Device, method for manufacturing laminate using said device, and method for manufacturing semiconductor device

Abstract

The present invention provides a device which makes it possible to accurately remove a part of a film and reduce damage sustained by a substrate and / or base thin film. This device is for film processing and comprises a processing part that removes a part of the film, said processing part having a fiber-reinforced resin tip section.

Description

Apparatus, laminate manufacturing method using said apparatus, and semiconductor device manufacturing method - Patents.com

[0001] The present invention relates to an apparatus, a method for manufacturing a stack using the apparatus, and a method for manufacturing a semiconductor device.

[0002] Various methods are known for partially removing a film at a predetermined location in a semiconductor device such as a solar cell device. For example, circuit formation in a semiconductor device is mainly performed by lithography. In contrast, for example, in solar cells and some sensors, where the processing dimensions are coarse, mask deposition, laser scribing, or mechanical scribing is used.

[0003] Laser scribing is a method of removing film in the laser irradiated area using laser energy.Mechanical scribing is a method of removing film using mechanical energy.It mainly refers to a method of using mechanical processing for device processing.

[0004] Patent Documents 1 and 2 disclose techniques for performing laser scribing. Patent Document 3 discloses a technique for using mechanical scribing and laser scribing in combination. Patent Documents 4 and 5 disclose techniques for performing mechanical scribing.

[0005] JP 2019-107692 A JP 11-312815 A JP 2013-93375 A JP 2004-115356 A JP 2005-64273 A

[0006] In Patent Documents 1 to 5, problems with film removal include the inability to completely remove the desired areas while completely preventing damage to the areas that should not be processed. Furthermore, altered portions are formed as a result of the processing. More specifically, these problems are as follows:

[0007] First, let's discuss the problems associated with laser scribing. Laser processing involves heat, which can cause thermal damage to some films, resulting in the formation of thermally altered layers. Depending on the material combination, the underlying layer can absorb some of the laser energy, damaging the underlying layer and the substrate. Furthermore, the film removal rate is slow. According to Patent Document 2, the scribed grooves removed by irradiating each thin film suffer from problems such as thermal swelling 21 ( FIG. 8( a) ), residue 24 in the scribed groove ( FIG. 8( b) ), melt drips 25 ( FIG. 8( c) ), and even film quality degradation. While Patent Document 3 describes solutions to these problems, there is still room for improvement. Regarding laser scribing, the insulating separation line created by the light beam is narrow, approximately 100 μm wide, making it difficult to achieve high insulation between the solar cell active area and the peripheral area. Insufficient insulation can lead to leakage current between cells, resulting in reduced module output characteristics. While Patent Document 3 describes solutions to these problems, there is still room for improvement. For example, when a portion of a photoelectric conversion layer is thermally removed by laser scribing, the photoelectric conversion layer cannot be satisfactorily removed due to the low efficiency of converting laser light into heat in the organic semiconductor contained in the photoelectric conversion layer.

[0008] Mechanical scribing is preferable to laser scribing in terms of equipment and ease of processing. However, mechanical scribing also has the following problems. During mechanical scribing, cracks, chips, etc. may occur in the film to be removed, potentially preventing satisfactory properties from being obtained. Furthermore, even when the position of the blade used for processing is controlled, some of the film may remain or the underlying substrate and / or electrode may be damaged. For example, when using the mechanical scribing device described in Patent Document 4, if the tip of the processing part is worn, scribing becomes insufficient, and the intended shape cannot be scribed. While it is known that mechanical scribing can be performed well when the target layer is amorphous, the following problems remain. Transparent electrodes are known to have an amorphous structure (e.g., Patent Document 5), and it has been technically difficult to process the layer above them by mechanical scribing without damaging the amorphous transparent electrode. When mechanically removing, for example, a portion of a photoelectric conversion layer by mechanical scribing, the organic semiconductor contained in the photoelectric conversion layer has greater elasticity than inorganic materials, and therefore it is not possible to completely scrape it off with a sharp blade, or the underlying thin film or substrate that should not be removed may be damaged, making it impossible to form a fine connection wiring path in the underlying thin film or substrate.

[0009] The present invention has been made in view of the above circumstances, and its object is to provide an apparatus that enables a portion of a film to be removed with high precision and damage to a substrate and / or an underlying thin film to be alleviated, a method for manufacturing a laminate using the apparatus, and a method for manufacturing a semiconductor device.

[0010] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that by using a fiber-reinforced resin in a processing section for mechanically removing a portion of the film, the portion of the film can be removed with high precision and scratches on the substrate and / or the underlying thin film can be alleviated, thereby completing the present invention. That is, the present invention can include the following aspects.

[0011] [1] An apparatus for processing a film, the apparatus having a processing unit that removes a portion of the film, the tip of the processing unit being made of fiber-reinforced resin. [2] The apparatus described in [1] above, the apparatus being an apparatus for mechanically removing a portion of the film provided on a substrate, the apparatus having the processing unit that contacts the film to mechanically remove the portion of the film, the apparatus having the processing unit that contacts the film and at least the portion of the processing unit that contacts the film being made of fiber-reinforced resin. [3] The apparatus described in [1] or [2] above, characterized in that the processing unit is brought into contact with the object at a constant pressure during the removal. [4] The apparatus described in [2] or [3] above, characterized in that the apparatus is capable of moving the position of the tip of the processing unit relative to the substrate in the X direction and Y direction parallel to the top surface of a stage on which the substrate is placed, and in the Z direction intersecting the top surface, by moving at least one of the processing unit and the substrate. [5] The apparatus according to any one of [1] to [4] above, characterized in that the fiber-reinforced resin is at least one selected from the group consisting of glass fiber-reinforced resin, carbon fiber-reinforced resin, and Zylon fiber-reinforced resin. [6] The apparatus according to any one of [1] to [5] above, characterized in that the fiber-reinforced resin is at least one selected from the group consisting of glass fiber-reinforced epoxy resin, carbon fiber-reinforced epoxy resin, Zylon fiber-reinforced epoxy resin, and carbon fiber-reinforced polyethylene resin. [7] The apparatus according to any one of [3] to [6] above, characterized in that the pressure is controlled to partially remove an upper layer without damaging a lower layer. [8] The apparatus according to any one of [2] to [7] above, characterized in that the substrate is a roll-to-roll substrate, and the removal is performed by bringing the processing unit into contact with the film provided on the roll-to-roll substrate at a constant pressure and processing it with a roll. [9] A method for producing a laminate, comprising the step of removing a portion of the film using the apparatus according to any one of [1] to [8] above.

[10] A method for manufacturing a semiconductor device, comprising the step of removing a portion of the film using the apparatus according to any one of [1] to [8] above.

[11] The method according to

[10] above, wherein the semiconductor device is a photoelectric conversion element.

[0012] According to the present invention, in an apparatus having a processing part that removes a part of a film, by making the tip part of the processing part a fiber-reinforced resin, it is possible to obtain an apparatus, a method for manufacturing a laminate using the apparatus, and a method for manufacturing a semiconductor device, in which the part of the film is accurately removed and scratches on the substrate and / or underlying thin film are alleviated.

[0013] 1A to 1B show an example of the configuration of an apparatus according to the first embodiment. FIGS. 2A to 2C are diagrams for explaining several examples of the shape of the processing portion of the apparatus according to the first embodiment. FIGS. 3A to 3G are diagrams for explaining an example of a method for manufacturing a stacked body and a method for manufacturing a semiconductor device according to the first embodiment. FIGS. 4A to 4H are diagrams for explaining another example of a method for manufacturing a stacked body and a method for manufacturing a semiconductor device according to the first embodiment. FIGS. 5A to 5B show an example of the configuration of an apparatus according to a second embodiment.

[0014] The present invention provides a membrane processing device. The device of the present invention has a processing part that removes a part of the membrane, and the tip of the processing part is made of fiber-reinforced resin.

[0015] The present invention will be described in more detail below based on the following embodiments. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the above and below-described purposes, and all such modifications are included within the technical scope of the present invention. In addition, hatching and component symbols may be omitted in each drawing for convenience. In such cases, reference should be made to the specification and other drawings. Furthermore, the dimensions of various components in the drawings may differ from the actual dimensions, as priority is given to helping understand the features of the present invention.

[0016] In the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. In addition, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example.

[0017] In this specification, the expressions "contain" and "comprise" include the concepts of "contain," "include," "consist essentially of," and "consist only of."

[0018] In this specification, "A and / or B" means "one of A and B" or "both A and B," and specifically means "A," "B," or "A and B."

[0019] 1 shows an example of the configuration of an apparatus 100 according to a first embodiment. The apparatus 100 includes, for example, a tool 3, a spring 10, a ball spline shaft 11, a ball spline 12, a Z-axis unit 15, and a substrate holder (X- and Y-axis units) 16 that fixes a substrate 1.

[0020] The apparatus 100 has a tool (processing unit) 3 that removes a portion of the film 20, and is capable of mechanically removing a portion of the film 20 by bringing the tool 3 into contact with the film 20 provided on the substrate 1. This forms a recessed structure in which a portion of the film 20 has been removed. In this specification, the tool 3 refers to a processing part that comes into direct contact with the workpiece, i.e., the film 20, to process the film 20. As will be described in detail later, the tip of the tool (processing unit) 3 is made of fiber-reinforced resin, and the tip of the tool (processing unit) 3 can be brought into contact with the film 20 to perform processing to remove a portion of the film 20.

[0021] By moving at least one of the tool 3 and the substrate 1, the apparatus 100 can move the position of the tip of the tool 3 relative to the substrate 1 in the X and Y directions parallel to the top surface of the stage on which the substrate 1 is placed, and in the Z direction intersecting the top surface. The X and Y directions are, for example, perpendicular to each other. The Z direction is, for example, perpendicular to the X and Y directions. The apparatus 100 achieves this relative movement between the tool 3 and the substrate 1 by, for example, moving the substrate holder 16 to which the substrate 1 is fixed in the X and Y directions, and by moving the tool 3 in the Z direction using the ball spline shaft 11, the ball spline 12, and the Z axis 15. A mechanism for achieving this relative movement between the tool 3 and the substrate 1 includes an existing movable XY stage and a Z axis, but the embodiment is not limited to this. For example, a tool may be used in which the stage on which the substrate 1 is placed moves in the Y direction while the tool 3 moves in the X and Z directions, or the substrate 1 is fixed and does not move while the tool 3 moves in the X, Y, and Z directions.

[0022] The apparatus 100 can move the position of the tip of the tool 3 relative to the substrate 1, thereby moving the tool 3 to a position corresponding to the start position of processing of the film 20. Furthermore, the apparatus 100 can form a desired recessed structure in processing by moving the position of the tip of the tool 3 that is in contact with the film 20 relative to the substrate 1 during processing of the film 20. Fig. 1(A) shows how the position of the tip of the tool 3 is controlled relative to the substrate 1 before processing of the film 20 begins, and Fig. 1(B) shows how the film 20 is being processed.

[0023] The substrate 1 may be made of, for example, an organic material, a metal material, a fabric material, a paper material, a ceramic material, a glass material, or a combination thereof, and may be selected depending on the device to be used (e.g., a semiconductor device such as a solar cell device). The substrate 1 is used as a substrate on which a thin film, as described below, is deposited. Materials constituting the substrate 1 are preferably, for example, semiconductor materials such as Si, Ge, and GaAs, glass, metals (e.g., SUS foil, copper foil, Al foil), polymer films (e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), or polyester elastomers (preferably Pelprene (registered trademark)), nylon, PVC, polyolefin). The substrate 1 may also include an upper substrate and a lower substrate made of a combination of the above-mentioned materials, such as glass with a varnish layer deposited thereon, a metal-coated substrate, or a multilayer film. From the viewpoint of improving film formation efficiency, the size of the substrate 1 is preferably large enough to accommodate multiple cell units constituting a semiconductor device or the like. The substrate 1 is preferably in the form of a film or a roll from the viewpoint of improving the efficiency of film formation.

[0024] The film 20 may be a single layer (film) or may include two or more layers (films). The film 20 may include only organic and / or inorganic films. The film 20 may refer to an entire film formed using existing means. The film 20 may be a laminate of several layers, including, for example, a layer containing an organic semiconductor. The film 20 may include an inorganic layer that accounts for up to 40% of the total film thickness.

[0025] The film 20 may be, for example, a layer that functions as any one of an electron transport layer, a photovoltaic layer (which may include a p-type semiconductor layer and / or an n-type semiconductor layer) (which may also be referred to as a photoelectric conversion 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, or may include two or more of these layers. The film 20 may be, or may include, a layer that functions as a p-type semiconductor and / or an n-type semiconductor for amplification, switching, sensing, or a computing element.

[0026] FIG. 1 shows an example in which the film 20 is provided directly on the substrate 1, but the embodiment is not limited to this. An underlayer may be provided between the substrate 1 and the film 20, such that the underlayer is provided on the substrate 1 and the film 20 is provided on the underlayer. In this specification, this case is also referred to as the film 20 being provided on the substrate 1. For example, a conductive layer such as a transparent conductive layer may be provided on the substrate 1, the film 20 may be provided on the conductive layer, and the film 20 may include a photovoltaic layer. The film 20 may include at least one of an electron transport layer and a hole transport layer in addition to the photovoltaic layer. In these cases, the film 20 does not include the conductive layer such as the transparent conductive layer described above.

[0027] Materials constituting such an underlayer film include metals such as aluminum (Al), gold (Au), platinum (Pt), iridium (Ir), ruthenium (Ru), titanium (Ti), molybdenum (Mo), tantalum (Ta), copper (Cu), and silver (Ag); indium tin oxide (ITO), iridium oxide (IrO ２ ), ruthenium oxide (RuO ２ ), LaNiO ３ , SrRuO ３ , AZO, SiOx, SiON, SiOC, SiOCN, ZnO, TiOx, and other metal oxides. Only one of these materials may be used, or a combination of two or more selected materials may be used. Some of these materials may also be used as film-forming materials depending on the film-forming method.

[0028] As described above, the tool 3 is brought into contact with the film 20 in order to mechanically remove a portion of the film 20. At least the portion of the tool 3 that comes into contact with the film 20 is made of fiber reinforced plastics (FRP). The entire tool 3 may be made of the fiber reinforced resin described in this specification. A single type of fiber reinforced resin may be used, or two or more types may be used.

[0029] Examples of the fiber reinforced resin include glass fiber, Zylon (registered trademark) fiber, carbon fiber, Kevlar (registered trademark) fiber, Dyneema (registered trademark), aramid fiber, boron fiber, and SiC. Zylon fiber refers to polyparaphenylene benzobisoxazole (PBO) fiber. The fiber reinforced resin used in the tool 3 is preferably at least one selected from the group consisting of glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), and Zylon fiber reinforced plastic.

[0030] As the resin for the fiber reinforced resin, a thermosetting resin such as an unsaturated polyester is often used, but epoxy resin, polyethylene resin, polyamide resin, phenolic resin, vinyl ester resin, methyl (meth)acrylate, or liquid crystal polymer may also be used. As the resin for the fiber reinforced resin, it is preferable to use an epoxy resin or a polyethylene resin.

[0031] The fiber reinforced resin used in the tool 3 is preferably at least one selected from the group consisting of glass fiber reinforced epoxy resin, carbon fiber reinforced epoxy resin, Zylon fiber reinforced epoxy resin, and carbon fiber reinforced polyethylene resin.

[0032] FIG. 2 is a diagram illustrating several examples of the shape of the tool 3 included in the device 100 according to the first embodiment, but the embodiment is not limited to the following diagram. FIG. 2A illustrates an example in which the tip of the tool 3 has a right-angled shape. The tip of the tool 3 may have other angular shapes, such as an acute angle. FIG. 2B illustrates an example in which the tool 3 has a circular shape (wheel shape). FIG. 2C illustrates an example in which the tip of the tool 3 has a curved shape (circular). Regarding the shape of the tool 3, it is known that the smaller the tip angle, the narrower the scribe width obtained. However, as the scribing process continues, the scribe width changes, and frequent tool replacement or shape reshaping may be required for stabilization. The greater the curvature of the tip of the tool 3, the wider and more stable the scribe width becomes.

[0033] The apparatus 100 is capable of forming a recessed structure in which a portion of the film 20 has been removed by bringing the tool 3 into contact with the film 20 provided on the substrate 1 and removing a portion of the film 20. When forming the recessed structure, at least the portion of the tool 3 that comes into contact with the film 20 is made of fiber-reinforced resin, thereby allowing the portion of the film 20 to be accurately removed while reducing damage to the substrate 1. In the case where a base thin film such as a transparent conductive layer is provided on the substrate 1 and the film 20 is provided on the base thin film, when forming the recessed structure, at least the portion of the tool 3 that comes into contact with the film 20 is made of fiber-reinforced resin, allowing the portion of the film 20 to be accurately removed while reducing damage to the substrate 1 and / or the base thin film.

[0034] Methods for controlling the pressure applied by the tool 3 to the film 20 and substrate 1 during processing using the tool 3 include existing mechanisms such as springs, gas pressure, torque-controlled motors, and piezoelectric elements. The apparatus 100 contacts the tool 3 with the object at a constant pressure while contacting the tool 3 with the film 20 to form the recessed structure. The pressure is preferably 10 MPa or more, more preferably 15 MPa or more, and even more preferably 20 MPa or more, while preferably 60 MPa or less, more preferably 55 MPa or less, and even more preferably 50 MPa or less. In this specification, "constant" means that the pressure is controlled to be constant, and some degree of error is acceptable. FIG. 1A shows a spring 10 that enables such control. Such pressure control makes it possible, for example, to partially remove an upper layer while leaving a lower layer undamaged, as described above. Such pressure has little effect on the scribe shape, such as the scribe width, described below.

[0035] The apparatus 100 may be connected to a tool cleaning device (not shown). The tools 3 provided in the apparatus 100 are fixed to the apparatus 100, and the substrate 1 is loaded and unloaded by, for example, a robot hand. As another embodiment, the scope of the present invention also includes a case where the substrate holder 16 is movable and loads and unloads the substrate 1.

[0036] The apparatus 100 may be connected to a substrate cleaning apparatus (not shown). The tool 3 is fixed to the apparatus 100, and the substrate 1 is loaded and unloaded by, for example, a robot hand. As another embodiment, the present invention also falls within the scope of the present invention, in which the substrate holder 16 is movable and loads and unloads the substrate 1.

[0037] A substrate position measuring device (not shown) may be installed in the apparatus 100. Controlling the position of the substrate or the scribe position relative to the shape of the underlying thin film is also within the scope of the present invention.

[0038] The system 100 may also include a tool changer and / or tool forming system (not shown), and this is within the scope of the present invention.

[0039] <Methods for Manufacturing Stack and Semiconductor Device> Hereinafter, a method for manufacturing a stack and a semiconductor device such as a solar cell device, which are realized by the apparatus 100 according to the first embodiment, will be described.

[0040] The film forming material of the film 20 may be either an inorganic material or an organic material, and may be appropriately selected depending on the desired configuration of the film 20. As the film forming material, it is preferable to use a material that forms a film with nanoparticles, a material that forms a film using a chemical reaction using heat or other energy, for example, a material that forms a film by a reaction such as sol-gel, a material that forms a film by forming an oxide by oxidation treatment, a material that forms a film by forming a nitride by nitriding treatment, a material that forms a film by drying a solvent, etc. ｘ , CdO ｘ , TiO ｘ , MoO ｘ , InSbO ４ , CdSnO ４ , Zn ２ SnO ４ , In ２ O ３ It is more preferable to use ZnO, ITO, FTO, AZO, ATO, SnOx, aluminum oxide, silicon oxide, silicon nitride, silicon oxynitride, PEIE (polyethyleneimine ethoxylated), and PEI (polyethyleneimine). However, even with the same material, removal may become impossible depending on the vacuum thin film preparation conditions.

[0041] The method for forming the films included in film 20 is not particularly limited, and a vacuum process such as vapor deposition or a solution process such as spin coating can be used. The films included in film 20 are preferably formed by any of spin coating, bar coating, blade coating, spray coating, dip coating, printing, and, for some materials, vacuum deposition, and may be formed by two or more of these methods. The films included in film 20 are more preferably formed by spin coating.

[0042] A p-type semiconductor material may be used as the film forming material of the film 20. Specific examples of p-type semiconductor materials include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylenevinylene and derivatives thereof, polythienylenevinylene and derivatives thereof, polyfluorene and derivatives thereof, and polybenzobisthiazole and derivatives thereof.

[0043] An n-type semiconductor material may be used as the film-forming material for the film 20. The n-type semiconductor material may be a low-molecular-weight compound or a high-molecular-weight compound. Examples of n-type semiconductor materials that are low-molecular-weight compounds include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, phenanthrene derivatives such as bathocuproine, fullerene derivatives, naphthalenetetracarboxylic acid imide derivatives, perylene tetracarboxylic acid derivatives, and perylene diimide derivatives. Examples of n-type semiconductor materials that are polymer compounds include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylenevinylene and derivatives thereof, polythienylenevinylene and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof.

[0044] After forming the film 20 on the substrate 1, the device 100 is used to bring the tool 3 into contact with the film 20 to remove a portion of the film 20, thereby forming a recessed structure in which a portion of the film 20 has been removed. This produces a laminate including the substrate 1 and the film 20 and having a recessed structure.

[0045] When processing using such a tool 3, the pressure used when bringing the tool 3 into contact with the object is, for example, a constant pressure as described above. The speed of the tool 3 when removing the film 20 using the tool 3 in this manner is preferably 10 mm / sec or more, more preferably 15 mm / sec or more, and even more preferably 20 mm / sec or more, and is preferably 500 mm / sec or less, more preferably 300 mm / sec or less, and even more preferably 200 mm / sec or less. Such a speed has almost no effect on the scribe shape, such as the scribe width described below.

[0046] When removing a portion of the film 20, at least the portion of the tool 3 that comes into contact with the film 20 is made of fiber-reinforced resin, so that the portion of the film 20 is removed with precision while reducing damage to the substrate 1.

[0047] This embodiment is also applicable to the formation of the film 20 on the substrate 1 when a base thin film such as a transparent conductive layer is formed on the substrate 1 and the film 20 is then formed on the base thin film. When forming the base thin film, it is preferable to form an ITO film by sputtering. When removing a portion of the film 20, at least the portion of the tool 3 that comes into contact with the film 20 is made of fiber-reinforced resin, thereby accurately removing the portion of the film 20 while improving damage to the substrate 1 and / or the base thin film. In this specification, the term "manufactured laminate" refers to a laminate including the substrate 1 and the film 20 after other processes have been performed after the formation of the recessed structure. It is possible that the recessed structure may no longer be visible due to the other processes.

[0048] The method for manufacturing a stack and a method for manufacturing a semiconductor device such as a solar cell device will be specifically described with reference to Fig. 3. Fig. 3 is a diagram for explaining an example of the method for manufacturing a stack and a semiconductor device according to the first embodiment. Fig. 3 shows 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.

[0049] 3A to 3G show an example of a device manufacturing process for manufacturing a semiconductor device such as a solar cell device in two cell units in chronological order, with the two cell units being arranged so as to be connected in series on a substrate 1.

[0050] FIG. 3A shows a process for preparing a substrate 1. FIG. 3B shows a process for forming a plurality of mutually separated transparent conductive layers 21 on the substrate 1, the number of which corresponds to the number of cell units to be connected in series. In the example shown in FIG. 3B, the transparent conductive layer 21 is divided into three. The division method may be a known method, such as placing a metal mask on the substrate and performing ITO sputtering, forming an ITO film on the entire surface followed by ITO etching, or forming an ITO film on the entire surface followed by laser irradiation to remove the ITO in the irradiated areas. FIG. 3C shows a process for forming an electron transport layer 22 on the transparent conductive layer 21 and the exposed substrate 1, including the areas where the transparent conductive layer 21 has been removed. FIG. 3D shows a process for forming a photovoltaic layer 23 on the electron transport layer 22. FIG. 3E shows a process for forming a hole transport layer 24 on the photovoltaic layer 23. FIG. 3F shows a process for dividing the substrate by partially removing the electron transport layer 22, photovoltaic layer 23, and hole transport layer 24. The electron transport layer 22, photovoltaic layer 23, and hole transport layer 24 correspond to the film 20 described with reference to FIG. 1 . The process shown in FIG. 3F is achieved by using an apparatus 100 to contact a tool 3 with the film 20 to form a recessed structure in which a portion of the film 20 is removed. When removing the portion of the film 20, at least the portion of the tool 3 that contacts the film 20 is made of a fiber-reinforced resin, thereby accurately removing the portion of the film 20 while improving damage to the transparent conductive layer 21. Through the process shown in FIG. 3F, a stack of each cell unit, each composed of the transparent conductive layer 21, the electron transport layer 22, the photovoltaic layer 23, the hole transport layer 24, and the electrode layer 25, is manufactured on the substrate 1 so that the stack is adjacent to the stack of other cell units with a predetermined gap therebetween. FIG. 3G shows the process of forming an electrode layer 25 on the hole transport layer 24 for each cell unit. For the series connection, the electrode layer 25 is formed so as to be provided on the transparent conductive layer 21 of an adjacent cell unit via the side surface of the stack of the cell unit. In this manner, a semiconductor device that is a photoelectric conversion element such as a solar cell device is manufactured.

[0051] In the example of the solar cell shown in Figure 3, it is preferable to laminate a transparent conductive layer 21, an electron transport layer 22, a photovoltaic layer 23, a hole transport layer 24, and an electrode layer 25 in this order on a substrate 1. Furthermore, in a semiconductor device, it is preferable to laminate a protective layer and a gas barrier layer on the electrode layer 25. It is also possible to laminate a transparent conductive layer 21, a hole transport layer 24, a photovoltaic layer 23, an electron transport layer 22, and an electrode layer 25 in this order on a substrate 1. In this case, it is also preferable to laminate a protective layer and a gas barrier layer on the electrode layer 25. 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.

[0052] Although the laminate and semiconductor device manufacturing methods have been described above with reference to FIG. 3, the present invention is not limited to this embodiment. For example, another example of the laminate manufacturing method and semiconductor device manufacturing method according to the first embodiment is shown in FIG. 4. FIGS. 4A to 4H sequentially show an example of a device manufacturing process for manufacturing a semiconductor device that is a photoelectric conversion element such as a solar cell device. The process differs significantly from FIG. 3 in that a portion of film 20 is removed in the process of FIG. 4F, and then a portion of film 20 is removed in the process of FIG. 4H at a location different from that of the process of FIG. 4F.

[0053] In the first embodiment, an apparatus has been described in which the tip of a processing part for mechanically removing a portion of a film is made of fiber-reinforced resin, and at least the portion that comes into contact with the film is also made of fiber-reinforced resin. By using this apparatus, a portion of the film can be accurately removed, damage to the substrate and / or the underlying thin film can be alleviated, and a method for manufacturing a laminate and a method for manufacturing a semiconductor device using this apparatus can also be obtained.

[0054] The apparatus, the method for manufacturing a laminate, and the method for manufacturing a semiconductor device have been described above. The techniques disclosed in this specification can be suitably used in various fields in which a portion of a film is removed, particularly in the field of semiconductor devices such as solar cell devices (organic thin-film solar cell devices), display devices, optical sensors, and touch panels.

[0055] This application claims the benefit of priority based on Japanese Patent Application No. 2023-108662, filed on June 30, 2023. The entire contents of the specification of Japanese Patent Application No. 2023-108662, filed on June 30, 2023, are incorporated herein by reference.

[0056] The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited to the following examples, and it is of course possible to carry out the invention by making appropriate modifications within the scope of the above and below-described aims, and all such modifications are included in the technical scope of the present invention.

[0057] <Formation of film on substrate> (1) Sample A: A laminate in which an electron transport layer, a photovoltaic layer, and a hole transport layer were sequentially formed on a substrate with a transparent conductive layer was obtained by the following treatment. This laminate was designated as Sample A.

[0058] (Preparation of Substrate with Transparent Conductive Layer) An ITO film was formed as a transparent conductive layer on the entire surface of an OA11 glass substrate manufactured by Nippon Electric Glass Co., Ltd. by sputtering, and then the ITO in the irradiated areas was removed by irradiation with a nanosecond laser having a wavelength of 355 nm, thereby obtaining a glass substrate with patterned ITO.

[0059] (Formation of Electron Transport Layer) An electron transport layer was formed by spin coating on the ITO film on the side where the ITO was partially present and on the exposed substrate, including the area where the ITO had been removed. More specifically, a ZnO nanoparticle dispersion (Avantama N-11) was dropped and applied by spin coating at 1500 rpm for 45 seconds, and the substrate was heated on a hot plate at 140°C for 10 minutes.

[0060] (Photovoltaic Layer Formation) A solution was prepared by mixing Poly(3-hexylthiophene) (abbreviated as P3HT), a fullerene derivative (E100H manufactured by Frontier Carbon), and chlorobenzene in a ratio of 16 mg:16 mg:1 mL. This solution was dropped onto the substrate on which the ZnO film had been formed as described above, and applied by spin coating at 1000 rpm for 45 seconds. The coated substrate was then heated on a hot plate at 140°C for 10 minutes.

[0061] (Formation of Hole Transport Layer) PEDOT:PSS (purchased from Ossila, HTL solar) was dropped onto the substrate after the photovoltaic layer was formed as described above, and applied by spin coating at 1000 rpm for 50 seconds. Immediately after application, the substrate was heated on a hot plate at 100° C. for 10 minutes.

[0062] (2) Sample B A laminate was obtained by carrying out the same processes as those carried out to obtain Sample A, except that the preparation of the substrate with a transparent conductive layer and the formation of the hole transport layer were carried out as follows. This laminate was designated Sample B.

[0063] (Preparation of substrate with transparent conductive layer) An ITO film was deposited on the smooth surface of a PET film A4160 (manufactured by Toyobo Co., Ltd.) by sputtering, and the ITO was partially removed with a nanosecond laser having a wavelength of 355 nm to form a pattern, after which the ITO was fixed onto an OA11 glass substrate (manufactured by Nippon Electric Glass Co., Ltd.).

[0064] (Formation of Hole Transport Layer) MoO was vacuum-deposited on the photovoltaic layer to form a hole transport layer.

[0065] (3) Sample C: The same process as that performed to obtain Sample A was carried out, except that the photovoltaic layer was formed as follows, to obtain a laminate in which an electron transport layer, a photovoltaic layer, and a hole transport layer were sequentially formed on a substrate with a transparent conductive layer. This laminate was designated Sample C.

[0066] (Photovoltaic Layer Formation) Poly[(2,6-(4,8-bis(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione)] (PM6), 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5'] A solution was prepared by mixing thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (Y6) and chlorobenzene in a ratio of 8.4 mg:8.4 mg:1 mL. This solution was dropped onto the substrate after ZnO deposition and applied by spin coating at 1000 rpm for 45 seconds. The coated substrate was then heated on a hot plate at 140 °C for 10 minutes.

[0067] <Manufacturing of Tools> Tools were manufactured using the following combinations of tool materials and tool shapes. A device was manufactured using the manufactured tools.

[0068] (Tool Materials) The following tool materials were used. 1: Glass fiber reinforced epoxy GFRP. Sanhayato Corporation Model No. 53 copper-clad laminate (glass epoxy single-sided) 0.4 mm thick (measured 0.43 mm). The copper was removed by etching with a ferric chloride solution, and then cut to the desired shape. 2: Carbon fiber reinforced epoxy CFRP. Three sheets of carbon fiber woven fabric, each 0.230 mm thick (measured), were stacked, thoroughly coated with a two-component epoxy adhesive (Cemedine High Super 30), covered on both sides with polyethylene film, compressed in a press, and left to dry for one day. After curing, the thickness was 0.74 mm (measured). Plate thickness was measured using a micrometer. The sheet was cut to the desired shape. 3: Zylon fiber-reinforced epoxy FRP. Three sheets of Zylon fabric, each 0.173 mm thick (measured), were stacked, thoroughly coated with a two-component epoxy adhesive (Cemedine High Super 30), covered on both sides with polyethylene film, compressed in a press, and left to dry for one day. After curing, the thickness was 0.74 mm (measured). Thickness was measured using a micrometer. The sheet was cut to the desired shape. 4: Carbon fiber-reinforced polyethylene CFRP. Three sheets of carbon fiber woven fabric, each 0.230 mm thick (measured), were stacked on top of each other and then overlaid with PE film. Both sides were sandwiched between 38 μm Toyobo XENOMAX films, and the sheet was heated and pressed in a press. After cooling, the thickness was 0.95 mm (measured). Thickness was measured using a micrometer. The sheet was cut to the desired shape. 5: Resinoid grindstone, #36, BA1938-KA-5P manufactured by Yanase Co., Ltd. was used. 6: Rubber grindstone, #400, DB1103 manufactured by MINITOR Co., Ltd. was used. The abrasive grain was GC7: Nylon resin plate. A nylon resin plate was machined and used.

[0069] (Tool Shape) The following tool shapes were used: 1: Round tip The tip was machined using a router to form an arc with a radius of 2.25 mm 2: Right-angle tip The tip was machined to cut at a right angle 3: Circular The tip was machined to a diameter of 25 mm with a mounting hole in the center

[0070] <Examples> For each example, a tool was brought into contact with a film (sample) provided on a substrate using an apparatus under the conditions shown in Table 1 to mechanically remove a portion of the film. At this time, the film was removed under the following conditions for tool pressure and tool speed. Table 1 also shows the results of evaluation of ITO scratches, measurement and evaluation of groove depth, and measurement of groove width for each example, which were performed using the methods described below.

[0071] (Tool pressure) The tool pressure applied to the film was constant at the following values. The pressure was confirmed using a Fujifilm Prescale. At this time, it was confirmed that the length of the spring was within a linear range and could be reproduced. 1: 30 MPa 2: 50 MPa 3: 20 MPa

[0072] (Tool speed) The tool speed during film removal was kept constant at the following values: 1: 20 mm / sec 2: 200 mm / sec

[0073] (ITO scratch evaluation method) Scribing was performed over a full width of 15 mm at the center of a 15 mm × 50 mm sample, and this was used as the center of the resistance measurement, and the resistance of the ITO film was measured using a four-terminal method. Resistance measurements were performed three times before and after scribing to calculate the average value, and a score of ◯ was given when the increase in ITO resistance was 1% or less, and an X was given when it exceeded 1%.

[0074] (Groove depth measurement method) The groove depth at the scribed area was measured using a stylus film thickness meter (Dektak-XTS, BRUKER). When the measurement result was within ±10% of the designed film thickness, it was marked as ◯, and when it was outside the range of ±10%, it was marked as ×.

[0075] (Groove Width Measurement Method) The groove width (hereinafter, may also be referred to as scribe width) at the scribed portion was measured using a stylus-type film thickness meter (Dektak-XTS, BRUKER).

[0076]

[0077] <Comparative Examples> For each comparative example, a tool was brought into contact with the film provided on the substrate to mechanically remove a portion of the film under the conditions shown in Table 2. The tool pressure and tool speed were the same as those described in the examples. The results for each comparative example are shown in Table 2.

[0078]

[0079] From Tables 1 and 2, it can be seen that when the tool was made of a fiber-reinforced resin such as glass fiber-reinforced epoxy resin, carbon fiber-reinforced epoxy resin, Zylon fiber-reinforced epoxy resin, or carbon fiber-reinforced polyethylene resin, as in Examples 1 to 8, the evaluation of ITO scratches and the evaluation of groove depth were good, that is, part of the film was accurately removed while scratches on the ITO film as a base thin film were improved. On the other hand, in Comparative Examples 1 to 3, the tool was made of a resinoid grindstone or a rubber grindstone, and the evaluation of ITO scratches was poor, and in Comparative Examples 4 and 5, the tool was made of nylon resin, and the evaluation of groove depth was poor.

[0080] 5 shows an example of the configuration of an apparatus 100a according to a second embodiment, which is different from the first embodiment. The following description will focus on the differences from the apparatus 100 according to the first embodiment. The apparatus 100a includes, for example, a tool 3, a spring 10, a ball spline shaft 11, a ball spline 12, a substrate fixing table 17, transport rollers 18, and an X, Y, and Z axis unit 19. The substrate 1 is transported by the transport rollers 18, and the substrate 1 functions as a roll-to-roll substrate.

[0081] The apparatus 100a is capable of moving the substrate 1 by raising and lowering the substrate fixing table 17. The apparatus 100a is capable of moving the tool 3 in the X, Y, and Z directions using the ball spline shaft 11, the ball spline 12, and the X, Y, and Z axes 19. In this manner, the apparatus 100a is capable of moving the position of the tip of the tool 3 relative to the substrate 1 in the X, Y, and Z directions by moving at least one of the tool 3 and the substrate 1.

[0082] The apparatus 100a can form a recessed structure by removing a part of the film 20 by bringing the tool 3 into contact with the film 20 provided on the substrate 1, which is the roll-to-roll substrate, at a constant pressure and processing it with a roll. The pressure is as described in the first embodiment.

[0083] As described above, this invention is not limited to the above-described embodiments, and the components can be modified and embodied in practice without departing from the spirit of the invention. Furthermore, various inventions can be formed by appropriately combining multiple components disclosed in the above-described embodiments. For example, some components may be omitted from all the components shown in the embodiments. Furthermore, components from different embodiments may be appropriately combined.

[0084] 1: Substrate 3: Tool 10: Spring 11: Ball spline shaft 12: Ball spline 15: Z axis section 16: Substrate holder (X, Y axis section) 17: Substrate fixing table (with lifting mechanism) 18: Transport roller 19: X, Y, Z axis section 20: Film 21: Transparent conductive layer 22: Electron transport layer 23: Photovoltaic layer 24: Hole transport layer 25: Electrode layer 100, 100a: Device

Claims

1. An apparatus for processing a membrane, the apparatus having a processing part for removing a part of the membrane, the tip part of the processing part being made of fiber reinforced resin.

2. The apparatus according to claim 1, which is an apparatus for mechanically removing a portion of the film provided on a substrate, has a processing part that comes into contact with the film to mechanically remove the portion of the film, and at least the part of the processing part that comes into contact with the film is made of fiber-reinforced resin.

3. The apparatus according to claim 1 or 2, characterized in that the processing part is brought into contact with the object with a constant pressure during the removal.

4. The apparatus according to claim 2, characterized in that the position of the tip of the processing part with respect to the substrate can be moved relatively in the X-direction and Y-direction parallel to the upper surface of a stage on which the substrate is placed, and in the Z-direction intersecting the upper surface, by moving at least one of the processing part and the substrate.

5. The device according to claim 1 or 2, characterized in that the fiber reinforced resin is at least one selected from the group consisting of glass fiber reinforced resin, carbon fiber reinforced resin, and Zylon fiber reinforced resin.

6. The device according to claim 1 or 2, characterized in that the fiber-reinforced resin is at least one selected from the group consisting of glass fiber-reinforced epoxy resin, carbon fiber-reinforced epoxy resin, Zylon fiber-reinforced epoxy resin, and carbon fiber-reinforced polyethylene resin.

7. The apparatus according to claim 3, characterized in that the pressure is controlled to partially remove an upper part of the layer while leaving a lower part of the layer undamaged.

8. The apparatus according to claim 2, wherein the substrate is a roll-to-roll substrate, and the removal is carried out by bringing the processing part into contact with the film provided on the roll-to-roll substrate at a constant pressure and processing it with a roll.

9. A method for producing a laminate, comprising the step of removing a portion of the film using the apparatus according to claim 1 or 2.

10. A method for manufacturing a semiconductor device, comprising the step of removing a portion of the film using the apparatus according to claim 1 or 2.

11. The method of claim 10, wherein the semiconductor device is a photoelectric conversion element.

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