WO2023234108A1 - Method for manufacturing laminate, method for manufacturing semiconductor device, and film forming apparatus - Google Patents

Method for manufacturing laminate, method for manufacturing semiconductor device, and film forming apparatus Download PDF

Info

Publication number
WO2023234108A1
WO2023234108A1 PCT/JP2023/019053 JP2023019053W WO2023234108A1 WO 2023234108 A1 WO2023234108 A1 WO 2023234108A1 JP 2023019053 W JP2023019053 W JP 2023019053W WO 2023234108 A1 WO2023234108 A1 WO 2023234108A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
film
container
containing gas
raw material
Prior art date
Application number
PCT/JP2023/019053
Other languages
French (fr)
Japanese (ja)
Inventor
哲雄 奥山
桂也 ▲徳▼田
啓介 松尾
奈織美 瀧本
Original Assignee
東洋紡株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Publication of WO2023234108A1 publication Critical patent/WO2023234108A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B1/00—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers

Definitions

  • the present invention relates to a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a film forming apparatus.
  • Patent Documents 1 to 5 In semiconductor devices such as solar cell devices, various methods are known for forming a predetermined film on a member to be processed (for example, a substrate) (Patent Documents 1 to 5).
  • problems when forming a film include contamination of the working environment, adhesion of the film-forming material to surfaces other than the substrate, and staining of the substrate and the film formed on the substrate. It is known that the formed film is not uniform.
  • Patent Document 1 discloses that a mist application method using a mist generator is performed in a booth (FIG. 1).
  • Patent Document 2 describes an apparatus in which a substrate is placed in a chamber and a mist generator is connected to the chamber as a film forming apparatus used in a method for manufacturing a dielectric film (FIG. 1).
  • Patent Document 3 discloses a dielectric thin film forming apparatus that includes a rotary stage on which a substrate is placed and a mist jetting means in a process chamber (FIG. 1).
  • Patent Document 4 teaches that a film forming method in which a mist coating material solution is applied to the surface of a member to be processed is performed in a processing chamber (FIG. 2).
  • Patent Document 5 discloses that a pattern forming device including a mist dispersion section and a substrate installation section is provided in a chamber (FIG. 1).
  • Patent Documents 1 to 5 a film is formed by placing a substrate in a forming apparatus. According to the film formation methods disclosed in Patent Documents 1 to 5, for example, steps such as transferring the substrate into the apparatus and aligning the substrate within the apparatus are required; Because of the need for installation, the time required for film formation becomes long, and there has been a need to improve the productivity of the resulting film.
  • metal masks and etching are often used in a working environment different from that for film formation, making the work process complicated and also increasing the time required for film formation. Furthermore, the number of members required for metal masks and etching increases, increasing costs, and it is desired to reduce the use of metal masks and etching as much as possible.
  • an object of the present invention is to provide a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a film forming apparatus that do not require a metal mask or etching and have improved film formation efficiency.
  • Another object of the present invention is to provide a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a film forming apparatus that make it possible to reduce costs and suppress pollution of the working environment.
  • the present inventors have found that by adopting a method of forming a film by bringing the opening of the container into contact with the substrate, metal masks and etching are not required. discovered that the film formation efficiency was improved and completed the present invention.
  • the present invention which has solved the above problems, is a method for manufacturing a laminate including a substrate and a film, comprising: (1) bringing the opening of a container having an opening into contact with one main surface side of the substrate; (2) introducing a film material-containing gas into the container; and (3) bringing the film material-containing gas into contact with the one main surface side of the substrate to form the film on the one main surface side of the substrate.
  • a method for manufacturing a laminate comprising the steps of: forming a laminate. According to the present invention, film formation efficiency can be improved without requiring a metal mask or etching. Further, according to the present invention, it may be possible to reduce costs and suppress pollution of the working environment.
  • the shape of the film viewed from the normal direction of the substrate and the shape of the opening viewed from the normal direction of the substrate are similar to each other.
  • the membrane raw material-containing gas contains a mist of a solution containing the membrane forming material.
  • the film is formed on the entire inner surface of the opening that comes into contact with the one main surface.
  • the method for manufacturing the laminate further includes, after the step (2), providing a time period for stopping the introduction of the membrane raw material-containing gas by stopping the introduction of the membrane raw material-containing gas into the container;
  • the ratio of (introduction time of membrane raw material containing gas)/(introduction stop time of membrane raw material containing gas) is 1/4 to 2.
  • the method for manufacturing the laminate preferably further includes the step of (1a) applying a potential to the container to prevent the membrane raw material-containing gas from adhering to the container.
  • the method for manufacturing the laminate preferably further includes the step of (4) introducing an inert gas into the container. In the step (3), it is also preferable that the film is formed by heating the substrate.
  • the film is selected from a conductive layer, an electron transport layer, an electrode layer, a photovoltaic layer, a hole transport layer, a protective layer, a p-type semiconductor layer, an n-type semiconductor layer, an insulating layer, a gas barrier layer, and an adhesive layer. It may contain one or more.
  • the film may be used in semiconductor devices such as solar cell devices.
  • Another aspect of the present invention is a method for manufacturing a semiconductor device, which includes the step of manufacturing the laminate using the method for manufacturing a laminate.
  • Another aspect of the present invention is an apparatus for forming a film on a substrate, including a holder for holding the substrate and a container provided opposite to the substrate, the container being arranged on one main surface of the substrate.
  • This is a film forming apparatus characterized by having an opening that abuts on the side and a film raw material containing gas inlet.
  • film formation efficiency can be improved without requiring a metal mask and etching. Further, according to the present invention, it may be possible to reduce costs and suppress pollution of the working environment.
  • the film forming apparatus further includes a first control mechanism that controls the holder and the container to be movable in a first axial direction so as to move them toward and away from each other.
  • the film forming apparatus preferably further includes a second control mechanism that controls the holder to be movable in a second axial direction different from the first axial direction.
  • the film forming apparatus preferably further includes an elastic body that seals a peripheral portion where the opening portion and the one main surface side of the substrate are in contact with each other from the outside of the container.
  • the film forming apparatus preferably further includes a mechanism for creating positive pressure in the container.
  • the container includes an electrically conductive member for applying the potential, and an insulating member provided between the member and another electrically conductive member. It is also preferable that a portion where the opening portion and the one main surface side of the substrate come into contact has a labyrinth. Further, it is also preferable that the film forming apparatus is connected to a substrate cleaning apparatus.
  • film formation efficiency can be improved without requiring a metal mask or etching. Further, according to the present invention, it may be possible to reduce costs and suppress pollution of the working environment.
  • FIG. 1 shows an overview of a method for manufacturing a laminate according to an embodiment of the present invention.
  • FIG. 2 shows a device manufacturing process diagram using the method for manufacturing a laminate according to an embodiment of the present invention.
  • FIG. 3 shows another device manufacturing process diagram using the laminate manufacturing method according to the embodiment of the present invention.
  • FIG. 4 depicts a film forming apparatus according to an embodiment of the present invention.
  • FIG. 1 shows an overview of a method for manufacturing a laminate according to an embodiment of the present invention.
  • the method for manufacturing a laminate of the present invention is a method for manufacturing a laminate including a substrate and a film, which includes: (1) placing the opening 2 of a container 1 having an opening 2 on one main surface side of the substrate 5; (2) introducing the membrane raw material-containing gas 7 into the container 1 (FIG. 1 (ii)), and (3) A step of forming the film 8 on the one main surface side of the substrate 5 by bringing the film material-containing gas 7 into contact with the one main surface side of the substrate 5 (FIG. 1(iii)). do.
  • the steps (1) to (3) can be performed continuously by changing the position of the container 1 after the steps (1) to (3).
  • the removal of the container 1 from the substrate 5 prior to changing the position of the container 1 is not limited to being performed after the step (3), and therefore, changing the position of the container 1 is also performed after the step (3). It is not limited to what is shown.
  • a film can be formed without requiring a metal mask or etching.
  • the laminate is, for example, formed by laminating at least one substrate and at least one film, preferably by laminating at least one substrate and two or more different films.
  • Step (1) is a step of bringing the opening 2 of the container 1 having the opening 2 into contact with one main surface side of the substrate 5.
  • a step of preparing the substrate 5 and a step of preparing the container 1 having the opening 2 may be performed.
  • the container 1 having the opening 2 is brought into contact with the prepared substrate 5 (FIGS. 1 (i-1) and (i-2)), and the substrate 5 and the opening 2 are brought into contact. It is preferable to maintain It is preferable that the container 1 and the substrate 5 in contact form a film forming chamber 6 . This makes it possible to fill the film material-containing gas 7, bring the film material-containing gas 7 into contact with one main surface side of the substrate 5, and form the film 8, as will be described later.
  • the shape of the container 1 includes shapes such as a rectangular parallelepiped, a cube, a cylinder, and a hemisphere.
  • the material of the container 1 either an organic material or an inorganic material may be used.
  • the container 1 is preferably lightweight, and the material of the container 1 is preferably an organic material.
  • it is plastic, and more preferably plastic.
  • the material of the container 1 is an inorganic material, it is more preferably metal.
  • the container 1 From the viewpoint of preventing membrane raw material-containing gas from adhering to the container 1 by applying a potential to the container 1, the container 1 has an electrically conductive member, and an insulator provided between the member and another electrically conductive member. It is preferable to have a member.
  • the container 1 may have corrosion resistance against membrane raw material-containing gas, water, oxygen, etc., and may be coated with a fluororesin or the like.
  • the container 1 and the opening 2 may have a shape corresponding to the step formed by the substrate 5 and/or the layers laminated on the substrate 5. Further, the number of openings 2 that the container 1 has may be one or more than two. When the container 1 has two or more openings 2, the film formation efficiency can be increased. When the container 1 has two or more openings 2, the two or more openings 2 may form a line-and-space, honeycomb, or other pattern. By having the opening 2 have the above-mentioned shape and/or by having two or more openings 2 forming the above-mentioned pattern, it is possible to impart an uneven pattern to the formed film without using a metal mask or etching. can.
  • two or more containers 1 may be used. In this case, two or more containers 1 may be connected or may be connected at a predetermined interval. If such a container is used, a plurality of films can be formed in parallel at different locations on the substrate 5, the time required for film formation can be shortened, and the film formation efficiency can be improved.
  • the container 1 includes a membrane raw material-containing gas inlet 3 and a membrane raw material-containing gas outlet 4. It is preferable that the membrane raw material-containing gas inlet 3 and the membrane raw material-containing gas outlet 4 each include at least one or more valves.
  • the container 1 may be equipped with one or more membrane raw material-containing gas inlets 3, and may also be equipped with one or more membrane raw material-containing gas discharge ports 4.
  • the membrane raw material-containing gas inlet 3 may be provided at any location in the container 1 as long as the membrane raw material-containing gas is introduced into the film forming chamber and a film is appropriately formed.
  • the membrane raw material-containing gas inlet 3 is From the viewpoint of diffusion and reaction of the membrane raw material-containing gas, it is more preferable to provide it on the upper side of the container 1.
  • the membrane raw material-containing gas outlet 4 may be provided at any location in the container 1, and may be provided on the side surface of the container 1, as long as unreacted membrane raw material-containing gas or byproducts are properly discharged from the container 1. It is more preferable to provide it at the lower side of the container 1 from the viewpoint of efficiently discharging unreacted membrane raw material-containing gas or by-products.
  • the membrane raw material containing gas inlet 3 may be connected to the membrane raw material containing tank via a membrane raw material containing gas supply line.
  • the membrane raw material-containing tank may be equipped with, for example, vaporization or spraying means (eg, heating means, bubbling means, ultrasonic means) for turning the membrane raw material into a membrane raw material-containing gas.
  • the membrane raw material containing tank is supplied with inert gas through an inert gas introduction line, and the membrane raw material (film forming material) filled in the tank is subjected to bubbling or ultrasonic waves.
  • the inert gas may be supplied through an inert gas introduction line, and the membrane material in the tank may be heated to supply the membrane raw material-containing gas. There may be.
  • the membrane raw material-containing gas inlet 3 may include a nozzle.
  • the nozzle is preferably a nozzle that uses vibrational energy, more preferably a nozzle that uses an ultrasonic atomizer. Thereby, the size of the mist contained in the membrane raw material containing gas 7 can be further reduced, and the membrane raw material containing gas 7 can be further diffused within the film forming chamber 6.
  • the substrate 5 is, for example, an organic material, a metal material, a cloth material, a paper material, a ceramic material, a glass material, or a combination thereof, and should be selected depending on the device used (for example, a semiconductor device such as a solar cell device).
  • a semiconductor device such as a solar cell device.
  • Substrate 5 is used as a substrate on which thin films are deposited.
  • Materials constituting the substrate 5 include, for example, semiconductor materials such as Si, Ge, and GaAs, glass, metals (for example, SUS), and polymer films (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polycarbonate (PC)). , polyimide (PI), or polyester elastomer (preferably Perprene (registered trademark), nylon).
  • the substrate 5 may include an upper substrate and a lower substrate in which the above-mentioned materials are combined, such as glass with a varnish layer deposited, metal coated, a multilayer film, etc. good.
  • the size of the substrate 5 is preferably large enough to accommodate a plurality of cell units constituting a semiconductor device or the like.
  • the shape of the substrate 5 is preferably a film shape or a roll shape from the viewpoint of improving film formation efficiency.
  • Other layers may be laminated on the substrate 5, and the other layers include a transparent conductive layer, an electron transport layer, an electrode layer, and an optical layer (which may include a p-type semiconductor layer and/or an n-type semiconductor layer).
  • Examples include an electromotive force layer, a hole transport layer, a protective layer, a p-type semiconductor layer, an n-type semiconductor layer, an insulating layer, a gas barrier layer, and an adhesive layer.
  • the film can be formed directly on the substrate 5, or it is also possible to form the film on the substrate 5 on which other layers are laminated.
  • a material preferably an elastic body, more preferably a rubber elastic body
  • a material that seals the peripheral area where the opening 2 and one main surface side of the substrate 5 are in contact with each other from the outside of the container 1 may be fitted to the outer periphery of the container 1.
  • the method of the present invention further includes the step of (1a) applying a potential to the container 1 that prevents the membrane raw material-containing gas 7 from adhering to the container 1.
  • the step (1a) may be performed at any timing. Specifically, the step (1a) may be performed before the step (1), during the step (1), or after the step (1), or before the step (2), or after the step (2). 2) During the step, it may be performed after the step (2), before the step (3), during the step (3), or after the step (3), and the film 8 is formed. It may be done continuously until it is completed. Note that when a step is described herein as being performed during another step, it is also intended that the two steps may be performed partially in parallel.
  • the potential application may be adjusted according to the electric charge that the membrane raw material-containing gas 7 has, and is preferably one that charges the membrane raw material-containing gas 7 to the same polar charge. , it is more preferable to apply a potential.
  • a potential For example, when the membrane raw material-containing gas 7 has a positive charge, it is preferable to apply a potential so that the inner wall of the side surface of the container 1 is charged with a positive charge, and the positive side of the power source is connected to the side surface of the container 1. It is more preferable to connect the negative side of the power supply to ground.
  • the membrane raw material-containing gas 7 has a negative charge
  • the electric charge possessed by the membrane raw material-containing gas 7 may be adjusted, for example, a power source may be provided on the membrane raw material-containing gas supply line to apply a potential.
  • a power source may be provided on the membrane raw material-containing gas supply line to apply a potential.
  • the membrane raw material-containing gas 7 when the membrane raw material-containing gas 7 is charged to a positive side, it is preferable to connect the positive side of the power source to the membrane raw material-containing gas supply line and connect the negative side of the power source to ground.
  • the negative side of the power source is connected to the membrane raw material containing gas supply line, and the positive side of the power source is connected to ground.
  • Step (2) is a step of introducing the film material-containing gas 7 into the container 1 into the film forming chamber 6 formed by the contact between the opening 2 of the container 1 and one main surface side of the substrate 5. It is preferable to introduce the membrane raw material-containing gas 7. That is, the step (2) is preferably performed while the opening 2 and the substrate 5 are in contact with each other in the step (1). Note that the step (2) may be performed before the step (1), during the step (1), or after the step (1), but from the viewpoint of stably introducing the membrane raw material-containing gas 7. Therefore, it is preferable to carry out after the step (1).
  • the membrane raw material-containing gas 7 may be either a gas containing a liquid (also called a solution) or a gas, and may be a membrane raw material in which the liquid is vaporized into solid particles, or a membrane raw material in which solids are dispersed in the liquid. It may include.
  • the membrane raw material (film forming material) contained in the membrane raw material containing gas 7 may be gas, liquid, or solid. If the membrane forming material is solid, it is dissolved or dispersed in a solvent and used as a liquid. When the film-forming material is a liquid, it is preferable to use the film-forming material as a liquid to which a solvent is further added.
  • the film forming material contained in the film raw material containing gas 7 may be either an inorganic material or an organic material, and may be appropriately selected depending on the desired film.
  • Film-forming materials include materials that form films with nanoparticles, materials that form films through reactions such as sol-gel, materials that form films by forming oxides through oxidation treatment, and materials that form films by forming nitrides through nitriding treatment. etc., and more preferably ZnOx, TiOx, MoOx, ITO, FTO, aluminum oxide, and silicon oxide.
  • the solvent used in the solution may be any solvent that can dissolve or disperse the film-forming material, such as ester solvents, ether solvents, ether ester solvents, ketone solvents, alcohol solvents, aromatic hydrocarbon solvents, and amide solvents. Examples include solvents, water, and mixed solutions of the above.
  • the concentration of the film-forming material in the solution may be adjusted depending on the film to be formed and the film-forming time, and is preferably in the range of 10% by mass or less and 0.1 ppm or more.
  • the membrane raw material-containing gas 7 contains an inert gas as a carrier gas.
  • an inert gas as a carrier gas, the concentration of the membrane raw material (film forming material) contained in the membrane raw material containing gas 7 can be adjusted.
  • oxygen and water are removed from the inert gas, but when forming a film using a sol-gel reaction, the inert gas may contain water to some extent.
  • the inert gas include nitrogen, helium, neon, argon, etc. From the viewpoint of versatility, the inert gas is preferably nitrogen, helium, or argon, and more preferably nitrogen or argon.
  • clean dry air may be used for membrane raw materials that are selectively active with water.
  • the membrane raw material-containing gas 7 preferably contains the film forming material as a gas or liquid (solution), and more preferably contains a solution containing the film forming material in the form of a mist.
  • Methods for creating mist include bubbling; methods using pressure energy such as single injection hole nozzles, impingement type injection valves, fan spray nozzles, and spiral injection valves; methods using vibration energy such as vibration nozzles, ultrasonic waves, and acoustics.
  • Methods Methods using gas energy such as air assist atomizers and air blast atomizers; Methods using centrifugal force such as rotating nozzle holes, rotating disks, rotating cups, rotating wheels; Methods using electrical energy such as electrostatics ; evaporation condensation method (a method in which a liquid is heated to vaporize, then cooled and condensed to produce fine particles), vacuum boiling method (a method in which a liquid is rapidly reduced in pressure and boiled, and vapor bubbles grow and the liquid breaks up); methods that use thermal energy, such as a method of generating fine particles; and methods of generating fine particles as a result of bursting of bubbles. Other known methods may be used to create a mist.
  • gas energy such as air assist atomizers and air blast atomizers
  • centrifugal force such as rotating nozzle holes, rotating disks, rotating cups, rotating wheels
  • electrical energy such as electrostatics
  • evaporation condensation method a method in which a liquid is heated to vaporize, then cooled and condensed
  • the membrane raw material containing gas 7 may be introduced from the membrane raw material containing gas inlet 3.
  • the film forming chamber 6 is preferably filled with the film material-containing gas 7 introduced from the film material-containing gas inlet 3 .
  • the amount of the film material-containing gas 7 introduced can be adjusted depending on the film to be formed and the film formation time.
  • the amount of the film material-containing gas 7 introduced is in the range of 1/3 to 20 times the volume of the film forming chamber 6 formed by the contact between the opening 2 of the container 1 and one main surface of the substrate 5. This is desirable.
  • the membrane raw material (solution containing the membrane forming material) filled in the membrane raw material tank is subjected to ultrasonic waves to turn the solution containing the membrane forming material into a mist, and then the solution containing the membrane forming material is turned into a mist.
  • An example of this method is to introduce the membrane raw material-containing gas into the container by pressure-feeding the supplied inert gas. Thereby, the membrane raw material containing gas containing the membrane forming material as a mist can be introduced into the membrane forming chamber from the membrane raw material containing gas inlet.
  • the method of the present invention further includes, after the step (2), a step (2a) of providing a time period for stopping the introduction of the membrane raw material-containing gas 7 by stopping the introduction of the membrane raw material-containing gas 7 into the container 1. It is preferable.
  • the step (2a) is preferably performed while the opening 2 and the substrate 5 are in contact with each other in the step (1).
  • the ratio of (introduction time of membrane raw material containing gas 7)/(introduction stop time of membrane raw material containing gas 7) is preferably 1/4 to 2, more preferably 1/3 to 1.5, More preferably, it is 1/2 to 1. If the ratio of (introduction time of membrane raw material containing gas 7)/(introduction stop time of membrane raw material containing gas 7) satisfies the above range, the membrane raw material containing gas 7 is further diffused in the film forming chamber 6 to form a uniform film. In addition, it becomes possible to reduce the amount of membrane raw material-containing gas 7 used.
  • Step (2a) may be performed at any timing after step (2).
  • the step (2a) may be performed before the step (3), during the step (3), or after the step (3).
  • the introduction of the membrane raw material-containing gas 7 may be stopped once or twice or more, and in the case of twice or more, (total introduction time of the membrane raw material containing gas 7)/(introduction stop time of the membrane raw material containing gas 7) It is sufficient that the ratio of the sum of
  • step (3) is a step of bringing the film material-containing gas 7 into contact with the one main surface side of the substrate 5 to form a film 8 on the one main surface side of the substrate 5. .
  • the film material-containing gas 7 and one main surface side of the substrate 5 come into contact while the opening 2 and the substrate 5 are in contact with each other in the step (1).
  • the step (3) may be performed during the step (2) or after the step (2), and is preferably performed after the step (2).
  • the film 8 may be formed under heating, and it is preferable to form the film 8 by heating the substrate 5.
  • the heating may be performed while the container 1 is in contact with the substrate 5, but if necessary, the heating may be performed by removing the container 1, or by releasing the contact between the container 1 and the substrate 5. You may go.
  • heating also includes heating the film material-containing gas 7 and/or heating the container. Further, heating may be performed before the step (2) (excluding heating of the membrane raw material-containing gas), during the step (2), after the step (2), or before the step (3). , may be carried out during or after the step (3).
  • the heating evaporates the solvent contained in the film raw material-containing gas 7 present on the substrate 5, and when the film 8 is formed on the substrate 5 with a sol-gel reaction, the inside of the film forming chamber 6 or the inside of the film 8 is heated. Promoting the sol-gel reaction with moisture etc., curing the organic material contained in the film 8, and controlling the phase separation of the donor and acceptor when the photovoltaic layer contained in the film 8 contains a donor and an acceptor. It becomes possible.
  • the shape of the film 8 as viewed from the normal direction of the substrate 5 (also referred to as the normal direction to the one main surface of the substrate 5) and the opening as seen from the normal direction of the substrate 5. 2 are similar to each other, and the shape of the film 8 viewed from the normal direction of the substrate 5 and the shape of the opening 2 viewed from the normal direction of the substrate 5 are congruent with each other. It is more preferable.
  • the film 8 is formed on the entire inner surface of the opening 2 that comes into contact with the one main surface.
  • the film 8 is selected from a conductive layer, an electron transport layer, an electrode layer, a photovoltaic layer, a hole transport layer, a protective layer, a p-type semiconductor layer, an n-type semiconductor layer, an insulating layer, a gas barrier layer, and an adhesive layer. Preferably, it includes one or more of the following.
  • the conductive layer and the electrode layer preferably constitute different electrodes (positive electrode, negative electrode), and the conductive layer may be transparent.
  • the film 8 is preferably a film having at least a conductive layer, a photovoltaic layer, and an electrode layer, and preferably a film having at least a conductive layer, an electron transport layer, a photovoltaic layer, a hole transport layer, and an electrode layer.
  • the film 8 is preferably a film having at least a conductive layer, a p-type semiconductor and/or an n-type semiconductor, and an electrode layer; More preferably, the film has at least a hole transport layer and an electrode layer.
  • the method of the present invention may further include a step (4) of introducing an inert gas into the container 1.
  • the inert gas used may be the same as those described above.
  • the material present in the film forming chamber 6 is discharged before introducing the membrane raw material containing gas 7, the membrane raw material containing gas 7 is diffused when the membrane raw material containing gas 7 is introduced, and after the membrane raw material containing gas 7 is introduced. /Or it becomes possible to discharge the material remaining in the film forming chamber 6 before heating, and to eliminate the gas etc. generated in the film forming chamber 6 after heating.
  • the amount of inert gas introduced is preferably 10 to 500 volume %, more preferably 20 to 400 volume %, still more preferably 30 to 300 volume %, and even more preferably 40 volume % to 100% volume of the film forming chamber 6. ⁇ 200% by volume, particularly preferably 50-100% by volume.
  • the step (4) may be performed during the step (1), after the step (1), or before the step (2), during the step (2), or after the step (2). It may be performed before the step (3), during the step (3), after the step (3), or after heating the substrate in the step (3) as described above. good.
  • the method of the present invention may further include a step (5) of removing the container 1 from the one main surface side. Through this step, it becomes possible to release the contact between the opening 2 of the container 1 and the substrate 5, and to take out the substrate 5 and the film 8 formed on the substrate 5.
  • Examples of means for removing the container 1 from the one main surface side include removing the container 1 from the substrate 5 manually, using a predetermined conveying roller, a uniaxially movable substrate holder, a robot arm, or a robot hand. .
  • the step (5) may be performed after the step (3), or after the step (4), or before the heating in the step (3).
  • step (5) may be performed after the last step (3) or step (4).
  • this is preferably carried out when forming a film under heating.
  • the step (1) may be omitted and the steps (2) to (3) or the steps (2) to (4) Steps may be performed.
  • unnecessary portions may be cut off from the film using a laser, a cutter, etc. . Additionally, unnecessary portions may be wiped off before drying the solvent. Further, the substrate 5 and the film 8 formed on the substrate 5 may be subjected to a sealing process.
  • a conductive layer 21, an electron transport layer 22, a photovoltaic layer 23, a hole transport layer 24, and an electrode layer 25 are laminated in this order on the substrate 5, and a protective layer and a gas barrier layer are formed on the electrode layer 25.
  • the layers are laminated.
  • an electrode layer 25, a hole transport layer 24, a photovoltaic layer 23, an electron transport layer 22, and a conductive layer 21 are laminated in this order on the substrate 5, and a protective layer is provided on the conductive layer 21.
  • a gas barrier layer it is preferable to laminate a gas barrier layer.
  • semiconductor devices such as solar cell devices (organic thin film solar cell devices), display devices, optical sensors, and touch panels can be manufactured.
  • FIG. 2 shows a diagram of a device manufacturing process using the method for manufacturing a laminate according to an embodiment of the present invention
  • FIG. 3 shows another device manufacturing process using the method for manufacturing a laminate according to an embodiment of the present invention. represent a diagram
  • FIGS. 2 and 3 show an example in which two cell units are manufactured in parallel, but only a single cell unit may be manufactured, or three or more cell units may be manufactured in parallel. may be manufactured in parallel.
  • FIG. 2(a) to (f) sequentially show a device manufacturing process for manufacturing a semiconductor device such as a solar cell device in two cell units, and the two cell units are arranged so as to be connected in series on the substrate 5.
  • FIG. 2(a) shows the process of preparing the substrate 5
  • FIG. 2(b) shows the step of preparing the substrate 5 with a plurality of conductive layers 21 separated from each other, the number of which corresponds to the number of cells connected in series.
  • FIG. 2(c) is a step of forming an electron transport layer 22 on the exposed substrate 5 and the conductive layer 21 for each cell
  • FIG. 2(d) is a step of forming an electron transport layer 22 on the exposed substrate 5 and the conductive layer 21 for each cell.
  • the step of forming a photovoltaic layer 23 on the electron transport layer 22 for each cell unit, FIG. 2(e), is the step of forming a hole transport layer 24 on the photovoltaic layer 23 for each cell unit, FIG. 2(f). shows the process of forming the electrode layer 25 on the hole transport layer 24 for each cell unit. Because of the series connection, the electrode layer 25 is formed, for example, so as to be provided also on the conductive layer 21 of an adjacent cell unit.
  • each cell unit laminate consisting of the conductive layer 21, electron transport layer 22, photovoltaic layer 23, hole transport layer 24, and electrode layer 25 is separated at a predetermined interval. It is formed on the substrate 5 adjacent to other stacked cells in units of cells. To form such a laminate, a plurality of containers 1 are placed on the conductive layer 21 so as to be adjacent to each other with a gap between them (FIG. 2(c)).
  • the method described with reference to FIG. 1 is preferably used in the steps of FIGS. 2(c) to (e).
  • the electron transport layer 22 by bringing the container 1 having the opening 2 into contact with the conductive layer 21 and introducing the film material-containing gas 7 ( Figure 2(c)).
  • the photovoltaic layer 23 by introducing a changed film material-containing gas 7 (FIG. 2(d)).
  • the hole transport layer 24 by introducing a changed membrane raw material-containing gas 7 (FIG. 2(e)).
  • the electrode layer 25 may be formed using the container 1 and then etched. As shown in FIGS. 2(c) to 2(e), by using a plurality of containers 1, a plurality of cell units can be manufactured in parallel, and film formation efficiency can be improved. The same applies to FIGS. 3(c) to 3(e), which will be described later.
  • 3(a) to (f) sequentially show another device manufacturing process in which a semiconductor device such as a solar cell device is manufactured in two cell units, and the two cell units are connected in series on the substrate 5. It will be placed in 3(a) shows a step of preparing the substrate 5, and FIG. 3(b) shows a step of preparing a plurality of conductive layers 21 separated from each other on the substrate 5, the number of which corresponds to the number of cell units to be connected in series. 3(c) is a step of forming an electron transport layer 22 on the exposed substrate 5 and the conductive layer 21 for each cell unit, FIG.
  • FIG. 3(d) is a step of forming an electron transport layer 22 on the exposed substrate 5 and the conductive layer 21 for each cell unit
  • the step of forming a photovoltaic layer 23 on the electron transport layer 22 for each cell unit, FIG. 3(e), is the step of forming a hole transport layer 24 on the photovoltaic layer 23 for each cell unit, FIG. 3(f). shows the process of forming the electrode layer 25 on the hole transport layer 24 for each cell unit.
  • the electrode layer 25 is also provided, for example, on the conductive layer 21 of an adjacent cell unit and on the substrate 5 whose upper surface is exposed between the hole transport layer 24 and the conductive layer 21. It is formed so that it is In the step of FIG.
  • the stacked body of each cell unit composed of the conductive layer 21, the electron transport layer 22, the photovoltaic layer 23, the hole transport layer 24, and the electrode layer 25 is separated at a predetermined interval. It is formed on the substrate 5 adjacent to other stacked cells in units of cells. To form such a laminate, a plurality of containers 1 are placed on the conductive layer 21 so as to be adjacent to each other with a gap between them (FIG. 3(c)).
  • the method described with reference to FIG. 1 is preferably used in the steps of FIGS. 3(c) to (e).
  • the container 1 having the opening 2 (the opening 2 has portions having different heights from the top surface of the container 1) is exposed.
  • the electron transport layer 22 is formed (FIG. 3(c)).
  • the photovoltaic layer 23 it is preferable to form the photovoltaic layer 23 by introducing a changed film material-containing gas 7 (FIG. 3(d)).
  • the hole transport layer 24 After forming the photovoltaic layer 23, it is preferable to form the hole transport layer 24 by introducing a changed membrane raw material-containing gas 7 (FIG. 3(e)).
  • the electrode layer 25 may be formed using the container 1, or may be etched after being formed using the container 1.
  • FIG. 4 depicts a film forming apparatus according to an embodiment of the present invention. This apparatus can carry out the method of manufacturing a stacked body described with reference to FIG. 1 and the method of manufacturing a semiconductor device described with reference to FIGS. 2 and 3.
  • a film forming apparatus 10 of the present invention is an apparatus for forming a film on a substrate 5, and includes a holder 9 for holding the substrate 5, and a container 1 provided opposite to the substrate 5. is characterized by having an opening 2 that abuts one main surface side of the substrate 5 and a film raw material-containing gas inlet 3.
  • the container 1 may further include a membrane raw material-containing gas outlet 4. According to the apparatus 10, film formation efficiency can be improved without requiring a metal mask or etching. Further, according to the device 10, it may be possible to reduce costs and suppress pollution of the working environment.
  • the same explanation as above applies to the substrate 5, container 1, opening 2, membrane raw material-containing gas inlet 3, and membrane raw material-containing gas outlet 4 related to the film forming apparatus 10.
  • the holder 9 can hold the substrate 5 so as to face the container 1, for example.
  • the holder 9 includes, for example, a stand on which the substrate 5 is placed, and a device (for example, a fastener, preferably a screw) for fixing the substrate 5.
  • the device 10 further includes a first control mechanism that controls the holder 9 and the container 1 to be movable in a first axial direction so as to move them toward and away from each other.
  • the holder 9 and the container 1 are controlled to be movable in the first axial direction so that they approach each other relatively, so that the opening 2 of the container 1 and the substrate 5 can come into contact with each other, and the film forming chamber 6 It becomes possible to form
  • the holder 9 and the container 1 are controlled to be movable in the first axial direction so that they are relatively spaced apart, so that it is possible to release the abutment between the opening 2 and the substrate 5, and further, the substrate 5 and membrane 8 can also be taken out.
  • the device 10 further includes a second control mechanism that controls the holder 9 to be movable in a second axial direction different from the first axial direction.
  • the holder 9 is controlled to be movable, for example, to a substrate cleaning device connected to the holder 9 in the second axial direction.
  • the contact between the opening 2 and the substrate 5 also referred to as first contact
  • the second control mechanism include, in addition to those described in connection with the first control mechanism, a conveying roller and the like.
  • the film forming apparatus 10 of the present invention may further include an elastic body that seals a peripheral portion where the opening 2 and one main surface side of the substrate 5 are in contact with each other from the outside of the container 1. By sealing the outer periphery of the container 1 with the elastic body, it is possible to prevent the membrane raw material-containing gas 7 from flowing out from the membrane forming chamber 6.
  • the film forming apparatus 10 of the present invention may further include a mechanism for creating a positive pressure inside the container 1.
  • a mechanism for creating a positive pressure inside the container 1 it is possible to prevent outside air from flowing into the film forming chamber 6 from the outside, and it is possible to reduce the influence of oxygen and water on film formation. Further, by combining with the above elastic body, the film 8 can be formed stably.
  • the mechanism for creating a positive pressure inside the container 1 can be controlled by controlling one or both of the amount of gas introduced and the amount of gas discharged.
  • any mechanism can be used as long as it can make the pressure inside the container 1 higher than that outside the container 1, and a mechanism for introducing an inert gas (for example, argon gas, helium gas, neon gas, krypton gas, etc.) is preferable.
  • an inert gas for example, argon gas, helium gas, neon gas, krypton gas, etc.
  • the film forming apparatus 10 of the present invention may further include a mechanism for applying a potential to the container 1 to prevent the film material-containing gas 7 from adhering to the container 1.
  • the charge application mechanism in the film forming apparatus 10 may be the same as that described in the potential application step.
  • the portion where the opening 2 and one main surface side of the substrate 5 come into contact has a labyrinth.
  • the labyrinth has a structure in which both the opening 2 and the substrate 5 have an uneven shape, for example, in the abutting portion, and the uneven shapes interlock with each other alternately. Since the abutting portion has a labyrinth, the abutting portion is stably fixed, and it is possible to prevent the membrane raw material-containing gas from flowing out from the abutting portion.
  • the film forming apparatus 10 is connected to a substrate cleaning apparatus. Since the holder 9 provided in the film forming apparatus 10 is controlled to be movable in the second axis direction, the substrate 5 on which the film has been formed can be transferred as is to the substrate cleaning apparatus.
  • the method for manufacturing a laminate, the method for manufacturing a semiconductor device, and the film forming apparatus of the present invention have been described above, but the present invention is applicable to the field of forming various films, particularly solar cell devices (organic thin film solar cell devices). It can be suitably used in the field of semiconductor devices such as display devices, optical sensors, and touch panels.
  • Container 2 Opening 3: Membrane raw material containing gas inlet 4: Membrane raw material containing gas outlet 5: Substrate 6: Film forming chamber 7: Membrane raw material containing gas 8: Membrane 9: Holder 10: Film forming apparatus 21 : Conductive layer 22: Electron transport layer 23: Photovoltaic layer 24: Hole transport layer 25: Electrode layer

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)

Abstract

The objective of the present invention is to provide: a method for manufacturing a laminate without the need for a metal mask or etching, thereby having an improved film formation efficiency; a method for manufacturing a semiconductor device; and a film forming apparatus.　The present invention relates to a method for manufacturing a laminate including a substrate and a film, the method being characterized by comprising: (1) a step for bringing an opening of a container into contact with one main surface side of the substrate; (2) a step for introducing a gas containing a raw material for film formation into the container; and (3) a step for forming the film on the one main surface side of the substrate by bringing the gas containing a raw material for film formation into contact with the one main surface side of the substrate.

Description

積層体の製造方法、半導体デバイスの製造方法、及び膜形成装置Laminated body manufacturing method, semiconductor device manufacturing method, and film forming apparatus
　本発明は、積層体の製造方法、半導体デバイスの製造方法、及び膜形成装置に関するものである。 The present invention relates to a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a film forming apparatus.
　太陽電池デバイス等の半導体デバイスにおいて、所定の膜を被処理部材（例えば基板）に形成する種々の方法が知られている（特許文献１～５）。
　これらの特許文献１～５において、膜を形成する際の問題点として、作業環境が汚染されること、膜形成材料が基板以外に付着すること、基板及び基板に形成される膜が汚損されること、形成される膜が均一でないこと等が知られている。 In semiconductor devices such as solar cell devices, various methods are known for forming a predetermined film on a member to be processed (for example, a substrate) (Patent Documents 1 to 5).
In these Patent Documents 1 to 5, problems when forming a film include contamination of the working environment, adhesion of the film-forming material to surfaces other than the substrate, and staining of the substrate and the film formed on the substrate. It is known that the formed film is not uniform.
特開平３－２６３７０号公報Japanese Patent Application Publication No. 3-26370 特開平１０－９２８０２号公報Japanese Patent Application Publication No. 10-92802 特開平１１－１３１２３８号公報Japanese Patent Application Publication No. 11-131238 特開２００３－２７３０９７号公報Japanese Patent Application Publication No. 2003-273097 特開２００７－２７５３６号公報Japanese Patent Application Publication No. 2007-27536
　特許文献１は、ミスト発生装置を用いたミストの塗布方法がブース内で行われることを開示する（図１）。特許文献２には、誘電体膜の製造方法に用いる成膜装置として、チャンバ内に基板を置き、ミスト発生器をこのチャンバに接続した装置が記載されている（図１）。特許文献３は、プロセスチャンバー内に、基板を載せる回転ステージと、ミスト噴出手段とを備える誘電体薄膜形成装置を開示する（図１）。特許文献４には、ミスト化した被膜材料溶液を被処理部材の表面に塗布する成膜方法が、処理室内で行われることが教示されている（図２）。特許文献５は、チャンバー内に、ミスト散布部と、基板設置部とを備えるパターン形成装置を有することを開示する（図１）。 Patent Document 1 discloses that a mist application method using a mist generator is performed in a booth (FIG. 1). Patent Document 2 describes an apparatus in which a substrate is placed in a chamber and a mist generator is connected to the chamber as a film forming apparatus used in a method for manufacturing a dielectric film (FIG. 1). Patent Document 3 discloses a dielectric thin film forming apparatus that includes a rotary stage on which a substrate is placed and a mist jetting means in a process chamber (FIG. 1). Patent Document 4 teaches that a film forming method in which a mist coating material solution is applied to the surface of a member to be processed is performed in a processing chamber (FIG. 2). Patent Document 5 discloses that a pattern forming device including a mist dispersion section and a substrate installation section is provided in a chamber (FIG. 1).
　この様に、前記特許文献１～５はいずれも、形成装置内に基板を設置して膜を形成している。特許文献１～５の膜形成によれば、例えば基板を前記装置内に移送して基板を前記装置内で位置合わせする手順等を要するため、また、膜を複数形成する場合に当該装置を複数設置することを要するため、膜形成に要する時間が長くなり、得られる膜の生産性を改善することが求められていた。 In this manner, in all of the above-mentioned Patent Documents 1 to 5, a film is formed by placing a substrate in a forming apparatus. According to the film formation methods disclosed in Patent Documents 1 to 5, for example, steps such as transferring the substrate into the apparatus and aligning the substrate within the apparatus are required; Because of the need for installation, the time required for film formation becomes long, and there has been a need to improve the productivity of the resulting film.
　他方、太陽電池デバイス等の半導体デバイスにおいて、積層された膜に凹凸パターンを形成する為、メタルマスク、エッチングを使用することが知られている。メタルマスク、エッチングは、膜形成の作業環境とは異なる作業環境で使用される場合が多く、作業工程が煩雑となり、かかる点でも膜形成に要する時間が長くなっていた。また、メタルマスク、エッチングに必要な部材も増えコストがかかっており、メタルマスク、エッチングの使用を極力減らすことが望まれる。 On the other hand, in semiconductor devices such as solar cell devices, it is known to use metal masks and etching to form uneven patterns in stacked films. Metal masks and etching are often used in a working environment different from that for film formation, making the work process complicated and also increasing the time required for film formation. Furthermore, the number of members required for metal masks and etching increases, increasing costs, and it is desired to reduce the use of metal masks and etching as much as possible.
　そこで、本発明は、メタルマスク及びエッチングを必要とせず、膜形成効率が改善された、積層体の製造方法、半導体デバイスの製造方法、及び膜形成装置を提供することを目的とする。
　本発明の他の目的は、コストの低減及び作業環境の汚染の抑制を可能とする、積層体の製造方法、半導体デバイスの製造方法、及び膜形成装置を提供することである。 SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a film forming apparatus that do not require a metal mask or etching and have improved film formation efficiency.
Another object of the present invention is to provide a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a film forming apparatus that make it possible to reduce costs and suppress pollution of the working environment.
　本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、容器の開口部を基板に当接させて膜を形成する手段を採用することにより、メタルマスク及びエッチングを必要とせず、膜形成効率が改善されることを見出し、本発明を完成した。 As a result of extensive research in order to solve the above problem, the present inventors have found that by adopting a method of forming a film by bringing the opening of the container into contact with the substrate, metal masks and etching are not required. discovered that the film formation efficiency was improved and completed the present invention.
　上記課題を解決した本発明は、基板と膜とを含む積層体の製造方法であって、（１）開口部を有する容器の前記開口部を前記基板の一方主面側に当接させる工程、（２）前記容器内に膜原料含有ガスを導入する工程、及び、（３）前記膜原料含有ガスを前記基板の前記一方主面側に接触させて前記基板の前記一方主面側に前記膜を形成する工程、を含むことを特徴とする積層体の製造方法である。
　本発明によれば、メタルマスク及びエッチングを必要とせず、膜形成効率を改善することができる。また、本発明によれば、コストの低減及び作業環境の汚染の抑制が可能となり得る。 The present invention, which has solved the above problems, is a method for manufacturing a laminate including a substrate and a film, comprising: (1) bringing the opening of a container having an opening into contact with one main surface side of the substrate; (2) introducing a film material-containing gas into the container; and (3) bringing the film material-containing gas into contact with the one main surface side of the substrate to form the film on the one main surface side of the substrate. A method for manufacturing a laminate, comprising the steps of: forming a laminate.
According to the present invention, film formation efficiency can be improved without requiring a metal mask or etching. Further, according to the present invention, it may be possible to reduce costs and suppress pollution of the working environment.
　前記基板の法線方向からみた前記膜の形状と、前記基板の法線方向からみた前記開口部の形状とは互いに相似であることが好ましい。 It is preferable that the shape of the film viewed from the normal direction of the substrate and the shape of the opening viewed from the normal direction of the substrate are similar to each other.
　前記膜原料含有ガスが、膜形成材料を含む溶液をミスト化したものを含むことが好ましい。 It is preferable that the membrane raw material-containing gas contains a mist of a solution containing the membrane forming material.
　前記膜が、前記一方主面に当接する前記開口部の内側全面に形成されるものであることが好ましい。 It is preferable that the film is formed on the entire inner surface of the opening that comes into contact with the one main surface.
　前記積層体の製造方法は、好ましくは、前記（２）工程の後、前記容器内への膜原料含有ガスの導入を停止することにより膜原料含有ガスの導入停止時間を設ける工程をさらに含み、（膜原料含有ガスの導入時間）／（膜原料含有ガスの導入停止時間）の比が１／４～２である。 Preferably, the method for manufacturing the laminate further includes, after the step (2), providing a time period for stopping the introduction of the membrane raw material-containing gas by stopping the introduction of the membrane raw material-containing gas into the container; The ratio of (introduction time of membrane raw material containing gas)/(introduction stop time of membrane raw material containing gas) is 1/4 to 2.
　前記積層体の製造方法は、好ましくは、（１ａ）前記膜原料含有ガスの前記容器への付着を防止するような電位を前記容器に印加する工程をさらに含む。前記積層体の製造方法は、好ましくは、（４）前記容器に不活性ガスを導入する工程をさらに含む。前記（３）工程において、前記基板を加熱して前記膜を形成することも好ましい。 The method for manufacturing the laminate preferably further includes the step of (1a) applying a potential to the container to prevent the membrane raw material-containing gas from adhering to the container. The method for manufacturing the laminate preferably further includes the step of (4) introducing an inert gas into the container. In the step (3), it is also preferable that the film is formed by heating the substrate.
　前記膜が、導電層、電子輸送層、電極層、光起電力層、ホール輸送層、保護層、ｐ型半導体層、ｎ型半導体層、絶縁層、ガスバリア層、及び接着剤層から選択される１つ以上を含んでいてもよい。前記膜が、太陽電池デバイス等の半導体デバイスに使用されてもよい。 The film is selected from a conductive layer, an electron transport layer, an electrode layer, a photovoltaic layer, a hole transport layer, a protective layer, a p-type semiconductor layer, an n-type semiconductor layer, an insulating layer, a gas barrier layer, and an adhesive layer. It may contain one or more. The film may be used in semiconductor devices such as solar cell devices.
　本発明の別態様は、前記積層体の製造方法により前記積層体を製造する工程を有する半導体デバイスの製造方法である。 Another aspect of the present invention is a method for manufacturing a semiconductor device, which includes the step of manufacturing the laminate using the method for manufacturing a laminate.
　本発明の別態様は、基板に膜を形成する装置であって、前記基板を保持する保持具と、前記基板に対向して設けられる容器とを備え、前記容器は、前記基板の一方主面側に当接する開口部と膜原料含有ガス導入口を有することを特徴とする膜形成装置である。
　本発明の別態様によれば、メタルマスク及びエッチングを必要とせず、膜形成効率を改善することができる。また、本発明によれば、コストの低減及び作業環境の汚染の抑制が可能となり得る。 Another aspect of the present invention is an apparatus for forming a film on a substrate, including a holder for holding the substrate and a container provided opposite to the substrate, the container being arranged on one main surface of the substrate. This is a film forming apparatus characterized by having an opening that abuts on the side and a film raw material containing gas inlet.
According to another aspect of the present invention, film formation efficiency can be improved without requiring a metal mask and etching. Further, according to the present invention, it may be possible to reduce costs and suppress pollution of the working environment.
　前記膜形成装置は、好ましくは、前記保持具と前記容器とを、相対的に接近および離間する第１軸方向に移動可能に制御する第１制御機構をさらに備える。 Preferably, the film forming apparatus further includes a first control mechanism that controls the holder and the container to be movable in a first axial direction so as to move them toward and away from each other.
　前記膜形成装置は、好ましくは、前記保持具を、前記第１軸方向とは異なる第２軸方向に移動可能に制御する第２制御機構をさらに備える。 The film forming apparatus preferably further includes a second control mechanism that controls the holder to be movable in a second axial direction different from the first axial direction.
　前記膜形成装置は、好ましくは、前記開口部と前記基板の前記一方主面側とが当接する周囲部を前記容器の外部から密閉するような弾性体をさらに備える。前記膜形成装置は、好ましくは、前記容器内を陽圧とする機構をさらに備える。
　前記容器は、上記電位の印加のため、導電性の部材を有し、当該部材と他の導電部材との間に設けられる絶縁性の部材を有することが好ましい。前記開口部と前記基板の前記一方主面側とが当接する部分はラビリンスを有していることも好ましい。また、前記膜形成装置は、基板洗浄装置に接続されていることも好ましい。 The film forming apparatus preferably further includes an elastic body that seals a peripheral portion where the opening portion and the one main surface side of the substrate are in contact with each other from the outside of the container. The film forming apparatus preferably further includes a mechanism for creating positive pressure in the container.
Preferably, the container includes an electrically conductive member for applying the potential, and an insulating member provided between the member and another electrically conductive member. It is also preferable that a portion where the opening portion and the one main surface side of the substrate come into contact has a labyrinth. Further, it is also preferable that the film forming apparatus is connected to a substrate cleaning apparatus.
　本発明によれば、メタルマスク及びエッチングを必要とせず、膜形成効率を改善することができる。また、本発明によれば、コストの低減及び作業環境の汚染の抑制が可能となり得る。 According to the present invention, film formation efficiency can be improved without requiring a metal mask or etching. Further, according to the present invention, it may be possible to reduce costs and suppress pollution of the working environment.
図１は、本発明の実施形態に係る積層体の製造方法の概要を表す。FIG. 1 shows an overview of a method for manufacturing a laminate according to an embodiment of the present invention. 図２は、本発明の実施形態に係る積層体の製造方法を用いたデバイス製造工程図を表す。FIG. 2 shows a device manufacturing process diagram using the method for manufacturing a laminate according to an embodiment of the present invention. 図３は、本発明の実施形態に係る積層体の製造方法を用いた他のデバイス製造工程図を表す。FIG. 3 shows another device manufacturing process diagram using the laminate manufacturing method according to the embodiment of the present invention. 図４は、本発明の実施形態に係る膜形成装置を表す。FIG. 4 depicts a film forming apparatus according to an embodiment of the present invention.
　以下、下記実施の形態に基づき本発明をより具体的に説明するが、本発明はもとより下記実施の形態によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。なお、各図面において、便宜上、ハッチングや部材符号等を省略する場合もあるが、かかる場合、明細書や他の図面を参照するものとする。また、図面における種々部材の寸法は、本発明の特徴の理解に資することを優先しているため、実際の寸法とは異なる場合がある。 Hereinafter, the present invention will be explained in more detail based on the following embodiments. However, the present invention is not limited by the following embodiments, and modifications may be made as appropriate within the scope that fits the spirit of the above and below. Of course, additional implementations are also possible, and all of these are included within the technical scope of the present invention. In addition, in each drawing, hatching, member codes, etc. may be omitted for convenience, but in such cases, the specification and other drawings shall be referred to. Further, the dimensions of various members in the drawings are given priority to help understanding the features of the present invention, and therefore may differ from actual dimensions.
１．積層体の製造方法
　図１を参照して、基板と当該基板に形成される膜とを含む積層体の製造方法の基本構成を説明する。図１は、本発明の実施形態に係る積層体の製造方法の概要を表す。 1. Method for manufacturing a laminate The basic configuration of a method for manufacturing a laminate including a substrate and a film formed on the substrate will be described with reference to FIG. FIG. 1 shows an overview of a method for manufacturing a laminate according to an embodiment of the present invention.
　本発明の積層体の製造方法は、基板と膜とを含む積層体の製造方法であって、（１）開口部２を有する容器１の前記開口部２を基板５の一方主面側に当接させる工程（図１（ｉ－１）、（ｉ－２））、（２）前記容器１内に膜原料含有ガス７を導入する工程（図１（ｉｉ））、及び、（３）前記膜原料含有ガス７を前記基板５の前記一方主面側に接触させて前記基板５の前記一方主面側に前記膜８を形成する工程（図１（ｉｉｉ））、を含むことを特徴とする。
　本発明によれば、前記（１）～（３）工程後に容器１の位置を変更することにより前記（１）～（３）工程を連続して行うことが可能である。また、複数の容器を用いて前記（１）～（３）工程を行うことにより複数の膜を並行して形成できる。したがって、膜形成効率を改善することができる。なお、後述するように、容器１の位置変更に先立つ容器１の基板５からの取り外しは（３）工程後に行われるものに限定されず、ゆえに、容器１の位置変更も（３）工程後に行われるものに限定されない。また、本発明によれば、メタルマスク及びエッチングを必要とせずに膜形成することができる。また、本発明によれば、コストの低減及び作業環境の汚染の抑制が可能となり得る。
　本発明において、積層体は、例えば、少なくとも１つの基板と、少なくとも１つの膜を積層してなるものであり、好ましくは、少なくとも１つの基板と、２つ以上の異なる膜を積層してなる。 The method for manufacturing a laminate of the present invention is a method for manufacturing a laminate including a substrate and a film, which includes: (1) placing the opening 2 of a container 1 having an opening 2 on one main surface side of the substrate 5; (2) introducing the membrane raw material-containing gas 7 into the container 1 (FIG. 1 (ii)), and (3) A step of forming the film 8 on the one main surface side of the substrate 5 by bringing the film material-containing gas 7 into contact with the one main surface side of the substrate 5 (FIG. 1(iii)). do.
According to the present invention, the steps (1) to (3) can be performed continuously by changing the position of the container 1 after the steps (1) to (3). Further, by performing the steps (1) to (3) above using a plurality of containers, a plurality of films can be formed in parallel. Therefore, film formation efficiency can be improved. As will be described later, the removal of the container 1 from the substrate 5 prior to changing the position of the container 1 is not limited to being performed after the step (3), and therefore, changing the position of the container 1 is also performed after the step (3). It is not limited to what is shown. Further, according to the present invention, a film can be formed without requiring a metal mask or etching. Further, according to the present invention, it may be possible to reduce costs and suppress pollution of the working environment.
In the present invention, the laminate is, for example, formed by laminating at least one substrate and at least one film, preferably by laminating at least one substrate and two or more different films.
　以下、本発明の積層体の製造方法を各工程に分けて説明する。 Hereinafter, the method for manufacturing a laminate of the present invention will be explained in each step.
（１）工程（当接工程）
　（１）工程は、開口部２を有する容器１の前記開口部２を前記基板５の一方主面側に当接させる工程である。前記（１）工程を行う前に、基板５を準備する工程、開口部２を有する容器１を準備する工程を行ってもよい。
　前記（１）工程は、準備した基板５に対し、開口部２を有する容器１を当接させ（図１（ｉ－１）、（ｉ－２））、基板５と開口部２の当接を維持することが好ましい。当接した容器１及び基板５は、膜形成室６を構成することが好ましい。これにより、後述するように、膜原料含有ガス７の充填、膜原料含有ガス７と基板５の一方主面側との接触、膜８の形成を行うことが可能となる。 (1) Process (contact process)
Step (1) is a step of bringing the opening 2 of the container 1 having the opening 2 into contact with one main surface side of the substrate 5. Before performing the step (1), a step of preparing the substrate 5 and a step of preparing the container 1 having the opening 2 may be performed.
In the step (1), the container 1 having the opening 2 is brought into contact with the prepared substrate 5 (FIGS. 1 (i-1) and (i-2)), and the substrate 5 and the opening 2 are brought into contact. It is preferable to maintain It is preferable that the container 1 and the substrate 5 in contact form a film forming chamber 6 . This makes it possible to fill the film material-containing gas 7, bring the film material-containing gas 7 into contact with one main surface side of the substrate 5, and form the film 8, as will be described later.
　容器１の形状としては、直方体、立方体、円柱、半球等の形状が挙げられる。
　容器１の材質としては、有機材料又は無機材料のいずれが用いられてもよい。
　上述したように容器１の位置を変更することにより例えば前記（１）～（３）工程を連続して行う観点から、容器１は軽量であることが好ましく、容器１の材質は、有機材料であることが好ましく、プラスチックであることがより好ましい。他方、容器１の材質は、無機材料である場合、金属であることがより好ましい。容器１への電位印加により膜原料含有ガスの容器１への付着を防止する観点からは、容器１は、導電性の部材を有し、当該部材と他の導電部材との間に設けられる絶縁部材を有することが好ましい
　容器１は、膜原料含有ガス、水、酸素等に対して耐食性を有していてもよく、フッ素樹脂等でコーティングされていてもよい。 The shape of the container 1 includes shapes such as a rectangular parallelepiped, a cube, a cylinder, and a hemisphere.
As the material of the container 1, either an organic material or an inorganic material may be used.
From the viewpoint of performing, for example, steps (1) to (3) continuously by changing the position of the container 1 as described above, the container 1 is preferably lightweight, and the material of the container 1 is preferably an organic material. Preferably, it is plastic, and more preferably plastic. On the other hand, when the material of the container 1 is an inorganic material, it is more preferably metal. From the viewpoint of preventing membrane raw material-containing gas from adhering to the container 1 by applying a potential to the container 1, the container 1 has an electrically conductive member, and an insulator provided between the member and another electrically conductive member. It is preferable to have a member. The container 1 may have corrosion resistance against membrane raw material-containing gas, water, oxygen, etc., and may be coated with a fluororesin or the like.
　容器１及び開口部２は、基板５及び／又は基板５に積層される層により形成される段差に応じた形状を有していてもよい。また、容器１が有する開口部２の数は、１つ又は２つ以上であってもよい。容器１が２つ以上の開口部２を有する場合、膜形成効率を高めることができる。容器１が２つ以上の開口部２を有する場合、２つ以上の開口部２は、ラインアンドスペース、ハニカム等のパターンを形成してもよい。開口部２が上記形状を有すること、及び／又は、２つ以上の開口部２が上記パターンを形成することにより、メタルマスク、エッチングを使用することなく、形成膜に凹凸パターンを付与することができる。 The container 1 and the opening 2 may have a shape corresponding to the step formed by the substrate 5 and/or the layers laminated on the substrate 5. Further, the number of openings 2 that the container 1 has may be one or more than two. When the container 1 has two or more openings 2, the film formation efficiency can be increased. When the container 1 has two or more openings 2, the two or more openings 2 may form a line-and-space, honeycomb, or other pattern. By having the opening 2 have the above-mentioned shape and/or by having two or more openings 2 forming the above-mentioned pattern, it is possible to impart an uneven pattern to the formed film without using a metal mask or etching. can.
　図１の例では１つの容器１のみが示されるが、２つ以上の容器１が用いられてもよい。この場合、２つ以上の容器１は、連結されていてもよく、所定の間隔を隔てて連結されていてもよい。かかる容器を使用すれば、基板５上の異なる場所に複数の膜を並行して形成でき、膜形成に要する時間を短縮することができ、膜形成効率を改善することができる。 Although only one container 1 is shown in the example of FIG. 1, two or more containers 1 may be used. In this case, two or more containers 1 may be connected or may be connected at a predetermined interval. If such a container is used, a plurality of films can be formed in parallel at different locations on the substrate 5, the time required for film formation can be shortened, and the film formation efficiency can be improved.
　容器１は、膜原料含有ガス導入口３及び膜原料含有ガス排出口４を備えていることが好ましい。膜原料含有ガス導入口３及び膜原料含有ガス排出口４はそれぞれ、少なくとも１つ以上のバルブを備えていることが好ましい。容器１は、１つ又は２つ以上の膜原料含有ガス導入口３を備えていてもよく、また、１つ又は２つ以上の膜原料含有ガス排出口４を備えていてもよい。
　膜原料含有ガス導入口３は、膜原料含有ガスが膜形成室に導入され膜が適切に形成される限り、容器１の任意の場所に設けられてもよく、容器１の上面又は側面に設けられることが好ましい。容器１の側面は、容器１の高さを基準に高さ１／２より上部側を側面上部、高さ１／２より下部側を側面下部とする場合、膜原料含有ガス導入口３は、膜原料含有ガスの拡散及び反応の観点から、容器１の側面上部に設けられることがより好ましい。
　膜原料含有ガス排出口４は、未反応の膜原料含有ガス又は副生成物が適切に容器１から排出される限り、容器１の任意の場所に設けてもよく、容器１の側面に設けられることが好ましく、未反応の膜原料含有ガス又は副生成物を効率的に排出する観点から、容器１の側面下部に設けられることがより好ましい。 Preferably, the container 1 includes a membrane raw material-containing gas inlet 3 and a membrane raw material-containing gas outlet 4. It is preferable that the membrane raw material-containing gas inlet 3 and the membrane raw material-containing gas outlet 4 each include at least one or more valves. The container 1 may be equipped with one or more membrane raw material-containing gas inlets 3, and may also be equipped with one or more membrane raw material-containing gas discharge ports 4.
The membrane raw material-containing gas inlet 3 may be provided at any location in the container 1 as long as the membrane raw material-containing gas is introduced into the film forming chamber and a film is appropriately formed. It is preferable that When the side surface of the container 1 is defined as the side above 1/2 of the height of the container 1 as the upper side, and the side below 1/2 of the height as the lower side, the membrane raw material-containing gas inlet 3 is From the viewpoint of diffusion and reaction of the membrane raw material-containing gas, it is more preferable to provide it on the upper side of the container 1.
The membrane raw material-containing gas outlet 4 may be provided at any location in the container 1, and may be provided on the side surface of the container 1, as long as unreacted membrane raw material-containing gas or byproducts are properly discharged from the container 1. It is more preferable to provide it at the lower side of the container 1 from the viewpoint of efficiently discharging unreacted membrane raw material-containing gas or by-products.
　膜原料含有ガス導入口３は、膜原料含有ガス供給ラインを介して、膜原料含有タンクと接続されていてもよい。膜原料含有タンクは、例えば、膜原料を膜原料含有ガスとする気化又は噴霧手段（例えば加熱手段、バブリング手段、超音波手段）を備えていてもよい。
　具体的には、膜原料含有タンクは、例えば、不活性ガス導入ラインにより不活性ガスが供給され、さらに、当該タンクに充填される膜原料（膜形成材料）をバブリング又は超音波に供した結果の、膜原料含有ガスを供給するものであってもよく、あるいは、不活性ガス導入ラインにより不活性ガスが供給され、当該タンク内の膜材料を加熱して膜原料含有ガスを供給するものであってもよい。 The membrane raw material containing gas inlet 3 may be connected to the membrane raw material containing tank via a membrane raw material containing gas supply line. The membrane raw material-containing tank may be equipped with, for example, vaporization or spraying means (eg, heating means, bubbling means, ultrasonic means) for turning the membrane raw material into a membrane raw material-containing gas.
Specifically, the membrane raw material containing tank is supplied with inert gas through an inert gas introduction line, and the membrane raw material (film forming material) filled in the tank is subjected to bubbling or ultrasonic waves. Alternatively, the inert gas may be supplied through an inert gas introduction line, and the membrane material in the tank may be heated to supply the membrane raw material-containing gas. There may be.
　膜原料含有ガス導入口３は、ノズルを備えていてもよい。ノズルは、振動エネルギーを使用するノズルであることが好ましく、超音波アトマイザーを使用するノズルであることがより好ましい。これにより、膜原料含有ガス７に含まれるミストの大きさをさらに小さくすることができ、膜原料含有ガス７を膜形成室６内でより一層拡散させることができる。 The membrane raw material-containing gas inlet 3 may include a nozzle. The nozzle is preferably a nozzle that uses vibrational energy, more preferably a nozzle that uses an ultrasonic atomizer. Thereby, the size of the mist contained in the membrane raw material containing gas 7 can be further reduced, and the membrane raw material containing gas 7 can be further diffused within the film forming chamber 6.
　基板５は、例えば、有機材料、金属材料、布帛材料、紙材料、セラミック材料、ガラス材料、又はこれらの組み合わせであり、使用されるデバイス（例えば太陽電池デバイス等の半導体デバイス）に応じて選択すればよい。
　基板５は、薄膜を堆積させる基板として使用される。基板５を構成する材料は、例えばＳｉ、Ｇｅ、及びＧａＡｓ等の半導体材料、ガラス、金属（例えばＳＵＳ）、高分子フィルム（例えばポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリカーボネート（ＰＣ）、ポリイミド（ＰＩ）、あるいはポリエステルエラストマー（好ましくはペルプレン（登録商標））、ナイロン）であることが好ましい。
　また、基板５は、ガラスにワニス層が堆積したもの、金属がコーティングされたもの、多層のフィルム等のように、上述した材料が組み合わされた上部基板と下部基板とを含むものであってもよい。
　基板５の大きさは、膜形成効率を改善する観点から、半導体デバイス等を構成するセル単位を複数配置可能な大きさであることが好ましい。
　基板５の形状は、膜形成効率を改善する観点から、フィルム形状又はロール形状であることが好ましい。
　基板５には、他の層が積層されていてもよく、他の層としては、透明導電層、電子輸送層、電極層、（ｐ型半導体層及び／又はｎ型半導体層を含み得る）光起電力層、ホール輸送層、保護層、ｐ型半導体層、ｎ型半導体層、絶縁層、ガスバリア層、及び接着剤層等が挙げられる。本発明では、基板５に直接膜を形成することができ、他の層が積層された基板５に膜を形成することもできる。 The substrate 5 is, for example, an organic material, a metal material, a cloth material, a paper material, a ceramic material, a glass material, or a combination thereof, and should be selected depending on the device used (for example, a semiconductor device such as a solar cell device). Bye.
Substrate 5 is used as a substrate on which thin films are deposited. Materials constituting the substrate 5 include, for example, semiconductor materials such as Si, Ge, and GaAs, glass, metals (for example, SUS), and polymer films (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polycarbonate (PC)). , polyimide (PI), or polyester elastomer (preferably Perprene (registered trademark), nylon).
Further, the substrate 5 may include an upper substrate and a lower substrate in which the above-mentioned materials are combined, such as glass with a varnish layer deposited, metal coated, a multilayer film, etc. good.
From the viewpoint of improving film formation efficiency, the size of the substrate 5 is preferably large enough to accommodate a plurality of cell units constituting a semiconductor device or the like.
The shape of the substrate 5 is preferably a film shape or a roll shape from the viewpoint of improving film formation efficiency.
Other layers may be laminated on the substrate 5, and the other layers include a transparent conductive layer, an electron transport layer, an electrode layer, and an optical layer (which may include a p-type semiconductor layer and/or an n-type semiconductor layer). Examples include an electromotive force layer, a hole transport layer, a protective layer, a p-type semiconductor layer, an n-type semiconductor layer, an insulating layer, a gas barrier layer, and an adhesive layer. In the present invention, the film can be formed directly on the substrate 5, or it is also possible to form the film on the substrate 5 on which other layers are laminated.
　開口部２を有する容器１の前記開口部２を基板５の一方主面側に当接させる手段として、（ａ）容器１の開口部２の一部を基板５に当て、次いで開口部２の残りの部分を順次又は同時に基板５に当てること、（ｂ）容器１の開口部２全体を基板５に同時に当てることが挙げられる。
　基板５に対する容器１の位置決めを調節しながら当接させる観点から、前記（ａ）が好ましい。また、基板５に対する容器１の位置決めの為に画像認識を使うことが好ましい。 As a means for bringing the opening 2 of the container 1 having the opening 2 into contact with one main surface side of the substrate 5, (a) a part of the opening 2 of the container 1 is brought into contact with the substrate 5, and then the opening 2 is brought into contact with the substrate 5; (b) applying the entire opening 2 of the container 1 to the substrate 5 simultaneously; (b) applying the entire opening 2 of the container 1 to the substrate 5 simultaneously.
The above (a) is preferable from the viewpoint of bringing the container 1 into contact with the substrate 5 while adjusting its positioning. Further, it is preferable to use image recognition for positioning the container 1 with respect to the substrate 5.
　本発明の方法において、前記開口部２と前記基板５の一方主面側とが当接する周囲部を前記容器１の外部から密閉するような材料（好ましくは弾性体、より好ましくはゴム弾性体）を容器１の外周部に嵌めてもよい。これにより、容器１の開口部２と基板５との間に隙間が発生することを防止でき、膜原料含有ガス７の容器１からの流出を防止することができる。 In the method of the present invention, a material (preferably an elastic body, more preferably a rubber elastic body) that seals the peripheral area where the opening 2 and one main surface side of the substrate 5 are in contact with each other from the outside of the container 1 may be fitted to the outer periphery of the container 1. Thereby, it is possible to prevent a gap from being generated between the opening 2 of the container 1 and the substrate 5, and to prevent the film material-containing gas 7 from flowing out from the container 1.
（１ａ）工程（電位印加工程）
　本発明の方法は、（１ａ）前記膜原料含有ガス７の前記容器１への付着を防止するような電位を前記容器１に印加する工程をさらに含むことが好ましい。前記（１ａ）工程は、どのタイミングで行ってもよい。
　具体的には、前記（１ａ）工程は、前記（１）工程の前、前記（１）工程の間、前記（１）工程の後に行ってもよく、前記（２）工程の前、前記（２）工程の間、前記（２）工程の後に行ってもよく、前記（３）工程の前、前記（３）工程の間、前記（３）工程の後に行ってもよく、膜８が形成されるまで連続して行ってもよい。なお、本明細書において、或る工程が別の工程の間に行われると説明される場合、当該２つの工程が部分的に並行して実行され得ることも意図されている。 (1a) Process (potential application process)
Preferably, the method of the present invention further includes the step of (1a) applying a potential to the container 1 that prevents the membrane raw material-containing gas 7 from adhering to the container 1. The step (1a) may be performed at any timing.
Specifically, the step (1a) may be performed before the step (1), during the step (1), or after the step (1), or before the step (2), or after the step (2). 2) During the step, it may be performed after the step (2), before the step (3), during the step (3), or after the step (3), and the film 8 is formed. It may be done continuously until it is completed. Note that when a step is described herein as being performed during another step, it is also intended that the two steps may be performed partially in parallel.
　電位印加は、膜原料含有ガス７が有する電荷に応じて調整すればよく、膜原料含有ガス７が有する同極性電荷に帯電させるものであることが好ましく、容器１の側面に電源を接続して、電位を印加することがより好ましい。
　例えば、膜原料含有ガス７がプラスの電荷を有する場合、容器１の側面の内壁がプラスの電荷を帯びるように電位を印加することが好ましく、電源のプラス側を容器１の側面に接続し、電源のマイナス側をアース接続することがより好ましい。
　他方、膜原料含有ガス７がマイナスの電荷を有する場合、容器１の側面の内壁がマイナスの電荷を帯びるように電位を印加することが好ましく、電源のマイナス側を容器１の側面に接続し、電源のプラス側をアース接続することがより好ましい。 The potential application may be adjusted according to the electric charge that the membrane raw material-containing gas 7 has, and is preferably one that charges the membrane raw material-containing gas 7 to the same polar charge. , it is more preferable to apply a potential.
For example, when the membrane raw material-containing gas 7 has a positive charge, it is preferable to apply a potential so that the inner wall of the side surface of the container 1 is charged with a positive charge, and the positive side of the power source is connected to the side surface of the container 1. It is more preferable to connect the negative side of the power supply to ground.
On the other hand, when the membrane raw material-containing gas 7 has a negative charge, it is preferable to apply a potential so that the inner wall of the side surface of the container 1 is charged with a negative charge, and the negative side of the power source is connected to the side surface of the container 1, It is more preferable to connect the positive side of the power supply to ground.
　他方、膜原料含有ガス７が有する電荷を調節してもよく、例えば膜原料含有ガス供給ライン上に電源を設けて電位を印加してもよい。例えば、膜原料含有ガス７が有する電荷をプラス側に帯電させる場合、電源のプラス側を膜原料含有ガス供給ラインに接続し、電源のマイナス側をアース接続することが好ましい。他方、膜原料含有ガス７が有する電荷をマイナス側に帯電させる場合、電源のマイナス側を膜原料含有ガス供給ラインに接続し、電源のプラス側をアース接続することが好ましい。 On the other hand, the electric charge possessed by the membrane raw material-containing gas 7 may be adjusted, for example, a power source may be provided on the membrane raw material-containing gas supply line to apply a potential. For example, when the membrane raw material-containing gas 7 is charged to a positive side, it is preferable to connect the positive side of the power source to the membrane raw material-containing gas supply line and connect the negative side of the power source to ground. On the other hand, when charging the membrane raw material containing gas 7 to a negative side, it is preferable that the negative side of the power source is connected to the membrane raw material containing gas supply line, and the positive side of the power source is connected to ground.
（２）工程（膜原料含有ガス導入工程）
　（２）工程は、前記容器１内に膜原料含有ガス７を導入する工程であり、容器１の開口部２と基板５の一方主面側との当接により形成される膜形成室６に膜原料含有ガス７を導入することが好ましい。すなわち、（２）工程は、（１）工程により開口部２と基板５とが当接されている間に行われることが好ましい。なお、前記（２）工程は、前記（１）工程の前、前記（１）工程の間、前記（１）工程の後に行ってもよいが、膜原料含有ガス７を安定して導入する観点から、前記（１）工程の後に行うことが好ましい。 (2) Process (membrane raw material-containing gas introduction process)
Step (2) is a step of introducing the film material-containing gas 7 into the container 1 into the film forming chamber 6 formed by the contact between the opening 2 of the container 1 and one main surface side of the substrate 5. It is preferable to introduce the membrane raw material-containing gas 7. That is, the step (2) is preferably performed while the opening 2 and the substrate 5 are in contact with each other in the step (1). Note that the step (2) may be performed before the step (1), during the step (1), or after the step (1), but from the viewpoint of stably introducing the membrane raw material-containing gas 7. Therefore, it is preferable to carry out after the step (1).
　膜原料含有ガス７は、液体（溶液ともいう）を含む気体、及び気体のいずれでもよく、液体が気化する事で膜原料が固体微粒子化したもの、液体中に固体が分散しているものを含むものであってもよい。
　膜原料含有ガス７に含まれる膜原料（膜形成材料）は気体、液体、固体のいずれであってもよく、膜形成材料が固体である場合は、溶剤に溶解又は分散させて液体として使用することが好ましく、膜形成材料が液体である場合は、溶剤をさらに加えた液体として使用することが好ましい。 The membrane raw material-containing gas 7 may be either a gas containing a liquid (also called a solution) or a gas, and may be a membrane raw material in which the liquid is vaporized into solid particles, or a membrane raw material in which solids are dispersed in the liquid. It may include.
The membrane raw material (film forming material) contained in the membrane raw material containing gas 7 may be gas, liquid, or solid. If the membrane forming material is solid, it is dissolved or dispersed in a solvent and used as a liquid. When the film-forming material is a liquid, it is preferable to use the film-forming material as a liquid to which a solvent is further added.
　膜原料含有ガス７に含まれる膜形成材料は、無機材料、有機材料のいずれでもよく、所望される膜に応じて適宜選択すればよい。
　膜形成材料は、ナノ粒子で膜形成する材料、ゾルゲル等の反応で膜形成する材料、酸化処理で酸化物を形成して膜形成する材料、窒化処理で窒化物を形成して膜形成する材料等であることが好ましく、ＺｎＯx、ＴｉＯx、ＭｏＯx、ＩＴＯ、ＦＴＯ、酸化アルミニウム、酸化シリコンであることがより好ましい。 The film forming material contained in the film raw material containing gas 7 may be either an inorganic material or an organic material, and may be appropriately selected depending on the desired film.
Film-forming materials include materials that form films with nanoparticles, materials that form films through reactions such as sol-gel, materials that form films by forming oxides through oxidation treatment, and materials that form films by forming nitrides through nitriding treatment. etc., and more preferably ZnOx, TiOx, MoOx, ITO, FTO, aluminum oxide, and silicon oxide.
　溶液に使用される溶媒は、膜形成材料の溶解又は分散が可能となるものであればよく、例えば、エステル溶剤、エーテル溶剤、エーテルエステル溶剤、ケトン溶剤、アルコール溶剤、芳香族炭化水素溶剤、アミド溶剤、水および上記の混合溶液等が挙げられる。
　溶液中の膜形成材料の濃度は、形成される膜や膜形成時間に応じて調整すればよく、１０質量％以下０．１ｐｐｍ以上の範囲が望ましい。 The solvent used in the solution may be any solvent that can dissolve or disperse the film-forming material, such as ester solvents, ether solvents, ether ester solvents, ketone solvents, alcohol solvents, aromatic hydrocarbon solvents, and amide solvents. Examples include solvents, water, and mixed solutions of the above.
The concentration of the film-forming material in the solution may be adjusted depending on the film to be formed and the film-forming time, and is preferably in the range of 10% by mass or less and 0.1 ppm or more.
　膜原料含有ガス７は、キャリアガスとして不活性ガスを含むことが好ましい。
　キャリアガスとして不活性ガスを使用することにより、膜原料含有ガス７に含まれる膜原料（膜形成材料）の濃度を調整することができる。また、不活性ガスは、酸素及び水が除去されていることが好ましいが、ゾルゲル反応を使用して膜を形成する場合、不活性ガスは、水をある程度含んでいてもよい。
　不活性ガスとしては窒素、ヘリウム、ネオン、アルゴン等が挙げられるが、汎用性の観点から、不活性ガスは、好ましくは窒素、ヘリウム、アルゴンであり、より好ましくは窒素、アルゴンである。
　また、本発明において、水と選択的に活性な膜原料に対してクリーンドライエアを使用してもよい。 It is preferable that the membrane raw material-containing gas 7 contains an inert gas as a carrier gas.
By using an inert gas as a carrier gas, the concentration of the membrane raw material (film forming material) contained in the membrane raw material containing gas 7 can be adjusted. Further, it is preferable that oxygen and water are removed from the inert gas, but when forming a film using a sol-gel reaction, the inert gas may contain water to some extent.
Examples of the inert gas include nitrogen, helium, neon, argon, etc. From the viewpoint of versatility, the inert gas is preferably nitrogen, helium, or argon, and more preferably nitrogen or argon.
In addition, in the present invention, clean dry air may be used for membrane raw materials that are selectively active with water.
　膜原料含有ガス７は、膜形成材料を気体又は液体（溶液）として含むことが好ましく、膜形成材料を含む溶液をミスト化したものを含むことがより好ましい。 The membrane raw material-containing gas 7 preferably contains the film forming material as a gas or liquid (solution), and more preferably contains a solution containing the film forming material in the form of a mist.
　ミスト化する方法としては、バブリング；単一噴孔ノズル、衝突型噴射弁、ファンスプレーノズル、渦巻き噴射弁等の圧力エネルギーを使用する方法；振動ノズル、超音波、音響等の振動エネルギーを使用する方法；エアーアシストアトマイザー、エアーブラストアトマイザー等の気体エネルギーを使用する方法；回転噴孔、回転円板、回転カップ、回転ホイール等の遠心力を使用する方法；静電等の電気エネルギーを使用する方法；蒸発凝縮法（液体を加熱して気化させて次いで冷却、凝集して微粒子を生成する方法）、減圧沸騰法（液体を急速に減圧して沸騰させ、蒸気泡が成長して液体を分裂させ微粒子を生成する方法）等の熱エネルギーを使用する方法；バブルの破裂に伴い微粒子を生成する方法等が挙げられる。ミスト化する方法としては、他の公知の手法が用いられてもよい。 Methods for creating mist include bubbling; methods using pressure energy such as single injection hole nozzles, impingement type injection valves, fan spray nozzles, and spiral injection valves; methods using vibration energy such as vibration nozzles, ultrasonic waves, and acoustics. Methods: Methods using gas energy such as air assist atomizers and air blast atomizers; Methods using centrifugal force such as rotating nozzle holes, rotating disks, rotating cups, rotating wheels; Methods using electrical energy such as electrostatics ; evaporation condensation method (a method in which a liquid is heated to vaporize, then cooled and condensed to produce fine particles), vacuum boiling method (a method in which a liquid is rapidly reduced in pressure and boiled, and vapor bubbles grow and the liquid breaks up); methods that use thermal energy, such as a method of generating fine particles; and methods of generating fine particles as a result of bursting of bubbles. Other known methods may be used to create a mist.
　前記（２）工程において、膜原料含有ガス７は、膜原料含有ガス導入口３から導入すればよい。これにより、膜形成室６は、膜原料含有ガス導入口３から導入された膜原料含有ガス７で充填されることが好ましい。
　膜原料含有ガス７の導入量は、形成される膜や膜形成時間に応じて調節可能である。例えば、膜原料含有ガス７の導入量は、容器１の開口部２と基板５の一方主面側の当接により形成される膜形成室６の体積の１／３～２０倍の範囲であることが望ましい。 In the step (2), the membrane raw material containing gas 7 may be introduced from the membrane raw material containing gas inlet 3. Thereby, the film forming chamber 6 is preferably filled with the film material-containing gas 7 introduced from the film material-containing gas inlet 3 .
The amount of the film material-containing gas 7 introduced can be adjusted depending on the film to be formed and the film formation time. For example, the amount of the film material-containing gas 7 introduced is in the range of 1/3 to 20 times the volume of the film forming chamber 6 formed by the contact between the opening 2 of the container 1 and one main surface of the substrate 5. This is desirable.
　前記（２）工程の好ましい態様として、膜原料タンクに充填された膜原料（膜形成材料を含む溶液）を超音波に供して膜形成材料を含む溶液をミスト化したものを、膜原料タンクに供給される不活性ガスで圧送することにより、容器内に膜原料含有ガスを導入することが挙げられる。これにより、膜形成材料をミストとして含む膜原料含有ガスを、膜原料含有ガス導入口から膜形成室に導入することができる。 In a preferred embodiment of the above step (2), the membrane raw material (solution containing the membrane forming material) filled in the membrane raw material tank is subjected to ultrasonic waves to turn the solution containing the membrane forming material into a mist, and then the solution containing the membrane forming material is turned into a mist. An example of this method is to introduce the membrane raw material-containing gas into the container by pressure-feeding the supplied inert gas. Thereby, the membrane raw material containing gas containing the membrane forming material as a mist can be introduced into the membrane forming chamber from the membrane raw material containing gas inlet.
（２ａ）工程（膜原料含有ガス導入の停止工程）
　本発明の方法は、前記（２）工程の後、前記容器１内への膜原料含有ガス７の導入を停止することにより膜原料含有ガス７の導入停止時間を設ける（２ａ）工程をさらに含むことが好ましい。（２ａ）工程は、（１）工程により開口部２と基板５とが当接されている間に行われることが好ましい。
　膜原料含有ガス７の導入を停止して膜原料含有ガス７の導入停止時間を設けることにより、膜形成室６において膜原料含有ガス７をさらに拡散させ、均一な膜を形成することが可能となり、また、膜原料含有ガス７の使用量を低減することも可能となる。 (2a) Process (stopping process of introducing gas containing membrane raw material)
The method of the present invention further includes, after the step (2), a step (2a) of providing a time period for stopping the introduction of the membrane raw material-containing gas 7 by stopping the introduction of the membrane raw material-containing gas 7 into the container 1. It is preferable. The step (2a) is preferably performed while the opening 2 and the substrate 5 are in contact with each other in the step (1).
By stopping the introduction of the membrane raw material-containing gas 7 and providing a time period for stopping the introduction of the membrane raw material-containing gas 7, it becomes possible to further diffuse the membrane raw material-containing gas 7 in the film forming chamber 6 and form a uniform film. Furthermore, it is also possible to reduce the amount of membrane raw material-containing gas 7 used.
　（膜原料含有ガス７の導入時間）／（膜原料含有ガス７の導入停止時間）の比が１／４～２であることが好ましく、１／３～１．５であることがより好ましく、１／２～１であることがさらに好ましい。（膜原料含有ガス７の導入時間）／（膜原料含有ガス７の導入停止時間）の比が上記範囲を満たせば、膜形成室６において膜原料含有ガス７をさらに拡散させ、均一な膜を形成することが可能となり、また、膜原料含有ガス７の使用量を低減することも可能となる。 The ratio of (introduction time of membrane raw material containing gas 7)/(introduction stop time of membrane raw material containing gas 7) is preferably 1/4 to 2, more preferably 1/3 to 1.5, More preferably, it is 1/2 to 1. If the ratio of (introduction time of membrane raw material containing gas 7)/(introduction stop time of membrane raw material containing gas 7) satisfies the above range, the membrane raw material containing gas 7 is further diffused in the film forming chamber 6 to form a uniform film. In addition, it becomes possible to reduce the amount of membrane raw material-containing gas 7 used.
　（２ａ）工程は、前記（２）工程の後であれば、どのタイミングで行ってもよい。
　前記（２ａ）工程は、前記（３）工程の前、前記（３）工程の間、前記（３）工程の後に行ってもよい。
　膜原料含有ガス７の導入停止は、１回又は２回以上行ってもよく、２回以上行う場合、（膜原料含有ガス７の導入時間の合計）／（膜原料含有ガス７の導入停止時間の合計）の比が上記数値範囲を満たせばよい。 Step (2a) may be performed at any timing after step (2).
The step (2a) may be performed before the step (3), during the step (3), or after the step (3).
The introduction of the membrane raw material-containing gas 7 may be stopped once or twice or more, and in the case of twice or more, (total introduction time of the membrane raw material containing gas 7)/(introduction stop time of the membrane raw material containing gas 7) It is sufficient that the ratio of the sum of
（３）工程（膜形成工程）
　本発明の方法において、（３）工程は、前記膜原料含有ガス７を前記基板５の前記一方主面側に接触させて前記基板５の前記一方主面側に膜８を形成する工程である。
　前記（３）工程において、膜原料含有ガス７と基板５の一方主面側との接触は、（１）工程により開口部２と基板５とが当接されている間に行うことが好ましい。
　前記（３）工程は、前記（２）工程の間、前記（２）工程の後に行ってもよく、前記（２）工程の後に行うことが好ましい。 (3) Process (film formation process)
In the method of the present invention, step (3) is a step of bringing the film material-containing gas 7 into contact with the one main surface side of the substrate 5 to form a film 8 on the one main surface side of the substrate 5. .
In the step (3), it is preferable that the film material-containing gas 7 and one main surface side of the substrate 5 come into contact while the opening 2 and the substrate 5 are in contact with each other in the step (1).
The step (3) may be performed during the step (2) or after the step (2), and is preferably performed after the step (2).
　前記（３）工程において、加熱下で膜８を形成してもよく、基板５を加熱して膜８を形成することが好ましい。
　前記（３）工程において、加熱は、容器１を当接したまま行ってもよいが、必要に応じて容器１を取り外して行ってもよく、容器１と基板５との当接を解除して行ってもよい。
　加熱には、基板５を加熱することに加え、又は、基板５を加熱する代わりに、膜原料含有ガス７を加熱すること、及び／又は、容器を加熱すること等も含まれる。
　また、加熱は、前記（２）工程の前（膜原料含有ガスの加熱を除く）、前記（２）工程の間、前記（２）工程の後に行ってもよく、前記（３）工程の前、前記（３）工程の間、前記（３）工程の後に行ってもよい。
　当該加熱により、基板５上に存在する、膜原料含有ガス７に含まれる溶剤を蒸発させること、膜８がゾルゲル反応を伴って基板５に形成される場合、膜形成室６内部又は膜８の水分等によりゾルゲル反応を促進させること、膜８に含まれる有機材料を硬化させること、膜８に含まれる光起電力層がドナーとアクセプターを含む場合、ドナーとアクセプターの相分離を調節することが可能となる。 In the step (3), the film 8 may be formed under heating, and it is preferable to form the film 8 by heating the substrate 5.
In the step (3), the heating may be performed while the container 1 is in contact with the substrate 5, but if necessary, the heating may be performed by removing the container 1, or by releasing the contact between the container 1 and the substrate 5. You may go.
In addition to heating the substrate 5 or instead of heating the substrate 5, heating also includes heating the film material-containing gas 7 and/or heating the container.
Further, heating may be performed before the step (2) (excluding heating of the membrane raw material-containing gas), during the step (2), after the step (2), or before the step (3). , may be carried out during or after the step (3).
The heating evaporates the solvent contained in the film raw material-containing gas 7 present on the substrate 5, and when the film 8 is formed on the substrate 5 with a sol-gel reaction, the inside of the film forming chamber 6 or the inside of the film 8 is heated. Promoting the sol-gel reaction with moisture etc., curing the organic material contained in the film 8, and controlling the phase separation of the donor and acceptor when the photovoltaic layer contained in the film 8 contains a donor and an acceptor. It becomes possible.
　本発明の方法において、前記基板５の法線方向（前記基板５の前記一方主面に対する法線方向ともいう）からみた前記膜８の形状と、前記基板５の法線方向からみた前記開口部２の形状とが互いに相似であることが好ましく、前記基板５の法線方向からみた前記膜８の形状と、前記基板５の法線方向からみた前記開口部２の形状とが互いに合同であることがより好ましい。 In the method of the present invention, the shape of the film 8 as viewed from the normal direction of the substrate 5 (also referred to as the normal direction to the one main surface of the substrate 5) and the opening as seen from the normal direction of the substrate 5. 2 are similar to each other, and the shape of the film 8 viewed from the normal direction of the substrate 5 and the shape of the opening 2 viewed from the normal direction of the substrate 5 are congruent with each other. It is more preferable.
　前記膜８は、前記一方主面に当接する前記開口部２の内側全面に形成されるものであることが好ましい。 It is preferable that the film 8 is formed on the entire inner surface of the opening 2 that comes into contact with the one main surface.
　前記膜８は、導電層、電子輸送層、電極層、光起電力層、ホール輸送層、保護層、ｐ型半導体層、ｎ型半導体層、絶縁層、ガスバリア層、及び接着剤層から選択される１つ以上を含むことが好ましい。
　導電層と電極層は、互いに異なる電極（正極、負極）を構成することが好ましく、導電層は、透明であってもよい。
　前記膜８は、導電層、光起電力層、及び電極層を少なくとも有する膜であることが好ましく、導電層、電子輸送層、光起電力層、ホール輸送層、及び電極層を少なくとも有する膜であることがより好ましい。
　他方、前記膜８は、導電層、ｐ型半導体及び／又はｎ型半導体、並びに電極層を少なくとも有する膜であることが好ましく、導電層、電子輸送層、ｐ型半導体及び／又はｎ型半導体、ホール輸送層、並びに電極層を少なくとも有する膜であることがより好ましい。 The film 8 is selected from a conductive layer, an electron transport layer, an electrode layer, a photovoltaic layer, a hole transport layer, a protective layer, a p-type semiconductor layer, an n-type semiconductor layer, an insulating layer, a gas barrier layer, and an adhesive layer. Preferably, it includes one or more of the following.
The conductive layer and the electrode layer preferably constitute different electrodes (positive electrode, negative electrode), and the conductive layer may be transparent.
The film 8 is preferably a film having at least a conductive layer, a photovoltaic layer, and an electrode layer, and preferably a film having at least a conductive layer, an electron transport layer, a photovoltaic layer, a hole transport layer, and an electrode layer. It is more preferable that there be.
On the other hand, the film 8 is preferably a film having at least a conductive layer, a p-type semiconductor and/or an n-type semiconductor, and an electrode layer; More preferably, the film has at least a hole transport layer and an electrode layer.
（４）工程（不活性ガス導入工程）
　本発明の方法は、（４）工程として、前記容器１に不活性ガスを導入する工程をさらに含むものであってもよい。使用する不活性ガスは、前述したものと同様であってもよい。
　当該工程により、膜原料含有ガス７導入前に膜形成室６に存在する材料を排出すること、膜原料含有ガス７導入時に膜原料含有ガス７を拡散すること、膜原料含有ガス７導入後及び／又は加熱前に膜形成室６に残った材料を排出すること、加熱後に膜形成室６に発生したガス等を排除することが可能となる。
　また、膜８形成後に不活性ガスを供給することより、ミスト及び溶剤の排出を促進することができ、形成した膜８から溶剤を揮発させて膜８中の溶剤濃度をコントロールすることができる。
　不活性ガスの導入量は、膜形成室６の体積１００％に対し、好ましくは１０～５００体積％、より好ましくは２０～４００体積％、さらに好ましくは３０～３００体積％、さらにより好ましくは４０～２００体積％、特に好ましくは５０～１００体積％である。 (4) Process (inert gas introduction process)
The method of the present invention may further include a step (4) of introducing an inert gas into the container 1. The inert gas used may be the same as those described above.
Through this step, the material present in the film forming chamber 6 is discharged before introducing the membrane raw material containing gas 7, the membrane raw material containing gas 7 is diffused when the membrane raw material containing gas 7 is introduced, and after the membrane raw material containing gas 7 is introduced. /Or it becomes possible to discharge the material remaining in the film forming chamber 6 before heating, and to eliminate the gas etc. generated in the film forming chamber 6 after heating.
Further, by supplying an inert gas after forming the film 8, discharge of the mist and solvent can be promoted, and the solvent concentration in the film 8 can be controlled by volatilizing the solvent from the formed film 8.
The amount of inert gas introduced is preferably 10 to 500 volume %, more preferably 20 to 400 volume %, still more preferably 30 to 300 volume %, and even more preferably 40 volume % to 100% volume of the film forming chamber 6. ~200% by volume, particularly preferably 50-100% by volume.
　前記（４）工程は、前記（１）工程の間、前記（１）工程の後に行ってもよく、前記（２）工程の前、前記（２）工程の間、前記（２）工程の後に行ってもよく、前記（３）工程の前、前記（３）工程の間、前記（３）工程の後に行ってもよく、前述したよう前記（３）工程において基板を加熱した後に行ってもよい。 The step (4) may be performed during the step (1), after the step (1), or before the step (2), during the step (2), or after the step (2). It may be performed before the step (3), during the step (3), after the step (3), or after heating the substrate in the step (3) as described above. good.
（５）工程（容器取り外し工程）
　本発明の方法は、（５）工程として、前記容器１を前記一方主面側から取り外す工程をさらに含むものであってもよい。
　当該工程により、容器１の開口部２と基板５との当接を解除して、基板５及び基板５に形成された膜８を取り出すことが可能となる。
　前記容器１を前記一方主面側から取り外す手段としては、手動、所定の搬送用コロ、一軸移動可能な基板ホルダー、ロボットアーム、ロボットハンドを介して容器１を基板５から取り外すこと等が挙げられる。
　前記（５）工程は、前記（３）工程の後に行ってもよく、前記（４）工程の後に行ってもよく、前記（３）工程の加熱の前に行ってもよい。 (5) Process (container removal process)
The method of the present invention may further include a step (5) of removing the container 1 from the one main surface side.
Through this step, it becomes possible to release the contact between the opening 2 of the container 1 and the substrate 5, and to take out the substrate 5 and the film 8 formed on the substrate 5.
Examples of means for removing the container 1 from the one main surface side include removing the container 1 from the substrate 5 manually, using a predetermined conveying roller, a uniaxially movable substrate holder, a robot arm, or a robot hand. .
The step (5) may be performed after the step (3), or after the step (4), or before the heating in the step (3).
　本発明の方法において、前記（１）～（３）工程又は前記（１）～（４）工程を繰り返して行うことが好ましい。
　前記（１）～（３）工程又は前記（１）～（４）工程を繰り返して行う場合、前記（５）工程は、最後の前記（３）工程又は前記（４）工程の後に行うことが好ましく、前記（３）工程において、加熱下で膜を形成する場合に行うことが好ましい。
　また、前記（１）～（３）工程又は前記（１）～（４）工程を行なった後、前記（１）工程を省略して前記（２）～（３）工程又は前記（２）～（４）工程を行ってもよい。
　これらにより、異なる複数膜を連続して形成することが可能となり、膜形成に要する時間を短縮でき、かつ膜形成効率を改善することができる。
　異なる膜を形成する際、膜原料含有ガス７に使用される膜形成材料や不活性ガスを変更してもよく、容器１の開口部２の形状を変更することにより凹凸形状を膜８に付与してもよい。 In the method of the present invention, it is preferable to repeat steps (1) to (3) or steps (1) to (4).
When steps (1) to (3) or steps (1) to (4) are repeated, step (5) may be performed after the last step (3) or step (4). Preferably, in the step (3), this is preferably carried out when forming a film under heating.
Further, after performing the steps (1) to (3) or the steps (1) to (4), the step (1) may be omitted and the steps (2) to (3) or the steps (2) to (4) Steps may be performed.
These make it possible to continuously form a plurality of different films, shorten the time required for film formation, and improve film formation efficiency.
When forming different films, the film forming material and inert gas used for the film raw material containing gas 7 may be changed, and by changing the shape of the opening 2 of the container 1, an uneven shape can be imparted to the film 8. You may.
　本発明の方法において、容器１の開口部２と膜８との接触部分に均一でない膜が形成されている場合には、レーザー又はカッター等を用いて不要な部分を膜から切除してもよい。また溶剤を乾燥させる前に不要な部分をふき取る操作をしてもよい。また、基板５及び基板５上に形成された膜８は封止工程に供されてもよい。 In the method of the present invention, if a non-uniform film is formed at the contact area between the opening 2 of the container 1 and the film 8, unnecessary portions may be cut off from the film using a laser, a cutter, etc. . Additionally, unnecessary portions may be wiped off before drying the solvent. Further, the substrate 5 and the film 8 formed on the substrate 5 may be subjected to a sealing process.
　本発明において、基板５上に、導電層２１、電子輸送層２２、光起電力層２３、ホール輸送層２４及び電極層２５の順に積層することが好ましく、電極層２５の上に保護層、ガスバリア層を積層することが好ましい。
　また、本発明において、基板５上に、電極層２５、ホール輸送層２４、光起電力層２３、電子輸送層２２、導電層２１の順に積層することが好ましく、導電層２１の上に保護層、ガスバリア層を積層することが好ましい。
　本発明の方法によれば、太陽電池デバイス（有機薄膜太陽電池デバイス）、表示デバイス、光センサー、及びタッチパネル等の半導体デバイスを製造することができる。 In the present invention, it is preferable that a conductive layer 21, an electron transport layer 22, a photovoltaic layer 23, a hole transport layer 24, and an electrode layer 25 are laminated in this order on the substrate 5, and a protective layer and a gas barrier layer are formed on the electrode layer 25. Preferably, the layers are laminated.
Further, in the present invention, it is preferable that an electrode layer 25, a hole transport layer 24, a photovoltaic layer 23, an electron transport layer 22, and a conductive layer 21 are laminated in this order on the substrate 5, and a protective layer is provided on the conductive layer 21. , it is preferable to laminate a gas barrier layer.
According to the method of the present invention, semiconductor devices such as solar cell devices (organic thin film solar cell devices), display devices, optical sensors, and touch panels can be manufactured.
太陽電池デバイス等の半導体デバイスの製造方法
　図２及び図３を参照して、太陽電池デバイス等の半導体デバイスの製造方法を具体的に説明する。図２は、本発明の実施形態に係る積層体の製造方法を用いたデバイス製造工程図を表し、図３は、本発明の実施形態に係る積層体の製造方法を用いた他のデバイス製造工程図を表す。以下、図２及び図３では、２つのセル単位が並行して製造される場合の例が示されるが、単一のセル単位のみが製造されるようにしてもよいし、３以上のセル単位が並行して製造されるようにしてもよい。 Method for manufacturing semiconductor devices such as solar cell devices A method for manufacturing semiconductor devices such as solar cell devices will be specifically described with reference to FIGS. 2 and 3. FIG. 2 shows a diagram of a device manufacturing process using the method for manufacturing a laminate according to an embodiment of the present invention, and FIG. 3 shows another device manufacturing process using the method for manufacturing a laminate according to an embodiment of the present invention. represent a diagram In the following, FIGS. 2 and 3 show an example in which two cell units are manufactured in parallel, but only a single cell unit may be manufactured, or three or more cell units may be manufactured in parallel. may be manufactured in parallel.
　図２（ａ）～（ｆ）は、太陽電池デバイス等の半導体デバイスを２つのセル単位で製造するデバイス製造工程を順次示し、２つのセル単位は、基板５上に直列接続されるように配置されることになる。
　図２（ａ）は、基板５を準備する工程、図２（ｂ）は、直列接続されるセル単位の数に応じた数の、互いに分離している複数の導電層２１を、基板５に形成する工程、図２（ｃ）は、各セル単位について、露出している基板５上、及び、導電層２１上に、電子輸送層２２を形成する工程、図２（ｄ）は、各セル単位について電子輸送層２２上に光起電力層２３を形成する工程、図２（ｅ）は、各セル単位について光起電力層２３上にホール輸送層２４を形成する工程、図２（ｆ）は、各セル単位について、ホール輸送層２４上に電極層２５を形成する工程を示す。直列接続のため、当該電極層２５は、例えば、隣接するセル単位の導電層２１上にも設けられるように形成される。図２（ｆ）の工程において、導電層２１、電子輸送層２２、光起電力層２３、ホール輸送層２４、及び電極層２５から構成される各セル単位の積層体は、所定の間隔を空けて、他のセル単位の積層体と隣接して基板５上に形成される。このような積層体の形成のため、複数の容器１が、互いに間隔を空けて隣接するよう、導電層２１上に設置される（図２（ｃ））。 2(a) to (f) sequentially show a device manufacturing process for manufacturing a semiconductor device such as a solar cell device in two cell units, and the two cell units are arranged so as to be connected in series on the substrate 5. will be done.
2(a) shows the process of preparing the substrate 5, and FIG. 2(b) shows the step of preparing the substrate 5 with a plurality of conductive layers 21 separated from each other, the number of which corresponds to the number of cells connected in series. FIG. 2(c) is a step of forming an electron transport layer 22 on the exposed substrate 5 and the conductive layer 21 for each cell, and FIG. 2(d) is a step of forming an electron transport layer 22 on the exposed substrate 5 and the conductive layer 21 for each cell. The step of forming a photovoltaic layer 23 on the electron transport layer 22 for each cell unit, FIG. 2(e), is the step of forming a hole transport layer 24 on the photovoltaic layer 23 for each cell unit, FIG. 2(f). shows the process of forming the electrode layer 25 on the hole transport layer 24 for each cell unit. Because of the series connection, the electrode layer 25 is formed, for example, so as to be provided also on the conductive layer 21 of an adjacent cell unit. In the process shown in FIG. 2(f), each cell unit laminate consisting of the conductive layer 21, electron transport layer 22, photovoltaic layer 23, hole transport layer 24, and electrode layer 25 is separated at a predetermined interval. It is formed on the substrate 5 adjacent to other stacked cells in units of cells. To form such a laminate, a plurality of containers 1 are placed on the conductive layer 21 so as to be adjacent to each other with a gap between them (FIG. 2(c)).
　図２において、図１を参照して説明した方法は、図２（ｃ）～（ｅ）の工程で使用されることが好ましい。例えば導電層２１を基板５に形成した後、開口部２を有する容器１を導電層２１に当接させて膜原料含有ガス７を導入することにより、電子輸送層２２を形成することが好ましい（図２（ｃ））。電子輸送層２２が形成された後、変更した膜原料含有ガス７を導入することにより、光起電力層２３を形成することが好ましい（図２（ｄ））。光起電力層２３を形成した後、変更した膜原料含有ガス７を導入することにより、ホール輸送層２４を形成することが好ましい（図２（ｅ））。
　電極層２５は、容器１を用いて形成した後、エッチングしてもよい。
　図２（ｃ）～（ｅ）に示すように、複数の容器１を使用することにより、複数のセル単位を並行して製造することができ、膜形成効率を改善することができる。後述する図３（ｃ）～（ｅ）についても同様である。 In FIG. 2, the method described with reference to FIG. 1 is preferably used in the steps of FIGS. 2(c) to (e). For example, after forming the conductive layer 21 on the substrate 5, it is preferable to form the electron transport layer 22 by bringing the container 1 having the opening 2 into contact with the conductive layer 21 and introducing the film material-containing gas 7 ( Figure 2(c)). After the electron transport layer 22 is formed, it is preferable to form the photovoltaic layer 23 by introducing a changed film material-containing gas 7 (FIG. 2(d)). After forming the photovoltaic layer 23, it is preferable to form the hole transport layer 24 by introducing a changed membrane raw material-containing gas 7 (FIG. 2(e)).
The electrode layer 25 may be formed using the container 1 and then etched.
As shown in FIGS. 2(c) to 2(e), by using a plurality of containers 1, a plurality of cell units can be manufactured in parallel, and film formation efficiency can be improved. The same applies to FIGS. 3(c) to 3(e), which will be described later.
　図３（ａ）～（ｆ）は、太陽電池デバイス等の半導体デバイスを２つのセル単位で製造する他のデバイス製造工程を順次示し、２つのセル単位は、基板５上に直列接続されるように配置されることになる。
　図３（ａ）は、基板５を準備する工程、図３（ｂ）は、直列接続されるセル単位の数に応じた数の、互いに分離している複数の導電層２１を、基板５に形成する工程、図３（ｃ）は、各セル単位について、露出している基板５上、及び、導電層２１上に、電子輸送層２２を形成する工程、図３（ｄ）は、各セル単位について電子輸送層２２上に光起電力層２３を形成する工程、図３（ｅ）は、各セル単位について光起電力層２３上にホール輸送層２４を形成する工程、図３（ｆ）は、各セル単位について、ホール輸送層２４上に電極層２５を形成する工程を示す。直列接続のため、当該電極層２５は、例えば、隣接するセル単位の導電層２１上、及び、当該ホール輸送層２４と当該導電層２１の間で上面が露出している基板５上にも設けられるように形成される。図３（ｆ）の工程において、導電層２１、電子輸送層２２、光起電力層２３、ホール輸送層２４、及び電極層２５から構成される各セル単位の積層体は、所定の間隔を空けて、他のセル単位の積層体と隣接して基板５上に形成される。このような積層体の形成のため、複数の容器１が、互いに間隔を空けて隣接するよう、導電層２１上に設置される（図３（ｃ））。 3(a) to (f) sequentially show another device manufacturing process in which a semiconductor device such as a solar cell device is manufactured in two cell units, and the two cell units are connected in series on the substrate 5. It will be placed in
3(a) shows a step of preparing the substrate 5, and FIG. 3(b) shows a step of preparing a plurality of conductive layers 21 separated from each other on the substrate 5, the number of which corresponds to the number of cell units to be connected in series. 3(c) is a step of forming an electron transport layer 22 on the exposed substrate 5 and the conductive layer 21 for each cell unit, FIG. 3(d) is a step of forming an electron transport layer 22 on the exposed substrate 5 and the conductive layer 21 for each cell unit, The step of forming a photovoltaic layer 23 on the electron transport layer 22 for each cell unit, FIG. 3(e), is the step of forming a hole transport layer 24 on the photovoltaic layer 23 for each cell unit, FIG. 3(f). shows the process of forming the electrode layer 25 on the hole transport layer 24 for each cell unit. For series connection, the electrode layer 25 is also provided, for example, on the conductive layer 21 of an adjacent cell unit and on the substrate 5 whose upper surface is exposed between the hole transport layer 24 and the conductive layer 21. It is formed so that it is In the step of FIG. 3(f), the stacked body of each cell unit composed of the conductive layer 21, the electron transport layer 22, the photovoltaic layer 23, the hole transport layer 24, and the electrode layer 25 is separated at a predetermined interval. It is formed on the substrate 5 adjacent to other stacked cells in units of cells. To form such a laminate, a plurality of containers 1 are placed on the conductive layer 21 so as to be adjacent to each other with a gap between them (FIG. 3(c)).
　図３において、図１を参照して説明した方法は、図３（ｃ）～（ｅ）の工程で使用されることが好ましい。図３の例では、例えば導電層２１を基板５に形成した後、開口部２を有する容器１（開口部２は容器１の上面からの高さが異なる部分を有する。）を、露出している基板５、及び、導電層２１に当接させて膜原料含有ガス７を導入することにより、電子輸送層２２が形成される（図３（ｃ））。電子輸送層２２が形成された後、変更した膜原料含有ガス７を導入することにより、光起電力層２３を形成することが好ましい（図３（ｄ））。光起電力層２３を形成した後、変更した膜原料含有ガス７を導入することにより、ホール輸送層２４を形成することが好ましい（図３（ｅ））。
　電極層２５は、容器１を用いて形成してもよく、容器１を用いて形成した後、エッチングしてもよい。 In FIG. 3, the method described with reference to FIG. 1 is preferably used in the steps of FIGS. 3(c) to (e). In the example of FIG. 3, for example, after the conductive layer 21 is formed on the substrate 5, the container 1 having the opening 2 (the opening 2 has portions having different heights from the top surface of the container 1) is exposed. By introducing the film material-containing gas 7 into contact with the substrate 5 and the conductive layer 21, the electron transport layer 22 is formed (FIG. 3(c)). After the electron transport layer 22 is formed, it is preferable to form the photovoltaic layer 23 by introducing a changed film material-containing gas 7 (FIG. 3(d)). After forming the photovoltaic layer 23, it is preferable to form the hole transport layer 24 by introducing a changed membrane raw material-containing gas 7 (FIG. 3(e)).
The electrode layer 25 may be formed using the container 1, or may be etched after being formed using the container 1.
２．膜形成装置
　図４を参照して、本発明の膜形成装置の基本構成を説明する。図４は、本発明の実施形態に係る膜形成装置を表す。当該装置は、図１を参照して説明した積層体の製造方法、ならびに、図２および図３を参照して説明した半導体デバイスの製造方法を実施可能である。 2. Film Forming Apparatus The basic configuration of the film forming apparatus of the present invention will be explained with reference to FIG. FIG. 4 depicts a film forming apparatus according to an embodiment of the present invention. This apparatus can carry out the method of manufacturing a stacked body described with reference to FIG. 1 and the method of manufacturing a semiconductor device described with reference to FIGS. 2 and 3.
　本発明の膜形成装置１０は、基板５に膜を形成する装置であって、前記基板５を保持する保持具９と、前記基板５に対向して設けられる容器１とを備え、前記容器１は、前記基板５の一方主面側に当接される開口部２と膜原料含有ガス導入口３を有することを特徴とする。容器１は、膜原料含有ガス排出口４をさらに有していてもよい。
　前記装置１０によれば、メタルマスク及びエッチングを必要とせず、膜形成効率を改善することができる。また、前記装置１０によれば、コストの低減及び作業環境の汚染の抑制が可能とされ得る。
　膜形成装置１０に係る基板５、容器１、開口部２、膜原料含有ガス導入口３、及び膜原料含有ガス排出口４については、前述したのと同様の説明が成り立つ。 A film forming apparatus 10 of the present invention is an apparatus for forming a film on a substrate 5, and includes a holder 9 for holding the substrate 5, and a container 1 provided opposite to the substrate 5. is characterized by having an opening 2 that abuts one main surface side of the substrate 5 and a film raw material-containing gas inlet 3. The container 1 may further include a membrane raw material-containing gas outlet 4.
According to the apparatus 10, film formation efficiency can be improved without requiring a metal mask or etching. Further, according to the device 10, it may be possible to reduce costs and suppress pollution of the working environment.
The same explanation as above applies to the substrate 5, container 1, opening 2, membrane raw material-containing gas inlet 3, and membrane raw material-containing gas outlet 4 related to the film forming apparatus 10.
　保持具９は、例えば基板５を容器１に対向するように保持可能である。
　保持具９は、例えば基板５を載せる台、基板５を固定する器具（例えば留め具、好ましくはネジ）を備えていることが好ましい。 The holder 9 can hold the substrate 5 so as to face the container 1, for example.
Preferably, the holder 9 includes, for example, a stand on which the substrate 5 is placed, and a device (for example, a fastener, preferably a screw) for fixing the substrate 5.
　前記装置１０は、前記保持具９と前記容器１とを、相対的に接近および離間する第１軸方向に移動可能に制御する第１制御機構をさらに備えることが好ましい。
　前記保持具９と前記容器１は、相対的に接近する第１軸方向に移動可能に制御されることにより、容器１の開口部２と基板５との当接が可能となり、膜形成室６の形成が可能となる。
　他方、前記保持具９と前記容器１は、相対的に離間する第１軸方向に移動可能に制御されることにより、開口部２と基板５との当接解除が可能となり、さらには、基板５と膜８の取り出し等も可能となる。 Preferably, the device 10 further includes a first control mechanism that controls the holder 9 and the container 1 to be movable in a first axial direction so as to move them toward and away from each other.
The holder 9 and the container 1 are controlled to be movable in the first axial direction so that they approach each other relatively, so that the opening 2 of the container 1 and the substrate 5 can come into contact with each other, and the film forming chamber 6 It becomes possible to form
On the other hand, the holder 9 and the container 1 are controlled to be movable in the first axial direction so that they are relatively spaced apart, so that it is possible to release the abutment between the opening 2 and the substrate 5, and further, the substrate 5 and membrane 8 can also be taken out.
　前記装置１０は、前記保持具９を、前記第１軸方向とは異なる第２軸方向に移動可能に制御する第２制御機構をさらに備えることも好ましい。当該制御では、保持具９が、例えば、保持具９の第２軸方向に接続される基板洗浄装置に、移動可能に制御されることがより好ましい。
　当該制御によると、開口部２と基板５との当接（第一当接ともいう）を解除して開口部２と基板５の異なる位置とを当接（第二当接ともいう）させることも可能となり得、ゆえに、膜形成に要する時間を短縮でき、膜形成効率を改善することが可能となりうる。
　第１制御機構としては、ロボットアーム、ロボットハンド、基板ホルダ等が挙げられ、第２制御機構としては、上記第１制御機構で説明したものに加えて、搬送用コロ等が挙げられる。 It is also preferable that the device 10 further includes a second control mechanism that controls the holder 9 to be movable in a second axial direction different from the first axial direction. In this control, it is more preferable that the holder 9 is controlled to be movable, for example, to a substrate cleaning device connected to the holder 9 in the second axial direction.
According to the control, the contact between the opening 2 and the substrate 5 (also referred to as first contact) is released, and the opening 2 and the substrate 5 are brought into contact at a different position (also referred to as second contact). Therefore, it may be possible to shorten the time required for film formation and improve film formation efficiency.
Examples of the first control mechanism include a robot arm, a robot hand, a substrate holder, etc., and examples of the second control mechanism include, in addition to those described in connection with the first control mechanism, a conveying roller and the like.
　本発明の膜形成装置１０は、前記開口部２と前記基板５の一方主面側とが当接する周囲部を前記容器１の外部から密閉するような弾性体をさらに備えていてもよい。当該弾性体で容器１の外周部を密閉することにより、膜形成室６から膜原料含有ガス７の流出を防止することができる。 The film forming apparatus 10 of the present invention may further include an elastic body that seals a peripheral portion where the opening 2 and one main surface side of the substrate 5 are in contact with each other from the outside of the container 1. By sealing the outer periphery of the container 1 with the elastic body, it is possible to prevent the membrane raw material-containing gas 7 from flowing out from the membrane forming chamber 6.
　本発明の膜形成装置１０は、前記容器１内を陽圧とする機構をさらに備えていてもよい。容器１内を陽圧とすることで外気が膜形成室６内部に外部から流入することを防止することができ、膜形成における酸素及び水の影響を低減することができる。また、上記弾性体と組み合わせることにより、膜８の形成を安定して行うことができる。
　容器１内を陽圧とする機構は、ガスの導入量と排出量の片方あるいは両方を制御することでコントロールできる。容器１外部よりも容器１内部の気圧が高い状態にできるものであればよく、不活性ガス（例えばアルゴンガス、ヘリウムガス、ネオンガス、クリプトンガス等）を導入する機構であることが好ましい。 The film forming apparatus 10 of the present invention may further include a mechanism for creating a positive pressure inside the container 1. By creating a positive pressure inside the container 1, it is possible to prevent outside air from flowing into the film forming chamber 6 from the outside, and it is possible to reduce the influence of oxygen and water on film formation. Further, by combining with the above elastic body, the film 8 can be formed stably.
The mechanism for creating a positive pressure inside the container 1 can be controlled by controlling one or both of the amount of gas introduced and the amount of gas discharged. Any mechanism can be used as long as it can make the pressure inside the container 1 higher than that outside the container 1, and a mechanism for introducing an inert gas (for example, argon gas, helium gas, neon gas, krypton gas, etc.) is preferable.
　本発明の膜形成装置１０は、前記膜原料含有ガス７の前記容器１への付着を防止するような電位を前記容器１に印加する機構をさらに備えていてもよい。膜形成装置１０における電荷印加機構は、前記電位印加工程で説明したものと同様であってもよい。 The film forming apparatus 10 of the present invention may further include a mechanism for applying a potential to the container 1 to prevent the film material-containing gas 7 from adhering to the container 1. The charge application mechanism in the film forming apparatus 10 may be the same as that described in the potential application step.
　本発明において、前記開口部２と前記基板５の一方主面側とが当接する部分はラビリンスを有していることも好ましい。
　ラビリンスは、例えば当接する部分において、開口部２と基板５の両方が、凹凸形状を有しており、凹凸形状が互い違いに噛み合っている構造であることが好ましい。
　当接する部分がラビリンスを有することで、当接する部分が安定して固定され、当接する部分からの膜原料含有ガスの流出を防止することができる。 In the present invention, it is also preferable that the portion where the opening 2 and one main surface side of the substrate 5 come into contact has a labyrinth.
It is preferable that the labyrinth has a structure in which both the opening 2 and the substrate 5 have an uneven shape, for example, in the abutting portion, and the uneven shapes interlock with each other alternately.
Since the abutting portion has a labyrinth, the abutting portion is stably fixed, and it is possible to prevent the membrane raw material-containing gas from flowing out from the abutting portion.
　また、前記膜形成装置１０は、基板洗浄装置に接続されていることも好ましい。
　前記膜形成装置１０に設けられている保持具９は、第２軸方向に移動可能に制御されていることから、膜を形成した基板５をそのまま基板洗浄装置に移送することが可能となる。 Further, it is also preferable that the film forming apparatus 10 is connected to a substrate cleaning apparatus.
Since the holder 9 provided in the film forming apparatus 10 is controlled to be movable in the second axis direction, the substrate 5 on which the film has been formed can be transferred as is to the substrate cleaning apparatus.
　以上、本発明の積層体の製造方法、半導体デバイスの製造方法、及び膜形成装置を説明したが、本発明は、種々の膜を形成する分野、特に、太陽電池デバイス（有機薄膜太陽電池デバイス）、表示デバイス、光センサー、及びタッチパネル等の半導体デバイスの分野に好適に利用することが可能である。 The method for manufacturing a laminate, the method for manufacturing a semiconductor device, and the film forming apparatus of the present invention have been described above, but the present invention is applicable to the field of forming various films, particularly solar cell devices (organic thin film solar cell devices). It can be suitably used in the field of semiconductor devices such as display devices, optical sensors, and touch panels.
　本願は、２０２２年６月３日に出願された日本国特許出願第２０２２－０９１１５８号に基づく優先権の利益を主張するものである。２０２２年６月３日に出願された日本国特許出願第２０２２－０９１１５８号の明細書の全内容が、本願に参考のため援用される。 This application claims the benefit of priority based on Japanese Patent Application No. 2022-091158 filed on June 3, 2022. The entire contents of the specification of Japanese Patent Application No. 2022-091158 filed on June 3, 2022 are incorporated by reference into this application.
　１：容器
　２：開口部
　３：膜原料含有ガス導入口
　４：膜原料含有ガス排出口
　５：基板
　６：膜形成室
　７：膜原料含有ガス
　８：膜
　９：保持具
　１０：膜形成装置
　２１：導電層
　２２：電子輸送層
　２３：光起電力層
　２４：ホール輸送層
　２５：電極層  1: Container 2: Opening 3: Membrane raw material containing gas inlet 4: Membrane raw material containing gas outlet 5: Substrate 6: Film forming chamber 7: Membrane raw material containing gas 8: Membrane 9: Holder 10: Film forming apparatus 21 : Conductive layer 22: Electron transport layer 23: Photovoltaic layer 24: Hole transport layer 25: Electrode layer

Claims (15)

  1. 　基板と膜とを含む積層体の製造方法であって、
    　（１）開口部を有する容器の前記開口部を前記基板の一方主面側に当接させる工程、
    　（２）前記容器内に膜原料含有ガスを導入する工程、及び、
    　（３）前記膜原料含有ガスを前記基板の前記一方主面側に接触させて前記基板の前記一方主面側に前記膜を形成する工程、
    　を含むことを特徴とする積層体の製造方法。     A method for manufacturing a laminate including a substrate and a film, the method comprising:
    (1) a step of bringing the opening of a container having an opening into contact with one main surface side of the substrate;
    (2) introducing a membrane raw material-containing gas into the container, and
    (3) forming the film on the one main surface side of the substrate by bringing the film material-containing gas into contact with the one main surface side of the substrate;
    A method for producing a laminate, comprising:
  2. 　前記基板の法線方向からみた前記膜の形状と、前記基板の法線方向からみた前記開口部の形状とは互いに相似である請求項１に記載の方法。 The method according to claim 1, wherein the shape of the film viewed from the normal direction of the substrate and the shape of the opening viewed from the normal direction of the substrate are similar to each other.
  3. 　前記膜原料含有ガスが、膜形成材料を含む溶液をミスト化したものを含む請求項１に記載の方法。 The method according to claim 1, wherein the membrane raw material-containing gas includes a mist of a solution containing the membrane forming material.
  4. 　前記膜が、前記一方主面に当接する前記開口部の内側全面に形成されるものである請求項１～３のいずれかに記載の方法。 The method according to any one of claims 1 to 3, wherein the film is formed on the entire inner surface of the opening that abuts the one principal surface.
  5. 　前記（２）工程の後、前記容器内への膜原料含有ガスの導入を停止することにより膜原料含有ガスの導入停止時間を設ける工程をさらに含み、（膜原料含有ガスの導入時間）／（膜原料含有ガスの導入停止時間）の比が１／４～２である請求項１～３のいずれかに記載の方法。 After the step (2), the step further includes a step of providing a stop time for the introduction of the membrane raw material containing gas by stopping the introduction of the membrane raw material containing gas into the container, (introduction time of the membrane raw material containing gas)/( The method according to any one of claims 1 to 3, wherein the ratio of introduction and stop time of membrane raw material-containing gas is 1/4 to 2.
  6. 　（１ａ）前記膜原料含有ガスの前記容器への付着を防止するような電位を前記容器に印加する工程をさらに含む請求項１～３のいずれかに記載の方法。 The method according to any one of claims 1 to 3, further comprising the step of (1a) applying a potential to the container to prevent the film material-containing gas from adhering to the container.
  7. 　（４）前記容器に不活性ガスを導入する工程をさらに含む請求項１～３のいずれかに記載の方法。 The method according to any one of claims 1 to 3, further comprising the step of (4) introducing an inert gas into the container.
  8. 　前記（３）工程において、前記基板を加熱して前記膜を形成する請求項１～３のいずれかに記載の方法。 The method according to any one of claims 1 to 3, wherein in the step (3), the film is formed by heating the substrate.
  9. 　前記膜が、導電層、電子輸送層、電極層、光起電力層、ホール輸送層、保護層、ｐ型半導体層、ｎ型半導体層、絶縁層、ガスバリア層、及び接着剤層から選択される１つ以上を含む請求項１～３のいずれかに記載の方法。 The film is selected from a conductive layer, an electron transport layer, an electrode layer, a photovoltaic layer, a hole transport layer, a protective layer, a p-type semiconductor layer, an n-type semiconductor layer, an insulating layer, a gas barrier layer, and an adhesive layer. 4. A method according to any one of claims 1 to 3, comprising one or more.
  10. 　請求項１～３のいずれかに記載の方法により前記積層体を製造する工程を有する半導体デバイスの製造方法。 A method for manufacturing a semiconductor device, comprising the step of manufacturing the laminate by the method according to any one of claims 1 to 3.
  11. 　基板に膜を形成する装置であって、
    　前記基板を保持する保持具と、
    　前記基板に対向して設けられる容器と
    　を備え、
    　前記容器は、前記基板の一方主面側に当接する開口部と膜原料含有ガス導入口を有する
    　ことを特徴とする膜形成装置。     An apparatus for forming a film on a substrate,
    a holder that holds the substrate;
    and a container provided opposite to the substrate,
    A film forming apparatus characterized in that the container has an opening that abuts one principal surface of the substrate and a film raw material-containing gas inlet.
  12. 　前記保持具と前記容器とを、相対的に接近および離間する第１軸方向に移動可能に制御する第１制御機構をさらに備える請求項１１に記載の装置。 12. The apparatus according to claim 11, further comprising a first control mechanism that controls the holder and the container to be movable in a first axial direction so as to move them toward and away from each other.
  13. 　前記保持具を、前記第１軸方向とは異なる第２軸方向に移動可能に制御する第２制御機構をさらに備える請求項１２に記載の装置。 The apparatus according to claim 12, further comprising a second control mechanism that controls the holder to be movable in a second axial direction different from the first axial direction.
  14. 　前記開口部と前記基板の前記一方主面側とが当接する周囲部を前記容器の外部から密閉するような弾性体をさらに備える請求項１１又は１２に記載の装置。 The device according to claim 11 or 12, further comprising an elastic body that seals a peripheral portion where the opening portion and the one main surface side of the substrate are in contact with each other from the outside of the container.
  15. 　前記容器内を陽圧とする機構をさらに備える請求項１１又は１２に記載の装置。 The device according to claim 11 or 12, further comprising a mechanism for creating positive pressure inside the container.
PCT/JP2023/019053 2022-06-03 2023-05-23 Method for manufacturing laminate, method for manufacturing semiconductor device, and film forming apparatus WO2023234108A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-091158 2022-06-03
JP2022091158 2022-06-03

Publications (1)

Publication Number Publication Date
WO2023234108A1 true WO2023234108A1 (en) 2023-12-07

Family

ID=89024792

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/019053 WO2023234108A1 (en) 2022-06-03 2023-05-23 Method for manufacturing laminate, method for manufacturing semiconductor device, and film forming apparatus

Country Status (1)

Country Link
WO (1) WO2023234108A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0633244A (en) * 1992-07-13 1994-02-08 Ricoh Co Ltd Thin film forming device and operation method therefor
JPH09246193A (en) * 1996-03-04 1997-09-19 Nippon Process Eng Kk Film formation device by chemical gas phase growing method
JPH10306373A (en) * 1997-04-30 1998-11-17 Murata Mfg Co Ltd Mocvd device
JP2004335892A (en) * 2003-05-09 2004-11-25 Asm Japan Kk Thin-film forming apparatus
JP2011224503A (en) * 2010-04-22 2011-11-10 Fujifilm Corp Method and apparatus for manufacturing thin film
JP2012256637A (en) * 2011-06-07 2012-12-27 Philtech Inc Film growth apparatus and manufacturing apparatus of solar cell

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0633244A (en) * 1992-07-13 1994-02-08 Ricoh Co Ltd Thin film forming device and operation method therefor
JPH09246193A (en) * 1996-03-04 1997-09-19 Nippon Process Eng Kk Film formation device by chemical gas phase growing method
JPH10306373A (en) * 1997-04-30 1998-11-17 Murata Mfg Co Ltd Mocvd device
JP2004335892A (en) * 2003-05-09 2004-11-25 Asm Japan Kk Thin-film forming apparatus
JP2011224503A (en) * 2010-04-22 2011-11-10 Fujifilm Corp Method and apparatus for manufacturing thin film
JP2012256637A (en) * 2011-06-07 2012-12-27 Philtech Inc Film growth apparatus and manufacturing apparatus of solar cell

Similar Documents

Publication Publication Date Title
KR20100021460A (en) Method and apparatus for thermal jet printing
KR100934544B1 (en) Apparatus for depositing multilayer coatings on discrete sheets
US20040209190A1 (en) Pattern forming method and apparatus used for semiconductor device, electric circuit, display module, and light emitting device
WO2004070809A1 (en) Method for manufacturing display
JP5988619B2 (en) Film forming apparatus and film forming method
JP3901156B2 (en) Mask forming method and removing method, and semiconductor device, electric circuit, display module, color filter, and light emitting element manufactured by the method
JP2005085799A (en) Film depositing method, method of forming circuit pattern, method of manufacturing semiconductor device, electrooptical device, and electronic apparatus
US20170333936A1 (en) Segmented or selected-area coating
WO2023234108A1 (en) Method for manufacturing laminate, method for manufacturing semiconductor device, and film forming apparatus
TWI233325B (en) Forming method of pattern, manufacturing method of apparatus, optoelectronic device and electronic machine
JP2001332398A (en) Electrostatic misting ionization device and method as well as charged particle conveying ionization device and method
WO2013172403A1 (en) Film-formation device and film-formation method
CN117038518A (en) Control modularized device for non-contact type wafer cleaning
WO2024090226A1 (en) Film forming apparatus, method for producing multilayer body, and method for producing semiconductor device
JP2024106251A (en) Film forming apparatus, laminate manufacturing method, and semiconductor device manufacturing method
JP7105649B2 (en) Substrate processing equipment
CN114178067B (en) Nanometer stamping colloid sputtering device and method
KR20120104876A (en) High aspect ratio pattern printing apparatus using electrospinning
JP2013211366A (en) Thin film formation method using electrostatic coating method
JP2006281070A (en) Ink jet coater
JP2006134826A (en) Manufacturing device of organic el element
KR101527715B1 (en) Apparatus for transfer process of large area nanoscale thin films
JP2004165399A (en) Pattern forming method and apparatus, and electronic device manufactured by the method and mount board
JP4396414B2 (en) Film pattern forming method and film pattern forming apparatus
TWI776399B (en) Wet processing apparatus and wet processing method

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2023573611

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23815867

Country of ref document: EP

Kind code of ref document: A1