was performed on both sides of the polyester film while moving in the first zone 201 by the guide roller 401a and the nip roller 502a.

  The polyester film in which trimethylaluminum was saturated and adsorbed on both sides was conveyed again to the third zone 203. Nitrogen gas was introduced into the third zone 203 as an inert gas. The gas flow rate in the third zone 203 was adjusted so that the pressure in the third zone 203 was approximately 50.5 Pa. While traveling through the third zone 203, excess trimethylaluminum was purged. After sufficient purging, the polyester film was conveyed to the second zone 202 by the guide roller 401 c and the nip roller 502 c in the third zone 203.

Nitrogen gas used as the carrier gas and ion-exchanged water used as the second precursor were introduced into the second zone 202. The flow rate of the gas supplied to the second zone 202 and the amount of exhaust (decompression) in the second zone 202 by the dry pump were adjusted so that the pressure in the second zone 202 was approximately 50 Pa.
While moving in the second zone 202 by the guide roller 401b and the nip roller 502b, trimethylaluminum on both sides of the polyester film reacted with ion-exchanged water, and one atomic layer was deposited on the polyester film.

In addition, the conveyance speed of the polyester film was determined by the required purge time in the third zone 203.
The temperatures of the first zone 201, the second zone 202, and the third zone 203 were all maintained at 90 ° C.

  Further, as the atomic layer deposition winding film forming apparatus 100 shown in FIG. 1, an apparatus that performs three cycles of atomic layer deposition by one transport is shown, but in reality, an apparatus capable of 100 cycles is shown. 100 cycles of atomic layer deposition were performed.

As a result, the thickness of the aluminum oxide film formed on the polyester film was 10 nm.
Although buckling was confirmed in the base material 105 during conveyance, rubbing with the opening 107 was not confirmed.
Further, the water vapor permeability of the aluminum oxide film was measured.

  The water vapor permeability of the aluminum oxide films formed in Example 2 and Comparative Examples 3, 4 and 5 was measured by the following method.

(Evaluation method)
"Water vapor permeability measurement"
The water vapor permeability was measured by the MOCON method (same pressure method). As a measuring instrument, MOCON
The measurement was performed at 40 ° C. and 90% Rh using an AQUATRAN model 1 (AQUATRAN, an ultra-high sensitivity water vapor permeability measuring device manufactured by MOCON).
Table 2 shows the water vapor permeability of the aluminum oxide films formed in Example 2 and Comparative Examples 3, 4 and 5.

"Scratch occurrence"
For the aluminum oxide films formed in Example 2 and Comparative Examples 3, 4 and 5, the occurrence of scratches was confirmed visually.
Table 1 shows the occurrence of scratches on the aluminum oxide films formed in Example 2 and Comparative Examples 3, 4 and 5.

  From the results in Table 2, it can be seen that the aluminum oxide film formed in the example is superior to the aluminum oxide film formed in Comparative Examples 3 to 5 in terms of water vapor permeability and the occurrence of scratches.

  The film forming apparatus of the atomic layer deposition method of the present invention can form a dense foil film by continuously forming a film on a thin wound substrate. As an application example, it can be used for the production of optical films such as metallic luster films used for gold and silver thread, gas barrier films for food packaging, electrodes for film capacitors, antireflection films and the like.

DESCRIPTION OF SYMBOLS 100 ... Atomic layer deposition winding film forming apparatus 101 ... Unwinding roller 102 ... Winding roller 103 ... Unwinding chamber (unwinding apparatus)
103a, 104a ... Partition plate 104 ... Winding chamber (winding device)
105 ... Rollable base material 106, 107, 107a, 107b ... Opening 108 ... Septum 111 ... Laminate base roller 112 ... Delaminate base roller 113 ... Laminate base material for carrier (conveying auxiliary material)
115 ... Laminated roll-up base material (film forming member)
401, 401a, 401b, 401c... Guide roller (holding portion)
502, 502a, 502b, 502c ... Nip roller (holding part)
201 ... first zone (first vacuum chamber)
202 ... Second zone (second vacuum chamber)
203 ... Third zone (third vacuum chamber)
501 ... Nip roller type nipping and conveying mechanism 503 ... Laminating roller 504 ... Delaminating roller 601 ... Guide rail

Claims (11)

An atomic layer deposition film forming apparatus,
Each of the base material and the transport auxiliary material is unwound, and a film forming member is formed on the one surface of the base material so that the transport auxiliary material is peelably laminated, and the film forming member is sent out. An unwinding device,
A first vacuum chamber into which the first precursor gas is introduced;
A second vacuum chamber into which the second precursor gas is introduced;
A third vacuum chamber provided between the first vacuum chamber and the second vacuum chamber, into which purge gas is introduced;
It has a holding part which holds the width direction both ends of the film-forming member, and conveys the film-forming member to the first vacuum air chamber, the second vacuum air chamber, and the third vacuum air chamber A transport mechanism;
A winding device that winds up the base material of the film forming member sent out from the transport mechanism;
With
By the transport mechanism, the film forming member is alternately passed through the first vacuum chamber and the second vacuum chamber a plurality of times, and an atomic layer is formed on the other surface of the substrate in the film forming member. Atomic layer deposition roll-up filming device that deposits to form an atomic layer deposition film.   The holding portion includes a roller that sandwiches both ends in the width direction of the film forming member from the front surface and the back surface of the film forming member, and the roller includes a guide roller and the film forming member. The atomic layer deposition winding film forming apparatus according to claim 1, further comprising a nip roller that is nipped between the guide roller and the nip roller.   3. The atomic layer deposition winding film forming apparatus according to claim 1, wherein the winding apparatus is configured to wind up the base material after peeling the conveyance auxiliary material from the film forming member.   3. The atomic layer according to claim 1, wherein the conveyance auxiliary material that is peelably laminated on the base material has an adhesive force in a range of 0.001 N / 25 mm to 5 N / 25 mm on a surface to be laminated with the base material. Deposition winding film forming equipment.   The winding device peels off the conveyance auxiliary material, and the peeled conveyance auxiliary material is again reused as a conveyance auxiliary material by which the unwinding device laminates on one surface of the base material before film formation. The atomic layer deposition winding film forming apparatus according to any one of claims 1 to 4, which is used.   The atomic layer deposition winding film forming apparatus according to claim 1, wherein the winding apparatus is configured to wind the film forming member.   The atomic layer deposition according to claim 2, wherein the guide roller and the nip roller are independently disposed in any one of the first vacuum chamber, the second vacuum chamber, and the third vacuum chamber. Winding film forming equipment. An atomic layer deposition method for transporting a long base material and continuously forming an atomic layer deposition film on the base material,
A film forming member is formed by laminating a conveyance auxiliary material on one surface of the substrate so as to be peelable with respect to the conveyance direction of the substrate,
Conveying the film-forming member and depositing an atomic layer on the other surface of the substrate to form an atomic layer deposition film,
An atomic layer deposition method in which the transport auxiliary material is peeled from the deposition target member after the deposition of the atomic layer volume film, and the atomic layer deposition film stack is taken out.   The atomic layer deposition method according to claim 8, wherein the peeled conveyance auxiliary material is reused for forming the film forming member that is laminated on one surface of the base material.   The atomic layer according to claim 8 or 9, wherein the conveyance auxiliary material that is detachably laminated on the substrate has an adhesive force in a range of 0.001 N / 25 mm to 5 N / 25 mm on a surface laminated with the substrate. Deposition method. The atomic layer deposition method according to any one of claims 8 to 10, wherein an atomic layer deposition film is formed on the base material that is thinner than the transport auxiliary material before lamination.

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