Photoelectric conversion element, photoelectric conversion module, electronic device, and power supply module

Abstract

To solve a problem in which an electrode peels off and the storage durability performance is lowered when a photoelectric conversion element having a surface protection portion on an electrode for the purpose of suppressing electrode peeling and improving storage durability is bent.SOLUTION: A photoelectric conversion element having a first electrode, a photoelectric conversion layer, and a second electrode in this order includes a surface protective portion adjacent to a surface of one electrode selected from the first electrode and the second electrode, which does not face the photoelectric conversion layer, and the surface protective portion contains a compound derived from a fluorine-based silane compound.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a photoelectric conversion element, a photoelectric conversion module, an electronic device, and a power supply module. [Background technology]

[0002] In recent years, there has been a growing expectation for the realization of an IoT (Internet of Things) society in which everything will be connected to the Internet and be able to be comprehensively controlled. To realize such an IoT society, it is necessary to attach numerous sensors to various objects and acquire data, but a power source is also required to operate these numerous sensors. Wiring multiple sensors or using storage batteries is not practical, and with the growing societal need to reduce environmental impact, there is hope for power supply from energy harvesting elements.

[0003] Among these, photoelectric conversion elements are attracting attention as elements that can generate electricity wherever there is light. Flexible photoelectric conversion elements in particular are expected to be highly efficient and also to be able to conform to various curved surfaces, making them suitable for use in wearable devices. For example, Non-Patent Documents 1 and 2 report the results of a study into the feasibility of using photoelectric conversion elements in wearable devices. Generally, organic thin-film solar cells are expected to be flexible and highly efficient energy harvesting elements, and Patent Document 1 proposes a photoelectric conversion element using a transparent substrate film as a substrate.

[0004] A photoelectric conversion element in a typical organic thin-film solar cell has a structure in which a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a second electrode are laminated in this order on a base material serving as a support substrate. Furthermore, in order to improve the durability of the photoelectric conversion element, a structure in which a surface protective layer and a sealing member are further laminated in this order on the electrode has become mainstream. A specific function of this surface protective layer is, for example, to improve the storage durability of the electrode, such as corrosion resistance and deterioration resistance. Another example is that the surface protective layer is provided between the electrode and the sealing member, preventing the adhesive member constituting the sealing member from coming into direct contact with the electrode, thereby suppressing peeling caused by the material constituting the electrode being transferred to the adhesive member. Summary of the Invention [Problem to be solved by the invention]

[0005] However, even in a photoelectric conversion element having a surface protection portion on the electrode, when the photoelectric conversion element is bent, there are problems in that the electrode peels off and that storage durability decreases. [Means for solving the problem]

[0006] The present invention relates to a photoelectric conversion element having, in order, a first electrode, a photoelectric conversion layer, and a second electrode, and further comprising a surface protective part adjacent to a surface of one of the electrodes selected from the first electrode and the second electrode that does not face the photoelectric conversion layer, wherein the surface protective part contains a compound derived from a fluorine-based silane compound. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a photoelectric conversion element in which peeling of the electrodes and a decrease in storage durability are suppressed even when the photoelectric conversion element is bent. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic overhead view showing an example of a photoelectric conversion element. [Figure 2] FIG. 2 is a schematic cross-sectional view showing an example of a photoelectric conversion element. [Figure 3A] FIG. 3A is a schematic diagram showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3B] FIG. 3B is a schematic view showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3C] FIG. 3C is a schematic view showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3D] FIG. 3D is a schematic diagram showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3E] FIG. 3E is a schematic view showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3F] FIG. 3F is a schematic view showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3G] FIG. 3G is a schematic view showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3H] FIG. 3H is a schematic view showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3I] FIG. 3I is a schematic view showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3J] FIG. 3J is a schematic view showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 3K] FIG. 3K is a schematic view showing an example of a method for manufacturing a photovoltaic conversion module. [Figure 4] FIG. 4 is a schematic diagram showing an example of the basic configuration of an electronic device. [Figure 5] FIG. 5 is a schematic diagram showing an example of the basic configuration of an electronic device. [Figure 6] FIG. 6 is a schematic diagram showing an example of the basic configuration of an electronic device. [Figure 7] FIG. 7 is a schematic diagram showing an example of the basic configuration of a power supply module. [Figure 8] FIG. 8 is a schematic diagram showing an example of the basic configuration of a power supply module. [Figure 9] FIG. 9 is a schematic diagram showing an example of the basic configuration of a mouse for a personal computer. [Figure 10] FIG. 10 is a schematic external view showing an example of the personal computer mouse shown in FIG. [Figure 11] FIG. 11 is a schematic diagram showing an example of the basic configuration of a keyboard for a personal computer. [Figure 12] FIG. 12 is a schematic external view showing an example of the personal computer keyboard shown in FIG. [Figure 13] FIG. 13 is a schematic external view showing another example of the personal computer keyboard shown in FIG. [Figure 14] FIG. 14 is a schematic diagram showing an example of the basic configuration of a sensor. [Figure 15] FIG. 15 is a schematic diagram showing an example of transmitting data acquired by a sensor to a PC, a smartphone, or the like via wireless communication. [Figure 16] FIG. 16 is a schematic diagram showing an example of the basic configuration of a turntable. DETAILED DESCRIPTION OF THE INVENTION

[0009] <<Photoelectric conversion element related to organic thin-film solar cells>> A "photoelectric conversion element" is an element that converts light energy into electrical energy or an element that converts electrical energy into light energy. Specific examples include elements that constitute solar cells and photodiodes. Examples of solar cells include organic thin-film solar cells, dye-sensitized solar cells, and perovskite solar cells. In this disclosure, first, a photoelectric conversion element that constitutes an organic thin-film solar cell will be described below, but dye-sensitized solar cells and perovskite solar cells will also be described later.

[0010] The photoelectric conversion element has at least a first electrode, a photoelectric conversion layer, and a second electrode, in that order. The term "sequentially" refers to the fact that these electrodes and layers are arranged in the above order as a whole, and other layers may be inserted between the electrodes and layers. Examples of cases in which other layers are inserted include a photoelectric conversion element having a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a second electrode, in that order. In this case, other layers may be inserted between the electrodes or between the layers. Furthermore, the term "sequentially" refers to the fact that these electrodes and layers may be stacked in order from the first electrode side, or from the second electrode side. Specifically, when observed from the light incident side, the photoelectric conversion element may be stacked in the order of the first electrode, photoelectric conversion layer, and second electrode, or the order of the second electrode, photoelectric conversion layer, and first electrode. Furthermore, when the photoelectric conversion element has an electron transport layer and a hole transport layer, the photoelectric conversion element may be stacked in the following order when observed from the light incident side: first electrode, electron transport layer, photoelectric conversion layer, hole transport layer, and second electrode; or may be stacked in the following order: second electrode, hole transport layer, photoelectric conversion layer, electron transport layer, and first electrode. This disclosure mainly describes a case where the first electrode, electron transport layer, photoelectric conversion layer, hole transport layer, and second electrode are stacked in this order when observed from the light incident side, but the present photoelectric conversion element is not limited to this embodiment. From this description, a person skilled in the art can easily understand other embodiments, such as a case where the second electrode, hole transport layer, photoelectric conversion layer, electron transport layer, and first electrode are stacked in this order when observed from the light incident side.

[0011] The photoelectric conversion element has a surface protection part. The surface protection part is provided adjacent to a surface of one electrode selected from the first electrode and the second electrode (hereinafter also referred to as "one electrode") that does not face the photoelectric conversion layer. In the present disclosure, "one electrode" refers to the electrode of the first electrode and the second electrode that is provided farther from the light incident surface. The other electrode selected from the first electrode and the second electrode (hereinafter also referred to as "the other electrode") refers to the electrode of the first electrode and the second electrode that is provided closer to the light incident surface. The "surface not facing the photoelectric conversion layer" refers to the surface located opposite the surface that faces the photoelectric conversion layer directly or indirectly via another layer.

[0012] The photoelectric conversion element preferably includes a sealing member. The sealing member is preferably provided adjacent to the surface protective part and encapsulates the surface protective part, one electrode, and the photoelectric conversion layer. When the photoelectric conversion element includes an electron transport layer and a hole transport layer, the sealing member preferably further encapsulates the electron transport layer and the hole transport layer.

[0013] Furthermore, the photoelectric conversion element may have a substrate, a UV-cut layer, and the like, as needed. When the photoelectric conversion element has a substrate, it is preferable that the photoelectric conversion element has a configuration in which the substrate, the first electrode, the electron transport layer, the photoelectric conversion layer, the hole transport layer, and the second electrode are laminated in this order when observed from the light incident side, or a configuration in which the substrate, the second electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer, and the first electrode are laminated in this order. Furthermore, it is preferable that the substrate is provided adjacent to the other electrode on the side of the other electrode that does not face the photoelectric conversion layer.

[0014] <Base material> The "substrate" is a member that supports the electrodes and layers that constitute the photoelectric conversion element. The substrate preferably has high light transmittance, and more preferably is transparent, from the viewpoint of increasing the photoelectric conversion efficiency. Furthermore, the substrate preferably has high flexibility from the viewpoint of expanding the range of applications of the photoelectric conversion element.

[0015] Examples of transparent and flexible substrate materials include resin films such as polyesters (e.g., polyethylene terephthalate), polycarbonates, polyimides, polymethyl methacrylates, polysulfones, and polyether ether ketones, as well as thin-film glass (glass having a thickness of 200 μm or less). Among these materials, polyester and polyimide resin films and thin-film glass are preferred from the viewpoints of ease of manufacture and cost. When using a resin film or thin-film glass as the substrate material, the thickness of the substrate is preferably 200 μm or less. Having a substrate thickness of 200 μm or less improves flexibility and improves durability even when the photoelectric conversion element is bent. The thickness of the substrate can be measured by known means, for example, using a contact thickness gauge. Examples of materials for the substrate that are transparent but not flexible include inorganic transparent crystals such as glass other than thin film glass (i.e., glass with a thickness of more than 200 μm). These materials are preferred because they are not flexible but have high flatness. The substrate preferably has gas barrier properties. Gas barrier properties are a function of suppressing the permeation of water vapor, oxygen, etc. In the present disclosure, the "substrate having gas barrier properties" is not limited to a substrate having gas barrier properties itself, but also includes a substrate having a gas barrier layer, which is a layer having gas barrier properties, located adjacent to the substrate. When the substrate has gas barrier properties, it is possible to provide a photoelectric conversion element with high storage durability in which the decrease in photoelectric conversion efficiency is further suppressed even when placed in a high-temperature, high-humidity environment for a long period of time. The gas barrier layer will be described later. The performance required for a substrate with gas barrier properties is generally expressed in terms of water vapor permeability and oxygen permeability. The water vapor permeability per day according to JIS K7129 B method is, for example, 10 g / m 2 The oxygen permeation rate per day according to JIS K7126-2 is preferably 1 cm or less, and the lower the better. 3 / m 2 It is preferable that it is below 1000 atm, and the lower the better. As the resin film having gas barrier properties, any known film can be used, and examples thereof include an aluminum-coated resin film and a silicon oxide-coated resin film.

[0016] <First electrode> The "first electrode" is an electrode that collects electrons generated by photoelectric conversion. When the first electrode is provided on the light incident side, the first electrode preferably has high light transmittance, and more preferably is transparent, from the viewpoint of increasing photoelectric conversion efficiency. However, when the first electrode is provided on the side opposite to the light incident side, the first electrode may have low light transmittance and transparency.

[0017] The first electrode having transparency can be a transparent electrode that is transparent to visible light. The transparent electrode is, for example, a structure in which a transparent conductive film, a metal thin film, and another transparent conductive film are sequentially stacked. The two transparent conductive films sandwiching the metal thin film may be made of the same material or different materials. Examples of materials for the transparent conductive film include tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), zinc oxide (ZnO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), tin oxide (SnO2), silver nanowires, and nanocarbons (carbon nanotubes, graphene, etc.). Among these materials, tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), and aluminum-doped zinc oxide (AZO) are preferred. Examples of materials for the metal thin film include thin films formed from metals such as aluminum, copper, silver, gold, platinum, and nickel. From the viewpoint of maintaining rigidity, the transparent first electrode is preferably integrated with the above-mentioned substrate, such as FTO-coated glass, ITO-coated glass, aluminum-coated glass, FTO-coated transparent plastic film, ITO-coated transparent plastic film, or ITO / silver / ITO laminated coated plastic film.

[0018] Examples of materials for the first electrode that do not have transparency include metals such as platinum, gold, silver, copper, and aluminum, as well as graphite.

[0019] The average thickness of the first electrode is preferably 5 nm or more and 10 μm or less, and more preferably 50 nm or more and 1 μm or less.

[0020] The sheet resistance of the first electrode is preferably 50 Ω / □ or less, more preferably 30 Ω / □ or less, and even more preferably 20 Ω / □ or less.

[0021] When the first electrode is transparent, the light transmittance of the first electrode is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. There is no particular upper limit, and it can be appropriately selected depending on the purpose.

[0022] The first electrode can be formed by a wet film-forming method, a dry film-forming method such as a vapor deposition method or a sputtering method, a printing method, or the like.

[0023] <Electron transport layer> The "electron transport layer" is a layer that transports electrons generated in the photoelectric conversion layer and suppresses the penetration of holes generated in the photoelectric conversion layer. The electron transport layer may have a structure consisting of one layer, or a structure having two or more layers. Hereinafter, as an example, a structure having two electron transport layers will be described. Specifically, it has a structure having a first electron transport layer and a second electron transport layer (also referred to as an "intermediate layer") provided between the first electron transport layer and the photoelectric conversion layer. Note that when the electron transport layer has a structure consisting of one layer, it is preferably the same layer as the first electron transport layer.

[0024] -First electron transport layer- The first electron transport layer is preferably a layer containing metal oxide particles. Examples of metal oxides include oxides of titanium, zinc, lithium, tin, etc., as well as ITO, FTO, ATO, AZO, and GZO. Among these, zinc oxide is preferred, and zinc oxide doped to enhance conductivity is more preferred. Examples of doped zinc oxide include aluminum-doped zinc oxide, gallium-doped zinc oxide, and lithium-doped zinc oxide. Metal oxides made from metal alkoxides or the like may also be used.

[0025] The average particle size of the metal oxide particles is preferably 1 nm or more and 50 nm or less, and more preferably 5 nm or more and 20 nm or less. The average particle size of metal oxide particles can be calculated, for example, by measuring the particle sizes of at least 100 randomly selected metal oxide particles and calculating the average value using the following method. First, a dispersion containing metal oxide particles is transferred to a glass nebulizer using a micropipette. Next, the dispersion is sprayed from the nebulizer onto a collodion-coated grid for TEM. Carbon deposition is performed on the grid using the PVD method, and an image of the metal oxide particles is obtained using an electron microscope. The obtained image is then subjected to image processing to measure the particle size of the metal oxide particles. Alternatively, the particle size of the metal oxide particles can be measured by observing the cross section of a photoelectric conversion element using a scanning transmission electron microscope (TEM) and recognizing the particles using image processing. Alternatively, the particle size distribution can be measured using laser diffraction / scattering methods, etc. The cross section of the photoelectric conversion element, TEM observation, and particle size distribution measurement can be performed using known methods.

[0026] The average thickness of the first electron transport layer is preferably 1 nm or more and 300 nm or less, and more preferably 10 nm or more and 150 nm or less.

[0027] The first electron transport layer can be produced, for example, by applying and drying a dispersion liquid containing metal oxide particles and a dispersion medium, such as alcohols such as methanol, ethanol, isopropanol, 1-propanol, 2-methoxyethanol, and 2-ethoxyethanol, or mixtures thereof.

[0028] -Second electron transport layer (intermediate layer)- The second electron transport layer is preferably a layer containing an amine compound. The amine compound is not particularly limited as long as it is a material that can improve the photoelectric conversion efficiency of the photoelectric conversion element by providing the second electron transport layer. For example, it is preferable to use an amine compound represented by the following general formula (4):

[0029] [ka]

[0030] In the general formula (4), R4 and R5 represent an alkyl group having 1 to 4 carbon atoms, which may have a substituent, or a ring structure to which R4 and R5 are bonded, and are preferably an alkyl group having 1 to 4 carbon atoms, which may have a substituent, and more preferably an alkyl group having 1 to 4 carbon atoms, which does not have a substituent. Examples of the substituent include a methyl group, an ethyl group, and a hydroxyl group. The ring structure preferably has 3 to 6 carbon atoms. When R4 and R5 are alkyl groups having 1 to 4 carbon atoms, which may have a substituent, the alkyl groups in R4 and R5 may be the same or different.

[0031] In the above general formula (4), X represents a divalent aromatic group having 6 to 14 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and is preferably a divalent aromatic group having 6 to 14 carbon atoms.

[0032] In the above general formula (4), A represents any of the substituents represented by the following structural formulas (1) to (3), and is preferably the substituent represented by structural formula (1).

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] Examples of amine compounds other than those represented by general formula (4) above include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-(2-aminoethylamino)propyltriethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, trimethoxy[3-(methylamino)propyl]silane, bis[3-(trimethoxyxylyl)propyl]amine, bis[3-(triethoxyxylyl)propyl]amine, and N,N'-bis[3-(trimethoxyxylyl)propyl]ethane-1,2-diamine.

[0037] The second electron transport layer can be produced, for example, by applying a solution containing an amine compound by spin coating, dipping, or the like, followed by drying.

[0038] <Photoelectric conversion layer> The "photoelectric conversion layer" is a layer that generates electrons and holes by absorbing light. The photoelectric conversion layer contains two or more organic materials, specifically, a donor organic material (also referred to as a p-type organic semiconductor material) and an acceptor organic material (also referred to as an n-type organic semiconductor material). The donor organic material and the acceptor organic material may each be made of multiple types of organic materials, and it is preferable that the photoelectric conversion layer contains three or more types of organic materials. Furthermore, in the photoelectric conversion layer, it is preferable that the donor organic material and the acceptor organic material are mixed to form a bulk heterostructure.

[0039] -Donor organic materials- The donor organic material is preferably a π-electron conjugated compound having a highest occupied molecular orbital (HOMO) level of 4.8 eV or more and 5.7 eV or less, more preferably a π-electron conjugated compound having ... The highest occupied molecular orbital (HOMO) level can be determined by photoelectron yield spectroscopy, cyclic voltammetry, etc. Specifically, it can be measured using an apparatus such as Riken Keiki AC-3.

[0040] Examples of donor organic materials include conjugated polymers in which various aromatic derivatives (e.g., thiophene, fluorene, carbazole, thienothiophene, benzodithiophene, dithienosilole, quinoxaline, benzothiadiazole, etc.) are coupled, and low-molecular-weight conjugated compounds such as porphyrins and phthalocyanines. The donor organic material may also be a donor-acceptor linked material having an electron-donating moiety and an electron-accepting moiety in the molecule.

[0041] The number average molecular weight (Mn) of the donor organic material is preferably 10,000 or less, more preferably 5,000 or less, if it is a low molecular weight material, and is preferably 10,000 or more, if it is a high molecular weight material.

[0042] A preferred example of the donor organic material is an organic material having a highest occupied molecular orbital (HOMO) level of 5.1 eV to 5.5 eV and a number average molecular weight (Mn) of 10,000 or less. Examples of such organic materials include compounds represented by the following general formula (1):

[0043] [ka]

[0044] In the above general formula (1), R1 represents an alkyl group having 2 to 8 carbon atoms.

[0045] In the above general formula (1), n ​​represents an integer of 1 or more and 3 or less.

[0046] In the above general formula (1), Y represents a halogen atom.

[0047] In the above general formula (1), m represents an integer of 0 or more and 4 or less.

[0048] In the above general formula (1), X represents the following general formula (2) or (3).

[0049] [ka]

[0050] [ka]

[0051] In the above general formula (2), R2 represents a linear or branched alkyl group, and is preferably a linear or branched alkyl group having 2 or more and 30 or less carbon atoms.

[0052] In the above general formula (3), R3 represents a linear or branched alkyl group, and is preferably a linear or branched alkyl group having 2 or more and 30 or less carbon atoms.

[0053] Another preferred example of the donor organic material is an organic material having a highest occupied molecular orbital (HOMO) level of 5.2 eV to 5.6 eV and a number average molecular weight (Mn) of 10,000 or more. This organic material is preferably used in combination with the above-mentioned organic material having a highest occupied molecular orbital (HOMO) level of 5.1 eV to 5.5 eV and a number average molecular weight (Mn) of 10,000 or less.

[0054] Examples of organic materials having a highest occupied molecular orbital (HOMO) level of 5.2 eV or more and 5.6 eV or less and a number average molecular weight (Mn) of 10,000 or more include 2,1,3-benzothiadiazole-thiophene copolymers, quinoxaline-thiophene copolymers, thiophene-benzodithiophene copolymers, and polyfluorene polymers.

[0055] The 2,1,3-benzothiadiazole-thiophene copolymer refers to a conjugated copolymer having a thiophene skeleton and a 2,1,3-benzothiadiazole skeleton in the main chain. Specific examples of the 2,1,3-benzothiadiazole-thiophene copolymer include the following general formulas (5) to (8). Note that in the following general formulas (5) to (8), n each independently represents an integer of 1 or more and 1,000 or less.

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] A quinoxaline-thiophene copolymer refers to a conjugated copolymer having a thiophene skeleton and a quinoxaline skeleton in the main chain. Specific examples of quinoxaline-thiophene copolymers include the following general formula (9). In the following general formula (9), n represents an integer of 1 or more and 1000 or less.

[0061] [ka]

[0062] The thiophene-benzodithiophene copolymer refers to a conjugated copolymer having a thiophene skeleton and a benzodithiophene skeleton in the main chain. Specific examples of the thiophene-benzodithiophene copolymer include the following general formulas (10) to (13). Note that in the following general formulas (10) to (13), n each independently represents an integer of 1 or more and 1000 or less.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] -Acceptor organic materials- The acceptor organic material is preferably a π-electron conjugated compound having a lowest unoccupied molecular orbital (LUMO) level of 3.5 eV or more and 4.5 eV or less.

[0068] Examples of the acceptor organic material include fullerene or a derivative thereof, a naphthalene tetracarboxylic acid imide derivative, a perylene tetracarboxylic acid imide derivative, etc. Among these, a fullerene derivative is preferable. Examples of fullerene derivatives include C 60 , phenyl-C 61 -methyl butyrate (known in the literature as PCBM,

[60] PCBM, or PC 61 BM), C 70 , phenyl-C 71-methyl butyrate (known in the literature as PCBM,

[70] PCBM, or PC 71 BM), and fulleropyrrolidine-based fullerene derivatives represented by the following general formula (14).

[0069] [ka]

[0070] In the general formula (14), Y1 and Y2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or an aralkyl group. However, Y1 and Y2 cannot both be hydrogen atoms. In addition, the alkyl group, alkenyl group, alkynyl group, aryl group, and aralkyl group may or may not have a substituent.

[0071] In the above general formula (14), Ar represents an aryl group, which may or may not have a substituent.

[0072] -Average thickness of photoelectric conversion layer- The average thickness of the photoelectric conversion layer is preferably 50 nm or more and 400 nm or less, and more preferably 60 nm or more and 250 nm or less. When the average thickness is 50 nm or more, the amount of carriers generated by light absorption in the photoelectric conversion layer is sufficient. Furthermore, when the average thickness is 400 nm or less, a decrease in carrier transport efficiency caused by light absorption is suppressed. The average thickness of the photoelectric conversion layer is calculated, for example, by measuring the thickness of the photoelectric conversion layer at nine random points and calculating the average value using the following method. First, a liquid containing the material that constitutes the photoelectric conversion layer is applied to a substrate and dried, and then any point is wiped with a solvent. The height of the step at the wiped location is measured using a DEKTAK manufactured by Bruker, and the obtained measurement value is used as the thickness. The average thickness of the photoelectric conversion layer may also be measured by observing the cross section of the photoelectric conversion element using a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

[0073] -Method for forming bulk heterojunction in photoelectric conversion layer- The photoelectric conversion layer may be a layer having a planar junction interface formed by sequentially stacking the above organic materials, but in order to increase the area of ​​the junction interface, it is preferable to form a bulk heterojunction having a structure in which the above organic materials are mixed three-dimensionally. The bulk heterojunction is formed, for example, as follows. When each organic material is highly soluble, the organic material is dissolved in a solvent to prepare a solution in which the organic materials are mixed in molecular form, and the solution is applied and dried to remove the solvent. In this case, a heat treatment may be further performed to optimize the aggregation state of each organic material. On the other hand, when using organic materials with low solubility, a liquid is prepared by dispersing one organic material in a solution in which the other organic material is dissolved, and then the liquid is applied and dried to remove the solvent. In this case, a heat treatment may be further performed to optimize the aggregation state of each organic material.

[0074] -Method for producing photoelectric conversion layer- The method for producing the photoelectric conversion layer includes a step of applying a liquid containing each of the above organic materials. Examples of the application method include spin coating, blade coating, slit die coating, screen printing, bar coating, casting, print transfer, immersion and lifting, ink jet printing, spraying, and vacuum deposition. An appropriate method is selected from these methods depending on the properties of the photoelectric conversion layer to be produced, such as thickness control and orientation control.

[0075] For example, when using a spin coating method, it is preferable to use a solution containing each of the above organic materials at a concentration of 5 mg / mL to 40 mg / mL. Note that the concentration refers to the total mass of each organic material relative to the volume of the solution containing each organic material. By setting the concentration above, a homogeneous photoelectric conversion layer can be easily produced.

[0076] Furthermore, in order to remove the solvent or dispersion medium from the applied liquid containing each organic material, annealing may be performed under reduced pressure or in an inert atmosphere (nitrogen or argon atmosphere). The temperature of the annealing is preferably 40°C or higher and 300°C or lower, and more preferably 50°C or higher and 150°C or lower. Note that annealing is preferable because it may increase the contact area at the interface between the stacked layers due to the materials constituting each layer penetrating each other, thereby increasing the short-circuit current.

[0077] Examples of solvents or dispersion media for dissolving or dispersing each organic material include methanol, ethanol, butanol, toluene, xylene, o-chlorophenol, acetone, ethyl acetate, ethylene glycol, tetrahydrofuran, dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, ortho-dichlorobenzene, chloronaphthalene, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and γ-butyrolactone. These may be used alone or in combination of two or more. Among these, chlorobenzene, chloroform, and ortho-dichlorobenzene are particularly preferred. The solvent or dispersion medium may contain various additives, such as diiodooctane and octanedithiol.

[0078] <Hole transport layer> The "hole transport layer" is a layer that transports holes generated in the photoelectric conversion layer and suppresses the penetration of electrons generated in the photoelectric conversion layer. The hole transport layer may have a structure consisting of one layer, or a structure having two or more layers. Hereinafter, as an example, a structure having one hole transport layer will be described.

[0079] The hole transport layer is preferably a layer containing at least one selected from organic compounds and inorganic compounds having hole transport properties. Examples of organic compounds having hole transport properties include conductive polymers such as PEDOT:PSS (polyethylenedioxythiophene:polystyrenesulfonic acid) and aromatic amine derivatives. Examples of inorganic compounds having hole transport properties include molybdenum oxide, tungsten oxide, vanadium oxide, nickel oxide, and copper(I) oxide. Among these compounds having hole transport properties, molybdenum oxide, tungsten oxide, and vanadium oxide are preferred.

[0080] The average thickness of the hole transport layer is preferably 200 nm or less, and more preferably 1 nm or more and 50 nm or less.

[0081] Examples of methods for producing the hole transport layer include a method of applying a liquid containing a compound having hole transport properties and a solvent or dispersion medium and then drying the applied liquid, such as spin coating, sol-gel coating, slit die coating, and sputtering.

[0082] <Second electrode> The "second electrode" is an electrode that collects holes generated by photoelectric conversion. When the second electrode is provided on the light incident side, the second electrode preferably has high light transmittance, and more preferably is transparent, from the viewpoint of increasing the photoelectric conversion efficiency. However, when the second electrode is provided on the side opposite to the light incident side, the second electrode may have low light transmittance and transparency. The second electrode can be the same as the first electrode, and therefore a description thereof will be omitted.

[0083] <Surface protection part> The "surface protective portion (also referred to as a "passivation layer" when it is layered)" is a member that prevents direct contact between the sealing member and one of the first and second electrodes, which is the electrode located farther from the light incident surface, and is provided between the one electrode and the sealing member. The shape of the surface protective portion is not particularly limited, but a layered structure is preferable. By providing such a surface protective portion on the one electrode (specifically, by providing it adjacent to the surface of the one electrode that does not face the photoelectric conversion layer), contact between the one electrode and water or oxygen that has entered from the outside is prevented. This prevents corrosion and deterioration of the one electrode over time and improves storage durability. Furthermore, a photoelectric conversion element can be configured so that the adhesive member that constitutes the sealing member does not come into direct contact with the one electrode, thereby preventing peeling problems that occur when the material constituting the one electrode is transferred to the adhesive member.

[0084] The surface protective part preferably covers the entire exposed surface of one electrode. Covering the entire exposed surface of one electrode further improves the function of the surface protective part. The exposed surface of one electrode specifically refers to the surface of the one electrode that does not face the photoelectric conversion layer, the side surface, etc.

[0085] The material constituting the surface protective portion is a compound derived from a fluorine-based silane compound (also referred to as a "fluorine-containing silane compound"). In other words, a fluorine-based silane compound is used as the material for forming the surface protective portion. Because fluorine-based silane compounds are highly reactive with various metals or metal oxides that can constitute one of the electrodes, a uniformly flat and thin surface protective portion can be formed on one of the electrodes. The ability to form such a thin-film surface protective portion improves the flexibility of the surface protective portion, suppressing damage to the surface protective portion even when the photoelectric conversion element is bent. As a result, electrode peeling and a decrease in storage durability of the first electrode of the photoelectric conversion element are suppressed. Furthermore, a surface protective portion containing a compound derived from a fluorine-based silane compound has high water repellency, antifouling properties, weather resistance, and abrasion resistance. Furthermore, considering that fluorine-based silane compounds can be used by dissolving them in non-fluorine-based organic solvents rather than fluorine-based organic solvents, they are also easy to handle. The fluorine-based silane compound is a fluorine-containing compound having an alkoxysilyl group. The alkoxysilyl group is not particularly limited as long as it is a group in which 1 to 3 alkoxy groups are bonded to a silicon atom, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Furthermore, as described above, the compound derived from the fluorine-based silane compound constituting the surface protective part may be chemically bonded to one electrode by the fluorine-based silane compound reacting with one electrode. In other words, the surface protective part is not limited to being an independent member that is not chemically bonded to one electrode, and may be chemically bonded to one electrode as long as it is functionally different from the one electrode.

[0086] As the fluorine-based silane compound, for example, a compound represented by the following general formula (A) is preferably used: By using the compound represented by general formula (A), peeling of the electrode and deterioration of storage durability in the photoelectric conversion element can be further suppressed. [ka] (In general formula (A), R 1 and R 2each independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, a represents an integer of 2 to 3, p represents an integer of 1 to 2, q represents an integer of 0 to 5, m represents an integer of 1 to 3, n represents an integer of 2 to 4, and p+q+2m+n is an integer of 5 to 14.

[0087] The average thickness of the surface protective part is preferably 1 μm or less. Having a thickness of 1 μm or less improves the flexibility of the surface protective part, suppressing damage to the surface protective part even when the photoelectric conversion element is bent. As a result, peeling of the first electrode in the photoelectric conversion element and deterioration of storage durability are further suppressed. The method for measuring the average thickness of the surface protective part is not particularly limited and can be measured using any known method. For example, it can be measured using a stylus-type thin film profilometer, a white light interference microscope, an atomic force microscope, or the like. Furthermore, the thickness is measured at five or more different locations on the surface protective part, and the average value of these measurements is used. Conventionally, materials used to form the surface protective portion include metal oxides such as SiOx, SiOxNy, and Al2O3, polyethylene, fluorine-based coating agents, and polymers such as polyparaxylylene. However, these conventional materials make it difficult to form a thin surface protective portion, particularly a thickness of 1 μm or less, and the flexibility of the surface protective portion is insufficient. As a result, when a photoelectric conversion element having a surface protective portion formed from a conventional material is bent, cracks form in the surface protective portion due to bending stress, allowing water and oxygen to penetrate through the cracks, resulting in reduced storage durability. In this regard, when a compound derived from a fluorine-based silane compound is used as the material to form the surface protective portion, it becomes easy to form the average thickness of the surface protective portion to 1 μm or less, improving the flexibility of the surface protective portion and improving storage durability.

[0088] Examples of methods for producing the surface protection portion include hand coating, nozzle flow coating, dipping, spraying, reverse coating, flow coating, spin coating, and roll coating.

[0089] <Sealing member> The "sealing member" is a member that suppresses the intrusion of external substances such as water and oxygen into the photoelectric conversion element and contact with each of the above layers, and is provided adjacent to the surface protection part. The sealing member preferably has a gas barrier member that suppresses the intrusion of external substances into the photoelectric conversion element and an adhesive member that adheres to the surface protection part, and it is more preferable that these members are an integrated film-like member. In addition, when the sealing member is provided on the opposite side of the light incident surface, the sealing member may not have light transmittance or transparency.

[0090] The functions required for the gas barrier member are generally expressed by the water vapor transmission rate and the oxygen transmission rate, etc. The water vapor transmission rate per day in accordance with JIS K7129 B method standard is, for example, 10 g / m 2 It is preferably as follows, and the lower it is, the more preferable. Also, the oxygen transmission rate per day in accordance with JIS K7126-2 is, for example, 1 cm 3 / m 2 ·atm or less is preferable, and the lower it is, the more preferable.

[0091] Examples of the material of the gas barrier member include a resin film coated with aluminum and a resin film coated with silicon oxide.

[0092] As the material of the adhesive member, for example, general materials used for sealing organic electroluminescent elements and organic transistors can be used. Specifically, pressure-sensitive adhesive resins, thermosetting resins, thermoplastic resins, photocurable resins, etc. can be mentioned. Among these, a pressure-sensitive adhesive resin that does not require heating in the sealing process is preferable. More specifically, ethylene-vinyl acetate copolymer resin, styrene-isobutylene resin, hydrocarbon-based resin, epoxy-based resin, polyester-based resin, acrylic-based resin, urethane-based resin, silicone-based resin, etc. can be mentioned. Various adhesive properties can be obtained by chemical modification, molecular weight adjustment, etc. at the main chain, branched chain, and terminal of these resins.

[0093] <UV cut layer> The "UV cut layer" is a layer provided on the light incident side to suppress deterioration of the photoelectric conversion element due to UV light. The UV cut layer is preferably a film-like member that absorbs UV light. The UV cut layer is also preferably provided on a substrate located on the light incident side.

[0094] The functionality required of a UV-cutting layer is generally expressed in terms of light transmittance, etc. The light transmittance for light with a wavelength of 370 nm or less is preferably, for example, less than 1%. Also, the light transmittance for light with a wavelength of 410 nm or less is preferably, for example, less than 1%.

[0095] <Gas barrier layer> The "gas barrier layer" is a layer that prevents external substances such as water and oxygen from penetrating into the photoelectric conversion element. The gas barrier layer is preferably a continuous film. The gas barrier layer is preferably provided adjacent to the substrate, and more preferably between the other electrode and the substrate. In the present disclosure, when the gas barrier layer is provided adjacent to the substrate, the gas barrier layer is considered to be one component constituting the substrate.

[0096] The performance required of a gas barrier layer is generally expressed in terms of water vapor permeability and oxygen permeability. The water vapor permeability per day according to JIS K7129 B method is, for example, 10 g / m 2 The oxygen permeation rate per day according to JIS K7126-2 is preferably 1 cm or less, and the lower the better. 3 / m 2 It is preferable that it is below 1000 atm, and the lower the better.

[0097] Examples of materials for the gas barrier layer include materials containing SiO2, SiNx, Al2O3, SiC, SiCN, SiOC, and SiOAl, and siloxane-based materials.

[0098] <Other layers> The photoelectric conversion element may further have other layers such as an insulating porous layer, a deterioration prevention layer, and a protective layer, if necessary.

[0099] <Configuration of photoelectric conversion element related to organic thin-film solar cell>

[0100] An example of the configuration of a photoelectric conversion element will be described with reference to Figures 1 and 2. Figure 1 is a schematic overhead view showing an example of a photoelectric conversion element. Figure 2 is a schematic cross-sectional view showing an example of a photoelectric conversion element.

[0101] As shown in the schematic overhead view of Figure 1, the photoelectric conversion element 1 has a photoelectric conversion region 2 which is an area capable of photoelectric conversion, a sealing region 3 which surrounds the photoelectric conversion region 2, and other regions 4 in which other components such as terminals are provided.

[0102] As shown in the cross-sectional schematic diagram of FIG. 2 , the photoelectric conversion element 1 has a structure (hereinafter also referred to as “Structure A”) in which, in the photoelectric conversion region 2, a UV-cut layer 11, a substrate 12, a first electrode 13, a first electron transport layer 14, a second electron transport layer (intermediate layer) 15, a photoelectric conversion layer 16, a hole transport layer 17, a second electrode 18, a surface protection portion (passivation layer) 19, and a sealing member 20 are stacked in the stacking direction z in this order from the light incident surface side. The photoelectric conversion element 1 also has a structure in the sealing region 3 in which, in the stacking direction z in this order from the light incident surface side, a UV-cut layer 11, a substrate 12, a first electrode 13, and a sealing member 20 are stacked. The sealing member 20 includes an adhesive member 21 and a gas barrier member 22. The sealing member 20 encapsulates the first electron transport layer 14, the second electron transport layer (intermediate layer) 15, the photoelectric conversion layer 16, the hole transport layer 17, the second electrode 18, and the surface protection portion (passivation layer) 19, and is bonded to the surface protection portion 19 (passivation layer) and the adhesive region 30 of the first electrode 13. In the photoelectric conversion element 1, the first electrode 13 corresponds to the "other electrode" described above, and the second electrode 18 corresponds to the "one electrode" described above. The photoelectric conversion element 1 may further include a connection portion for electrically connecting the photoelectric conversion element 1 to another photoelectric conversion element in series or parallel. The stacking direction z represents the direction perpendicular to the plane (xy plane) of each layer in the photoelectric conversion element.

[0103] As described above, the stacking order from the first electrode 13 to the second electrode 18 in the photoelectric conversion region 2 of the photoelectric conversion element 1 having Structure A is not limited to this order. Specifically, the photoelectric conversion element 1 may have a structure (hereinafter also referred to as "Structure B") in which a UV-cut layer 11, a substrate 12, a second electrode 13, a hole transport layer 14, a photoelectric conversion layer 15, a second electron transport layer (intermediate layer) 16, a first electron transport layer 17, a first electrode 18, a surface protection portion (passivation layer) 19, and a sealing member 20 are stacked in this order from the light incident surface side along the stacking direction z in the photoelectric conversion region 2. At this time, the sealing member 20 encapsulates the hole transport layer 14, the photoelectric conversion layer 15, the second electron transport layer (intermediate layer) 16, the first electron transport layer 17, the first electrode 18, and the surface protection portion (passivation layer) 19, and is adhered to the surface protection portion 19 (passivation layer) and an adhesion region 30 in the second electrode 13. In the photoelectric conversion element 1, the second electrode 13 corresponds to the above-mentioned "other electrode," and the first electrode 18 corresponds to the above-mentioned "one electrode." In the present disclosure, as shown in FIGS. 1 and 2, a photoelectric conversion element having structure A will be mainly described as an example, but a person skilled in the art can easily understand a photoelectric conversion element having structure B from such an explanation.

[0104] <<Photoelectric conversion module based on organic thin-film solar cells>> A "photoelectric conversion module" is a module having a plurality of electrically connected photoelectric conversion elements. The electrical connection may be either a case where the photoelectric conversion elements are connected in series or in parallel. Furthermore, a photoelectric conversion module may have both a plurality of photoelectric conversion elements connected in series and a plurality of photoelectric conversion elements connected in parallel. Note that "connection" in this disclosure is not limited to a physical connection, but also includes an electrical connection.

[0105] The photoelectric conversion module includes a plurality of photoelectric conversion elements, a connector that electrically connects the photoelectric conversion elements, and other components as needed. In other words, the photoelectric conversion module includes at least a first photoelectric conversion element, a second photoelectric conversion element adjacent to the first photoelectric conversion element, and a connector that electrically connects the first photoelectric conversion element and the second photoelectric conversion element, and other components as needed. Note that the photoelectric conversion elements and the connector may be functionally distinct components, and the photoelectric conversion elements and the connector may be separate components, or the photoelectric conversion elements and the connector may be provided as a continuous or integral component. For example, the electrodes and the connector, which are components of the photoelectric conversion element, may be separate components, or they may be provided as a continuous or integral component.

[0106] <<Photoelectric conversion element related to organic thin-film solar cell, and method of manufacturing photoelectric conversion module>> By describing an example of a method for manufacturing a photoelectric conversion module, an example of a method for manufacturing a photoelectric conversion element will also be described. Note that, in this disclosure, an example of a method for manufacturing a photoelectric conversion element having structure A as shown in Figure 2 will be described, but a person skilled in the art will easily understand from this description an example of a method for manufacturing a photoelectric conversion element having structure B.

[0107] A method for manufacturing a photoelectric conversion module having a photoelectric conversion element includes, for example, a gas barrier layer forming step of forming a gas barrier layer on a substrate, a first electrode forming step of forming a first electrode on the substrate having the gas barrier layer, an electron transport layer forming step of forming an electron transport layer on the first electrode, a photoelectric conversion layer forming step of forming a photoelectric conversion layer on the electron transport layer, a through-hole forming step of forming a through-hole that penetrates the electron transport layer and the photoelectric conversion layer, and a hole transport layer formed on the photoelectric conversion layer and coating the exposed surfaces of the first electrode, the electron transport layer, and the photoelectric conversion layer in the through-hole with a material for the hole transport layer. The method includes a hole transport layer forming step, a second electrode forming step of forming a second electrode on the hole transport layer and filling the through portion with the material of the second electrode to form a through structure, a surface protective portion forming step of forming a surface protective portion on the second electrode, an adhesive region forming step of forming an adhesive region on the first electrode by removing the outer periphery of the laminate from the electron transport layer to the surface protective portion, and a sealing member forming step of encapsulating the laminate from the electron transport layer to the surface protective portion in a sealing member and bringing the sealing member into contact with the surface protective portion and the adhesive region, and optionally includes other steps such as a UV-cut layer forming step.

[0108] <Gas barrier layer forming process> The method for producing a photoelectric conversion module having a photoelectric conversion element preferably includes a gas barrier layer forming step of forming a gas barrier layer on a substrate. Note that if the substrate itself has gas barrier properties, the gas barrier layer does not need to be formed.

[0109] <First electrode formation step> The method for producing a photoelectric conversion module having a photoelectric conversion element preferably includes a first electrode forming step of forming a first electrode on a substrate having a gas barrier layer. Note that, when the substrate does not have a gas barrier layer, the first electrode may be formed on the substrate. The method for forming the first electrode is as described in the description of the first electrode.

[0110] <Electron transport layer formation process> The method for manufacturing a photoelectric conversion module having a photoelectric conversion element preferably includes an electron transport layer forming step of forming an electron transport layer on a first electrode. When the electron transport layers include a first electron transport layer and a second electron transport layer (intermediate layer), the electron transport layer forming step preferably includes a first electron transport layer forming step of forming the first electron transport layer on the first electrode and a second electron transport layer forming step of forming the second electron transport layer on the first electron transport layer. The method for forming the electron transport layer is as described above in the description of the electron transport layer.

[0111] <Photoelectric conversion layer formation process> The method for producing a photoelectric conversion module having a photoelectric conversion element preferably includes a photoelectric conversion layer forming step of forming a photoelectric conversion layer on an electron transport layer. The method for forming the photoelectric conversion layer is as described in the description of the photoelectric conversion layer.

[0112] <Penetrating part formation process> The method for manufacturing a photoelectric conversion module having a photoelectric conversion element preferably includes a through-portion forming step of forming a through-portion that penetrates the electron transport layer and the photoelectric conversion layer. In the present disclosure, the through-portion refers to a hole, and in the case of a photoelectric conversion element having Structure A as shown in FIG. 2, it refers to a hole that penetrates the electron transport layer and the photoelectric conversion layer. The shape and size of the through-portion are not limited as long as it can electrically connect the photoelectric conversion elements. Examples of the through-portion include a linear or circular shape when the photoelectric conversion module is viewed from the second electrode side in a plan view, and a rectangular or square shape when the cross section of the photoelectric conversion element is observed. The through-portion divides each layer to form multiple photoelectric conversion elements. Examples of methods for forming the through-hole include laser deletion and mechanical scribing.

[0113] <Hole transport layer forming step> The method for manufacturing a photoelectric conversion module having a photoelectric conversion element preferably includes a hole transport layer formation step of forming a hole transport layer on the photoelectric conversion layer and coating the first electrode, the electron transport layer, and the exposed surfaces of the photoelectric conversion layer in the through-hole portion with a material for the hole transport layer. The method for forming the hole transport layer is as described above in the description of the hole transport layer.

[0114] <Second electrode formation step> The method for manufacturing a photoelectric conversion module having a photoelectric conversion element preferably includes a second electrode formation step of forming a second electrode on the hole transport layer and filling the through-hole with the material of the second electrode to form a through-hole structure. In the present disclosure, the through-hole structure refers to a structure that fills the inside of the through-hole, and in the case of a photoelectric conversion module having Structure A shown in Figure 2, it refers to a structure formed from the material of the hole transport layer and the material of the second electrode. This through-hole structure functions as a connection between photoelectric conversion elements. The method for forming the second electrode is as described in the description of the second electrode.

[0115] <Surface protection part formation process> The method for producing a photoelectric conversion module having a photoelectric conversion element preferably includes a surface protection part forming step of forming a surface protection part on the second electrode. The method for forming the surface protective portion is as described in the description of the surface protective portion.

[0116] <Adhesion area formation process> The method for manufacturing a photoelectric conversion module having a photoelectric conversion element preferably includes an adhesive region formation step of exposing the first electrode by removing the outer periphery of the laminate from the electron transport layer to the surface protection part (the laminate of the electron transport layer, photoelectric conversion layer, hole transport layer, second electrode, and surface protection part), and forming an adhesive region on the first electrode. Examples of methods for removing the outer periphery include laser deletion and mechanical scribing.

[0117] <Sealing member forming process> A method for manufacturing a photoelectric conversion module having a photoelectric conversion element may include a sealing member forming step of encapsulating a laminate from an electron transport layer to a surface protection part (a laminate of an electron transport layer, a photoelectric conversion layer, a hole transport layer, a second electrode, and a surface protection part) in a sealing member and bonding the sealing member by bringing it into contact with the surface protection part and an adhesion region. Further, the sealing member forming step may be performed by first applying an adhesive member and then sticking a gas barrier member on the adhesive member, or by sticking a previously prepared one in which the adhesive member is applied to the gas barrier member. Note that the sealing member encapsulates the above laminate in the photoelectric conversion element. However, as described in this manufacturing method, even in a mode where the sealing member encapsulates the photoelectric conversion module, as a result, the above laminate in the photoelectric conversion element may be encapsulated. In other words, it is not limited to a mode in which the above laminate is encapsulated in each photoelectric conversion element.

[0118] <UV Cut Layer Forming Step> A method for manufacturing a photoelectric conversion module having a photoelectric conversion element may include a UV cut layer forming step of forming a UV cut layer on the light incident surface side as needed.

[0119] <Other Processes> A method for manufacturing a photoelectric conversion module having a photoelectric conversion element may include, as needed, an insulating porous layer forming step, a deterioration prevention layer forming step, a protective layer forming step, and the like.

[0120] <Specific Examples of Manufacturing Methods for Photoelectric Conversion Elements and Photoelectric Conversion Modules Related to Organic Thin Film Solar Cells> An example of a method for manufacturing a photoelectric conversion module having a photoelectric conversion element will be described in detail using FIGS. 3A to 3M. FIGS. 3A to 3M are schematic diagrams showing an example of a method for manufacturing a photoelectric conversion module. As shown in FIG. 3A, first, a first electrode 13 (the other electrode) is formed on a substrate 12 having gas barrier properties. When forming multiple photoelectric conversion elements on one substrate 12, a portion of the formed first electrode 13 is removed to form a first dividing section 13′, as shown in FIG. 3B. In this case, the photoelectric conversion element formed on the left side of the dividing section 13′ is referred to as the first photoelectric conversion element, and the photoelectric conversion element formed on the right side of the dividing section 13′ is referred to as the second photoelectric conversion element. Next, as shown in FIGS. 3C and 3D, a first electron transport layer 14 and a second electron transport layer (intermediate layer) 15 are formed on the substrate 12 and the first electrode 13. Next, a photoelectric conversion layer 16 is formed on the formed second electron transport layer 15, as shown in FIG. 3E. After forming the photoelectric conversion layer 16, as shown in FIG. 3F, a predetermined region is removed so as to penetrate the first electron transport layer 14 and the second electron transport layer 15 formed on the first electrode 13 and the photoelectric conversion layer 16, thereby forming a through-hole 16'. After forming the through-hole 16', as shown in FIGS. 3G and 3H, a hole transport layer 17 and a second electrode 18 are formed. Furthermore, in conjunction with the formation of the hole transport layer 17 and the second electrode 18, a connection portion 18', which is a structure made of the material of the hole transport layer and the material of the second electrode, is formed in the through-hole 16'. When multiple photoelectric conversion elements are formed on one substrate 12, as shown in FIG. 3I, a predetermined region is removed so as to penetrate the second electrode 18 and the hole transport layer 17 between the second electrode 18 (one electrode) of the first photoelectric conversion element and the second electrode 18 (one electrode) of the second photoelectric conversion element, thereby forming a second dividing portion 13''. Next, as shown in FIG. 3J, a surface protection portion 19 is formed on the second electrode 18. At this time, as the surface protection section 19 is formed, a structure containing the material that constitutes the surface protection section (this structure is also considered to be one component of the dividing section) is formed in the second dividing section 13''. Note that, as shown in Figure 3J, the structure (dividing section) is continuous with each surface protection section 19 in the first photoelectric conversion element and the second photoelectric conversion element. Also, as shown in Figure 3J, the structure (dividing section) is in contact with the side surfaces of each second electrode 18 (one electrode) in the first photoelectric conversion element and the second photoelectric conversion element, the side surfaces of each hole transport layer 17 in the first photoelectric conversion element and the second photoelectric conversion element, and the photoelectric conversion layer 16.Since the structure (dividing portion) made of the same material as that of the surface protective portion contacts and covers the side surface and the photoelectric conversion layer, water or oxygen entering from the outside is prevented from contacting each layer, such as the photoelectric conversion layer, and corrosion and deterioration that occur over time in each layer, such as the photoelectric conversion layer, are suppressed, thereby improving storage durability. Next, as shown in Figure 3K, the outer periphery of the laminate from the electron transport layer 14 to the surface protective portion 19 is removed to expose the first electrode 13, and an adhesive region is formed on the first electrode 13. Furthermore, the laminate from the electron transport layer to the surface protective portion is enclosed in a sealing member 20 and brought into contact with the surface protective portion and the adhesive region to bond them.

[0121] <<Photoelectric conversion element related to dye-sensitized solar cell>> As an example of a photoelectric conversion element other than the above organic thin-film solar cell, a photoelectric conversion element related to a dye-sensitized solar cell will be described. The photoelectric conversion element includes at least a first electrode, a photoelectric conversion layer, and a second electrode, in that order. The photoelectric conversion layer includes an electron transport moiety, a photosensitizing compound, and a hole transport moiety. The photoelectric conversion element also has a surface protection part that is provided adjacent to a surface of one of the first electrode and the second electrode that does not face the photoelectric conversion layer. The photoelectric conversion element preferably includes a sealing member that is disposed adjacent to the surface protection part and that encloses the surface protection part, one electrode, and the photoelectric conversion layer. Furthermore, the photoelectric conversion element may optionally include a substrate, etc. The substrate is preferably provided adjacent to the other electrode on the side of the other electrode that does not face the photoelectric conversion layer. That is, the photoelectric conversion element has a configuration in which, for example, a substrate, a first electrode, a photoelectric conversion layer, a second electrode, a surface protective part, and a sealing member are sequentially laminated. Each configuration will be described below, but the substrate, the first electrode, the second electrode, the surface protective part, and the sealing member may be the same as those in the photoelectric conversion element related to the above-mentioned organic thin-film solar cell, and therefore description thereof will be omitted.

[0122] <Photoelectric conversion layer> The photoelectric conversion layer has an electron transporting portion that transports electrons, a photosensitizing compound that absorbs light and generates charges, and a hole transporting portion that transports holes.

[0123] -Electron Transport Department- The electron transport moiety transports electrons generated by the photosensitizing compound.

[0124] The electron transporting portion contains an electron transporting material and, if necessary, other materials. The electron transporting material is not particularly limited and can be appropriately selected depending on the purpose, but a semiconductor material is preferred. The semiconductor material preferably has a particulate shape, and these particles are bonded together to form a porous film. A photosensitizing compound is chemically or physically adsorbed onto the surface of the semiconductor particles that make up the porous electron transporting portion.

[0125] The semiconductor material is not particularly limited, and known materials can be used, such as elemental semiconductors, compound semiconductors, and compounds having a perovskite structure. Examples of elemental semiconductors include silicon and germanium. Compound semiconductors include, for example, metal chalcogenides, specifically oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum, etc.; sulfides of cadmium, zinc, lead, silver, antimony, bismuth, etc.; selenides of cadmium, lead, etc.; tellurides of cadmium, etc. Other compound semiconductors include phosphides of zinc, gallium, indium, cadmium, etc., gallium arsenide, copper-indium-selenide, copper-indium-sulfide, etc. Examples of compounds having a perovskite structure include strontium titanate, calcium titanate, sodium titanate, barium titanate, and potassium niobate. Among these, oxide semiconductors are preferred, and titanium oxide, zinc oxide, tin oxide, and niobium oxide are particularly preferred. When the electron transporting material of the electron transporting portion is titanium oxide, the conduction band is high and a high open circuit voltage is obtained. In addition, the refractive index is high and a high short circuit current is obtained due to the light confinement effect. Furthermore, it is advantageous in that a high dielectric constant and high mobility result in a high fill factor. These may be used alone or in combination of two or more. The crystal type of the semiconductor material is not particularly limited and can be appropriately selected depending on the purpose, and may be single crystal, polycrystalline, or amorphous.

[0126] The number-average particle size of the primary particles of the semiconductor material is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 1 nm to 100 nm, more preferably 5 nm to 50 nm. Furthermore, semiconductor materials larger than the number-average particle size may be mixed or layered, which may improve conversion efficiency by scattering incident light. In this case, the number-average particle size is preferably 50 nm to 500 nm.

[0127] The average thickness of the electron transporting portion is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 nm to 100 μm, more preferably 100 nm to 50 μm, and even more preferably 120 nm to 10 μm. When the average thickness of the electron transporting portion is within the preferred range, a sufficient amount of the photosensitizing compound per unit projected area can be secured, a high light capture rate can be maintained, and the diffusion distance of the injected electrons is unlikely to increase, which is advantageous in that loss due to charge recombination can be reduced.

[0128] -Photosensitizing compounds- The photosensitizing compound is adsorbed onto the surface of the semiconductor material that constitutes the electron transporting portion in order to further improve the output and photoelectric conversion efficiency.

[0129] The photosensitizing compound is not particularly limited as long as it is a compound that is photoexcited by light irradiated onto the photoelectric conversion element, and can be appropriately selected depending on the purpose. Examples of the photosensitizing compound include metal complex compounds, coumarin compounds, polyene compounds, indoline compounds, and thiophene compounds that are known as photosensitizing compounds. As the photosensitizing compound, it is preferable to use at least one selected from the compounds represented by the following general formula (15) and the compounds represented by the following general formula (16).

[0130] [ka] In general formula (15), Ar1 and Ar2 represent an aryl group which may have a substituent, R1 and R2 represent a linear or branched alkyl group having 4 to 10 carbon atoms, and X represents any of the substituents represented by the following structural formulas:

[0131] [ka]

[0132] [ka] In the general formula (16), n represents an integer of 0 or 1. R3 represents an aryl group which may have a substituent, or any of the substituents represented by the following structural formulas.

[0133] [ka]

[0134] Among the photosensitizing compounds represented by the above general formula (15), the compound represented by the following general formula (17) is more preferably used because it can provide high output even with low illuminance light.

[0135] [ka] In general formula (17), Ar4 and Ar5 represent a phenyl group which may have a substituent or a naphthyl group which may have a substituent, and Ar6 represents a phenyl group which may have a substituent or a thiophene group which may have a substituent.

[0136] -Hole transport part- The hole transport moiety can be any known material as long as it has the function of transporting holes, and examples thereof include an electrolytic solution in which a redox pair is dissolved in an organic solvent, a gel electrolyte in which a polymer matrix is ​​impregnated with a liquid in which a redox pair is dissolved in an organic solvent, a molten salt containing a redox pair, a solid electrolyte, an inorganic hole transport material, an organic hole transport material, etc. Among these, although an electrolytic solution or a gel electrolyte can be used, a solid electrolyte is preferred, and an organic hole transport material is more preferred.

[0137] Examples of the organic hole transport material include oxadiazole compounds, triphenylmethane compounds, pyrazoline compounds, hydrazone compounds, oxadiazole compounds, tetraarylbenzidine compounds, stilbene compounds, spiro compounds, etc. Among these, spiro compounds are more preferred.

[0138] As the spiro-type compound, for example, a compound represented by the following general formula (18) is preferable.

[0139] [ka] In the general formula (18), R 31 ~R 34 each independently represents a substituted amino group such as a dimethylamino group, a diphenylamino group, or a naphthyl-4-tolylamino group.

[0140] The hole transport layer preferably further contains a lithium salt represented by the following general formula (19).

[0141] [ka] In the general formula (3), A and B represent any one of the substituents F, CF3, C2F5, C3F7, and C4F9, and the substituents A and B are different.

[0142] Examples of these lithium salts include lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide (Li-FTFSI), lithium (fluorosulfonyl) (pentafluoroethanesulfonyl) imide (Li-FPFSI), lithium (fluorosulfonyl) (nonafluorobutanesulfonyl) imide (Li-FNFSI), lithium (nonafluorobutanesulfonyl) (trifluoromethanesulfonyl) imide (Li-NFTFSI), and lithium (pentafluoroethanesulfonyl) (trifluoromethanesulfonyl) imide (Li-PFTFSI). Of these, lithium (fluorosulfonyl) (trifluoromethylsulfonyl) imide (Li-FTFSI) is particularly preferred.

[0143] <<Photoelectric conversion element related to perovskite solar cells>> As an example of a photoelectric conversion element other than the above organic thin-film solar cell, a photoelectric conversion element related to a perovskite solar cell will be described. The photoelectric conversion element has at least a first electrode, a photoelectric conversion layer, and a second electrode in this order. In the case where another layer is inserted between the electrodes, for example, a photoelectric conversion element has a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a second electrode in this order. The photoelectric conversion element also has a surface protection part that is provided adjacent to a surface of one of the first electrode and the second electrode that does not face the photoelectric conversion layer. The photoelectric conversion element preferably includes a sealing member that is disposed adjacent to the surface protection part and that encloses the surface protection part, one electrode, and the photoelectric conversion layer. Furthermore, the photoelectric conversion element may optionally include a substrate, etc. The substrate is preferably provided adjacent to the other electrode on the side of the other electrode that does not face the photoelectric conversion layer. That is, the photoelectric conversion element has a configuration in which, for example, a substrate, a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, a second electrode, a surface protective part, and a sealing member are sequentially stacked. Each configuration will be described below, but the substrate, the first electrode, the second electrode, the surface protective part, and the sealing member may be the same as those in the photoelectric conversion element related to the above-mentioned organic thin-film solar cell, and therefore description thereof will be omitted.

[0144] <Electron transport layer> The electron transport layer transports electrons generated in the photoelectric conversion layer.

[0145] The electron transport layer contains an electron transport material. The electron transport material is not particularly limited and can be appropriately selected depending on the purpose, but a semiconductor material is preferred. The semiconductor material is not particularly limited and known materials can be used, for example, a simple semiconductor, a compound having a compound semiconductor, etc. Examples of elemental semiconductors include silicon and germanium. Examples of compound semiconductors include metal chalcogenides. Examples of metal chalcogenides include metal oxides (oxide semiconductors), metal sulfides, metal selenides, and metal tellurides. Examples of metal oxides (oxide semiconductors) include oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum. Examples of metal sulfides include sulfides of cadmium, zinc, lead, silver, antimony, and bismuth. Examples of metal selenides include selenides of cadmium and lead. Examples of metal tellurides include tellurides of cadmium and the like. Other compound semiconductors include phosphides of zinc, gallium, indium, cadmium, etc., gallium arsenide, copper-indium-selenide, copper-indium-sulfide, etc. Among these, metal oxides (oxide semiconductors) are preferred, and in particular, those containing at least one of titanium oxide, zinc oxide, tin oxide, and niobium oxide are more preferred, with tin oxide being particularly preferred. These may be used alone or in combination of two or more. The crystalline form of the semiconductor material is not particularly limited and can be appropriately selected depending on the purpose, and may be single crystal, polycrystalline, or amorphous.

[0146] <Photoelectric conversion layer> The photoelectric conversion layer is a layer that performs photoelectric conversion, and has a perovskite layer that contains a perovskite compound.

[0147] A perovskite compound is a composite material of an organic compound and an inorganic compound, and is represented by the following general formula (20).

[0148] [ka] In the above general formula (20), the ratio of α:β:γ is 3:1:1, and β and γ represent integers greater than 1. Furthermore, for example, X can be a halogen ion, Y can be an ion of an organic compound having an amino group, and M can be a metal ion.

[0149] X in the above general formula (20) is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include halogen ions such as chlorine, bromine, and iodine. These may be used alone or in combination of two or more.

[0150] Examples of Y in the above general formula (20) include organic cations such as alkylamine compound ions of methylamine, ethylamine, n-butylamine, and formamidine, and inorganic alkali metal cations such as cesium, potassium, and rubidium. These may be used alone or in combination of two or more, or inorganic alkali metal cations and organic cations may be used in combination.

[0151] M in the above general formula (20) is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ions of metals such as lead, indium, antimony, tin, copper, bismuth, etc. These may be used alone or in combination of two or more.

[0152] The perovskite layer preferably has a layered perovskite structure in which layers made of metal halide and layers in which organic cation molecules are arranged are alternately laminated.

[0153] <Hole transport layer> The hole transport layer transports holes generated in the photoelectric conversion layer.

[0154] The hole transport layer contains a hole transport material. The hole transport material is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable that the hole transport layer contains, for example, a compound having a repeating structure represented by the following general formula (21) and a compound represented by the following general formula (22).

[0155] [ka]

[0156] In the general formula (21), Ar1 represents an aryl group. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 9-anthracenyl group. The aryl group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and an aryl group. Ar2, Ar3, and Ar4 each independently represent an arylene group, a divalent heterocyclic group, or the like. Examples of the arylene group include 1,4-phenylene, 1,1'-biphenylene, and 9,9'-di-n-hexylfluorene. Examples of the divalent heterocyclic group include 2,5-thiophene. R1 to R4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or the like. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the aryl group include a phenyl group and a 2-naphthyl group. The alkyl group and the aryl group may have a substituent.

[0157] [ka]

[0158] In the general formula (22), R1 to R5 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and may be the same or different. X represents a cation. R1 and R2, or R2 and R3 may combine together to form a ring structure. Examples of halogen atoms include chlorine atoms, bromine atoms, and iodine atoms. Examples of the alkyl group include alkyl groups having a carbon number of 1 to 6. The alkyl group may be substituted with a halogen atom. Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms. The aryl group may, for example, be a phenyl group. The cation is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include alkali metal cations, phosphonium cations, iodonium cations, nitrogen-containing cations, sulfonium cations, etc. Here, the nitrogen-containing cation means an ion having a positive charge on the nitrogen atom, and examples thereof include ammonium cations, pyridinium cations, imidazolium cations, etc.

[0159] The hole transporting material other than the compound having a repeating structure represented by general formula (21) and the compound represented by general formula (22) is not particularly limited as long as it has the property of transporting holes, and can be appropriately selected depending on the purpose. However, an organic compound is preferable, and examples thereof include the following polymeric materials and low molecular weight materials.

[0160] The polymer material used for the hole transport layer is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include polythiophene compounds, polyphenylene vinylene compounds, polyfluorene compounds, polyphenylene compounds, and polythiadiazole compounds. Examples of polythiophene compounds include poly(3-n-hexylthiophene), poly(3-n-octyloxythiophene), poly(9,9'-dioctyl-fluorene-co-bithiophene), poly(3,3'''-didodecyl-quaterthiophene), poly(3,6-dioctylthieno[3,2-b]thiophene), and poly(2,5-bis(3-decylthiophen-2-yl)thieno[3,2 -b]thiophene), poly(3,4-didecylthiophene-co-thieno[3,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thieno[3,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thiophene), or poly(3,6-dioctylthieno[3,2-b]thiophene-co-bithiophene). Examples of polyphenylene vinylene compounds include poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene vinylene], and poly[(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene)-co-(4,4′-biphenylene vinylene)]. Examples of polyfluorene compounds include poly(9,9'-didodecylfluorenyl-2,7-diyl), poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co-(9,10-anthracene)], poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co-(4,4'-biphenylene)], poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co-(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene)], and poly[(9,9-dioctyl-2,7-diyl)-co-(1,4-(2,5-dihexyloxy)benzene)]. Examples of polyphenylene compounds include poly[2,5-dioctyloxy-1,4-phenylene] and poly[2,5-di(2-ethylhexyloxy-1,4-phenylene]]. Examples of polythiadiazole compounds include poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo(2,1′,3)thiadiazole], poly(3,4-didecylthiophene-co-(1,4-benzo(2,1′,3)thiadiazole), and the like.

[0161] The low molecular weight material used in the hole transport layer is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include oxadiazole compounds, triphenylmethane compounds, pyrazoline compounds, hydrazone compounds, tetraarylbenzidine compounds, stilbene compounds, spirobifluorene compounds, and thiophene oligomers.

[0162] <<Electronic equipment>> The electronic device includes at least the above-described photoelectric conversion element (which may be a photoelectric conversion module having a plurality of photoelectric conversion elements) and a device electrically connected to the photoelectric conversion element. The device electrically connected to the photoelectric conversion element is a device that operates using power generated by photoelectric conversion by the photoelectric conversion element. The electronic device may have a plurality of embodiments depending on the application, and examples thereof include the following first and second embodiments. The first type is an electronic device that has a photoelectric conversion element and a device electrically connected to the photoelectric conversion element, and optionally has other devices. The second form is an electronic device that has a photoelectric conversion element, a storage battery electrically connected to the photoelectric conversion element, and a device electrically connected to the photoelectric conversion element and the storage battery, and may also have other devices as necessary.

[0163] <<Power supply module>> The power supply module includes at least the above-described photoelectric conversion element and a power supply IC (Integrated Circuit) electrically connected to the photoelectric conversion element, and may include other devices as necessary.

[0164] <<Applications>> The photoelectric conversion element can function as a stand-alone power source, and can operate a device using the power generated by photoelectric conversion. Furthermore, since the photoelectric conversion element can generate electricity when irradiated with light, there is no need to connect the electronic device to an external power source or replace the battery. Therefore, the electronic device can be operated even in places without power supply facilities, can be worn and carried around, and can be operated without battery replacement even in places where battery replacement is difficult. Furthermore, when dry batteries are used in electronic devices, the electronic device becomes heavy and large, which can make it difficult to install on a wall or ceiling or to carry around. However, the photoelectric conversion element is lightweight and thin, allowing for a high degree of installation flexibility and offering great advantages in terms of being worn or carried around. As described above, photoelectric conversion elements can be used as a stand-alone power source, and therefore electronic devices incorporating photoelectric conversion elements can be used in a variety of applications. Examples of applications of electronic devices incorporating photoelectric conversion elements include display devices such as electronic desk calculators, wristwatches, mobile phones, electronic organizers, and electronic paper, computer accessories such as computer mice and computer keyboards, various sensor devices such as temperature and humidity sensors and motion sensors, transmitters such as beacons and GPS (Global Positioning System), auxiliary lights, and remote controls.

[0165] The photoelectric conversion element of the present disclosure can generate electricity even with low-illuminance light. Low-illuminance refers to, for example, the illuminance in an indoor environment illuminated by lighting or the like. Specifically, it refers to an illuminance of 20 lux to 1,000 lux, which is extremely weak compared to direct sunlight (approximately 100,000 lux). This means that power can be generated indoors and even in dimly lit areas, making it suitable for a wide range of applications. Furthermore, unlike dry batteries, it does not leak, and unlike button batteries, it is highly safe, preventing accidental ingestion. Furthermore, it can be used as an auxiliary power source to extend the continuous operating time of rechargeable or battery-powered electrical appliances. In this way, by combining a photoelectric conversion element with a device that operates using the power generated by the photoelectric conversion of the photoelectric conversion element, it is possible to obtain an electronic device that is lightweight, easy to use, has a high degree of installation flexibility, does not require replacement, is highly safe, and is effective in reducing environmental impact. Therefore, electronic devices equipped with photoelectric conversion elements can be used for a variety of purposes.

[0166] Figure 4 shows a schematic diagram of an example of the basic configuration of an electronic device that combines a photoelectric conversion element and a device circuit that operates using the power generated by the photoelectric conversion element. When light is irradiated onto the photoelectric conversion element, it generates power and can extract electricity, allowing the device circuit to operate using that power. However, since the output of the photoelectric conversion element varies depending on the ambient illuminance, the electronic device shown in Fig. 4 may not operate stably. In this case, it is preferable to incorporate a power supply IC between the photoelectric conversion element and the device circuit to supply a stable voltage to the device circuit side, as shown in the schematic diagram of an example of the basic configuration of an electronic device in Fig. 5. Furthermore, photoelectric conversion elements can generate electricity when irradiated with light of sufficient illuminance, but if the illuminance is insufficient to generate power, the desired power cannot be obtained, which is also a drawback of photoelectric conversion elements. In this case, as shown in the schematic diagram of an example of the basic configuration of an electronic device in Figure 6, by installing a power storage device such as a capacitor between the power supply IC and the equipment circuit, the surplus power from the photoelectric conversion element can be charged into the power storage device, and even if the illuminance is too low or no light hits the photoelectric conversion element, the power stored in the power storage device can be supplied to the equipment circuit, enabling stable operation of the equipment circuit. In this way, by combining a power supply IC and a power storage device with an electronic device that combines a photoelectric conversion element and an equipment circuit, it becomes possible to operate in an environment without a power source, eliminate the need for battery replacement, and enable stable operation. Electronic devices equipped with photoelectric conversion elements can be used for a variety of purposes.

[0167] Photoelectric conversion elements can also be used as power supply modules. For example, as shown in the schematic diagram of an example of the basic configuration of a power supply module in Figure 7, by connecting a photoelectric conversion element and a power supply IC, a DC power supply module can be configured in which the power generated by the photoelectric conversion element through photoelectric conversion can be supplied at a constant voltage level by the power supply IC. Furthermore, as shown in the schematic diagram of an example of the basic configuration of a power supply module in Figure 8, by adding a power storage device to the power supply IC, it becomes possible to charge the power generated by the photoelectric conversion element into the power storage device, making it possible to configure a power supply module that can supply power even when the illuminance is too low or when no light hits the photoelectric conversion element. The power supply modules shown in Figures 7 and 8 can be used as power supply modules without the need for battery replacement as with conventional primary batteries. Therefore, power supply modules equipped with photoelectric conversion elements can be used for a variety of purposes.

[0168] Specific applications of electronic devices having the above-described photoelectric conversion element and a device that operates on electric power will be described below.

[0169] <For use as a computer mouse> FIG. 9 is a schematic diagram showing an example of the basic configuration of a personal computer mouse (hereinafter also referred to as a "mouse") as an example of an electronic device. As shown in FIG. 9, the mouse has a photoelectric conversion element, a power supply IC, a power storage device, and a mouse control circuit. The power supply for the mouse control circuit is supplied with power from the connected photoelectric conversion element or power storage device. This allows the power storage device to be charged when the mouse is not in use and the mouse to be operated using that power, resulting in a mouse that does not require wiring or battery replacement. Furthermore, eliminating the need for a battery also allows for a lighter weight, making it suitable for use as a mouse.

[0170] FIG. 10 is a schematic external view showing an example of the personal computer mouse shown in FIG. 9. As shown in FIG. 10, the photoelectric conversion element, power supply IC, power storage device, and mouse control circuit are mounted inside the mouse, but the top of the photoelectric conversion element is covered with a transparent housing so that light can reach the photoelectric conversion element. It is also possible to mold the entire mouse housing from transparent resin. The arrangement of the photoelectric conversion element is not limited to this, and it can also be arranged in a position where light can reach the photoelectric conversion element even when the mouse is covered with a hand.

[0171] <For use as a computer keyboard> FIG. 11 is a schematic diagram showing an example of the basic configuration of a personal computer keyboard (hereinafter also referred to as "keyboard") as an example of an electronic device. As shown in FIG. 11, the keyboard has a photoelectric conversion element, a power supply IC, a power storage device, and a keyboard control circuit. The power supply for the keyboard control circuit is supplied with power from the connected photoelectric conversion element or power storage device. This allows the power storage device to be charged when the keyboard is not in use, and the keyboard to operate using that power, resulting in a keyboard that does not require wiring or battery replacement. Furthermore, eliminating the need for batteries allows for a lighter weight, making it suitable for keyboard applications.

[0172] FIG. 12 is a schematic external view showing an example of the personal computer keyboard shown in FIG. 11. As shown in FIG. 12, the photoelectric conversion element, power supply IC, power storage device, and keyboard control circuit are mounted inside the keyboard, but the upper part of the photoelectric conversion element is covered with a transparent housing so that light can reach the photoelectric conversion element. It is also possible to mold the entire keyboard housing from transparent resin. The arrangement of the photoelectric conversion element is not limited to this. For example, in the case of a small keyboard with limited space for incorporating the photoelectric conversion element, a small photoelectric conversion element can be embedded in part of the key, as shown in FIG. 13, a schematic external view showing another example of the personal computer keyboard shown in FIG. 11.

[0173] <Sensor applications> FIG. 14 is a schematic diagram showing an example of the basic configuration of a sensor as an example of an electronic device. As shown in FIG. 14, the sensor includes a photoelectric conversion element, a power supply IC, a power storage device, and a sensor circuit. The sensor circuit is powered by the connected photoelectric conversion element or power storage device. This eliminates the need to connect to an external power source or replace batteries. The sensor can sense temperature and humidity, illuminance, human presence, CO2, acceleration, UV, noise, geomagnetism, and air pressure. As shown in A in FIG. 15, the sensor preferably periodically senses the measurement target and transmits the acquired data to a PC (personal computer), smartphone, or the like via wireless communication.

[0174] With the advent of the Internet of Things (IoT), the number of sensors is expected to increase rapidly. However, replacing the batteries in these countless sensors one by one is extremely time-consuming and impractical. Furthermore, sensors are often placed in locations where battery replacement is difficult, such as on ceilings or walls, which reduces workability. Therefore, sensors that can be powered by photoelectric conversion elements offer significant advantages. Furthermore, the photoelectric conversion elements disclosed herein can obtain high output even in low illuminance and have little dependency on the light incident angle, resulting in high installation flexibility.

[0175] <Turntable use> FIG. 16 is a schematic diagram showing an example of the basic configuration of a turntable as an example of an electronic device. As shown in FIG. 16, the turntable has a photoelectric conversion element, a power supply IC, a power storage device, and a turntable control circuit. The turntable control circuit is powered by the connected photoelectric conversion element or power storage device. This makes it possible to configure a turntable without the need to connect to an external power source or replace batteries. Turntables are used, for example, in showcases for displaying merchandise. However, power wiring can be unsightly, and the display items must be removed when replacing the batteries, which is a significant hassle. Therefore, a turntable that can be powered by a photoelectric conversion element offers significant benefits. [Example]

[0176] Examples of the present invention will be described below, but the present invention is not limited to these examples in any way.

[0177] Example 1 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> -First electrode-attached substrate- First, a polyethylene terephthalate (PET) substrate (50 mm x 50 mm) with a gas barrier layer and a patterned indium-doped tin oxide (ITO) film was procured from Geomatec Co., Ltd. As shown in Figure 3B, a first dividing section was formed on the first electrode. The thickness of the substrate was 50 μm, and the daily water vapor permeation rate of the substrate was 3.0 × 10 -4 g / m 2 It was.

[0178] - Formation of the first electron transport layer - Next, zinc oxide nanoparticle liquid (manufactured by Aldrich, average particle diameter 12 nm) was spin-coated at 3,000 rpm onto an ITO gas barrier PET film (15 Ω / □) and dried at 100°C for 10 minutes to form an electron transport layer with an average thickness of 30 nm.

[0179] - Formation of the second electron transport layer (intermediate layer) - Next, dimethylaminobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in ethanol to prepare a 1 mg / ml solution, which was then spin-coated onto the first electron transport layer at 3,000 rpm to form a second electron transport layer with an average thickness of less than 10 nm.

[0180] - Formation of photoelectric conversion layer - 12 mg of exemplary compound 1 shown below (number average molecular weight (Mn) = 1,554, highest occupied molecular orbital (HOMO) level: 5.13 eV), 10 mg of exemplary compound 2 shown below (PC61BM, manufactured by Frontier Carbon Corp.), and 3 mg of exemplary compound 3 shown below (PTB7, manufactured by Lumtec Corp.) were dissolved in 1 mL of chloroform to prepare photoelectric conversion layer coating solution A.

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] Next, the photoelectric conversion layer coating solution A was spin-coated onto the intermediate layer at 600 rpm to form a photoelectric conversion layer with an average thickness of 200 nm.

[0185] - Formation of penetrations - Next, through-holes were formed as a preliminary step to forming connections that connect the photoelectric conversion elements in series. The through-holes were formed using laser deletion, and when the photoelectric conversion module was viewed in plan from the second electrode side, the through-holes had a rectangular shape and a width of 0.12 mm. When the photoelectric conversion module was viewed in plan from the second electrode side, the center-to-center distance between adjacent through-holes was 5.6 mm.

[0186] - Formation of hole transport layer, second electrode, and connection portion - Next, a hole transport layer material made of molybdenum oxide (manufactured by Kojundo Chemical Co., Ltd.) was deposited on the photoelectric conversion layer and through-hole portion to an average thickness of 20 nm, and a second electrode material made of silver was deposited on the photoelectric conversion layer and through-hole portion to an average thickness of 100 nm, successively by vacuum deposition to form a hole transport layer, a second electrode, and a connecting portion. As shown in Figure 3I, a second dividing portion was formed on the second electrode.

[0187] - Formation of surface protection part - Next, a surface protective layer material consisting of a fluorine-based silane compound (DURASURF DS-5935F130, manufactured by Harves Co., Ltd., a compound satisfying general formula (A)) was spin-coated onto the second electrode to form a surface protective layer with an average thickness of 50 nm. The formed surface protective layer covered the entire exposed surface of the second electrode.

[0188] - Formation of sealing material - The photovoltaic conversion module was covered with an aluminum PET-based sealing film with an adhesive layer (manufactured by Tesa Tape Co., Ltd.) as a sealing material, and a pressure of 5.0 × 10 was applied using a laminator. 5 The lamination was performed under the conditions of 1.0 m / min at a temperature of 70°C and a pressure of 1.0 Pa. The water vapor permeation rate of the gas barrier material of the sealing member per day was 10 g / m 2 It was as follows.

[0189] - Solar cell characteristic evaluation - First, the current-voltage characteristics of the photoelectric conversion element that constitutes the fabricated photoelectric conversion module were measured under white LED illumination (color temperature 5000K, illuminance 200lx). The photoelectric conversion efficiency was calculated from the obtained current-voltage curve. A bulb-shaped LED lamp (LDA11N-G / 100W, manufactured by Toshiba Lighting & Technology Corporation) was used as the white LED illumination, and measurements were taken using a KETSIGHT B2902A source meter as the evaluation equipment. The output of the LED light source was measured using a Sekonic C-7000 spectrophotometer.

[0190] -Electrode peelability evaluation- The fabricated photovoltaic conversion module was subjected to a U-shaped bending test 20 times with a bending radius of 15 mm and the light incident surface facing outward, using a tabletop durability testing machine and a planar body no-load U-shaped stretching test fixture (DMX-FS) manufactured by Yuasa System Equipment Co., Ltd. Next, in the photovoltaic conversion module after the U-shaped bending test, the current-voltage characteristics were measured in the same manner as in the solar cell characteristic evaluation before the U-shaped bending test, and the photovoltaic conversion efficiency was calculated. Thereafter, the rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test was calculated, and the results are shown in Table 1. However, for photoelectric conversion modules in which electrode peeling occurred after the U-shaped bending test, the rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test was not calculated, and this is shown as "electrode peeling" in Table 1. The rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test can be calculated using the following formula: "rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test = {(photoelectric conversion efficiency before the U-shaped bending test - photoelectric conversion efficiency after the U-shaped bending test) / photoelectric conversion efficiency before the U-shaped bending test)} × 100".

[0191] -Storage durability evaluation (at normal temperature and humidity)- The fabricated photovoltaic conversion module was subjected to a U-shaped bending test 20 times with a bending radius of 15 mm and the light incident surface facing outward, using a tabletop durability testing machine and a planar body no-load U-shaped stretching test fixture (DMX-FS) manufactured by Yuasa System Equipment Co., Ltd. Next, the photoelectric conversion module after the U-shaped bending test was left standing in a dark place at normal temperature and humidity (temperature: 25°C, humidity: 30%) for 500 hours. Next, for the photovoltaic conversion module after the room temperature and humidity storage test, the current-voltage characteristics were measured in the same manner as in the solar cell characteristic evaluation before the U-shaped bending test, and the photovoltaic conversion efficiency was calculated. Thereafter, the rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test and the room-temperature, normal humidity storage test was calculated, and the results are shown in Table 1. However, for photoelectric conversion modules in which electrode peeling occurred after the U-shaped bending test, the rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test and the room-temperature, normal humidity storage test was not calculated, and this was indicated as "electrode peeling" in Table 1. The rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test and the room-temperature, normal humidity storage test was calculated using the following formula: "rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test and the room-temperature, normal humidity storage test = {(photoelectric conversion efficiency before the U-shaped bending test and the room-temperature, normal humidity storage test - photoelectric conversion efficiency after the U-shaped bending test and the room-temperature, normal humidity storage test) / photoelectric conversion efficiency before the U-shaped bending test and the room-temperature, normal humidity storage test)} × 100."

[0192] -Storage durability evaluation (under high temperature and humidity)- The fabricated photovoltaic conversion module was subjected to a U-shaped bending test 20 times with a bending radius of 15 mm and the light incident surface facing outward, using a tabletop durability testing machine and a planar body no-load U-shaped stretching test fixture (DMX-FS) manufactured by Yuasa System Equipment Co., Ltd. Next, the photoelectric conversion module after the U-shaped bending test was left standing in a dark place at high temperature and humidity (temperature: 85° C., humidity: 85%) for 500 hours. Next, in the photovoltaic conversion module after the high-temperature, high-humidity storage test, the current-voltage characteristics were measured and the photovoltaic conversion efficiency was calculated in the same manner as in the solar cell characteristic evaluation before the U-shaped bending test. Thereafter, the rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test and the high-temperature, high-humidity storage test was calculated, and the results are shown in Table 1. However, for photoelectric conversion modules in which electrode peeling occurred after the U-shaped bending test, the rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test and the high-temperature, high-humidity storage test was not calculated, and this is shown as "electrode peeling" in Table 1. The rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test and the high-temperature, high-humidity storage test was calculated using the following formula: "rate of decrease in photoelectric conversion efficiency before and after the U-shaped bending test and the high-temperature, high-humidity storage test = {(photoelectric conversion efficiency before the U-shaped bending test and the high-temperature, high-humidity storage test - photoelectric conversion efficiency after the U-shaped bending test and the high-temperature, high-humidity storage test) / photoelectric conversion efficiency before the U-shaped bending test and the high-temperature, high-humidity storage test)} × 100.

[0193] Example 2 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that the average thickness of the surface protection portion was changed to 250 nm. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0194] Example 3 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that the average thickness of the surface protection portion was changed to 500 nm. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0195] Example 4 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that the average thickness of the surface protection portion was changed to 750 nm. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0196] Example 5 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution B described below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0197] -Photoelectric conversion layer coating solution B- 12 mg of the above-mentioned exemplary compound 1, 10 mg of the above-mentioned exemplary compound 2, and 3 mg of the following exemplary compound 4 (PBDB-T, manufactured by Brilliant Matters, number average molecular weight (Mn) = 15,000, highest occupied molecular orbital (HOMO) level: 5.33 eV) were dissolved in 1 mL of chloroform to prepare photoelectric conversion layer coating solution B.

[0198] [ka]

[0199] Example 6 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution C described below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0200] -Photoelectric conversion layer coating solution C- 12 mg of the following exemplary compound 5 (number average molecular weight (Mn) = 1,886, highest occupied molecular orbital (HOMO) level: 5.00 eV), 10 mg of the above exemplary compound 2, and 3 mg of the above exemplary compound 4 were dissolved in 1 mL of chloroform to prepare a photoelectric conversion layer coating solution C.

[0201] [ka]

[0202] Example 7 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution D described below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0203] -Photoelectric conversion layer coating solution D- 12 mg of the following exemplary compound 6 (number average molecular weight (Mn) = 1,806, highest occupied molecular orbital (HOMO) level: 5.20 eV), 10 mg of the above exemplary compound 2, and 3 mg of the above exemplary compound 4 were dissolved in 1 mL of chloroform to prepare a photoelectric conversion layer coating solution D.

[0204] [ka]

[0205] Example 8 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution E below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0206] -Photoelectric conversion layer coating solution E- 12 mg of the above exemplary compound 1, 10 mg of the below-described exemplary compound 7 (PC71BM, manufactured by Frontier Carbon Co., Ltd.), and 3 mg of the above exemplary compound 4 were dissolved in 1 mL of chloroform to prepare photoelectric conversion layer coating solution E.

[0207] [ka]

[0208] Example 9 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution F described below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0209] -Photoelectric conversion layer coating solution F- 12 mg of the above exemplary compound 1, 10 mg of the below-described exemplary compound 8 (PNP, manufactured by Harves Co., Ltd.), and 3 mg of the above exemplary compound 4 were dissolved in 1 mL of chloroform to prepare photoelectric conversion layer coating solution F.

[0210] [ka]

[0211] Example 10 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution G described below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0212] -Photoelectric conversion layer coating solution G- 12 mg of the following exemplary compound 9 (number average molecular weight (Mn) = 1,463, highest occupied molecular orbital (HOMO) level: 5.27 eV), 10 mg of the above exemplary compound 2, and 3 mg of the above exemplary compound 4 were dissolved in 1 mL of chloroform to prepare a photoelectric conversion layer coating solution G.

[0213] [ka]

[0214] Example 11 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution H described below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0215] -Photoelectric conversion layer coating solution H- 12 mg of the following exemplary compound 10 (number average molecular weight (Mn) = 2,029, highest occupied molecular orbital (HOMO) level: 5.50 eV), 10 mg of the above exemplary compound 2, and 3 mg of the above exemplary compound 4 were dissolved in 1 mL of chloroform to prepare photoelectric conversion layer coating solution H.

[0216] [ka]

[0217] Example 12 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was fabricated in the same manner as in Example 1, except that the substrate was changed to flexible glass (50 mm × 50 mm) on which an indium-doped tin oxide (ITO) pattern was formed. The thickness of the substrate was 50 μm, and the water vapor permeation rate of the substrate per day was 3.0 × 10 -4 g / m 2 It was. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0218] Example 13 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was fabricated in the same manner as in Example 5, except that the substrate was changed to flexible glass (50 mm × 50 mm) on which an indium-doped tin oxide (ITO) pattern was formed. The thickness of the substrate was 50 μm, and the water vapor permeation rate of the substrate per day was 3.0 × 10 -4 g / m 2 It was. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0219] Example 14 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> In the preparation of the photoelectric conversion module of Example 1, the material of the surface protection part was changed to a fluorine-based silane compound (DURASURF DP-508C, manufactured by Harves Co., Ltd., a compound satisfying general formula (A)), and the average thickness of the formed surface protection part was changed to 10 μm. A photoelectric conversion module was prepared in the same manner as in Example 1. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0220] Example 15 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> In the preparation of the photoelectric conversion module of Example 5, the material of the surface protection part was changed to a fluorine-based silane compound (DURASURF DP-508C, manufactured by Harves Co., Ltd., a compound satisfying general formula (A)), and the average thickness of the formed surface protection part was changed to 10 μm. A photoelectric conversion module was prepared in the same manner as in Example 5. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0221] Example 16 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution I described below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0222] -Photoelectric conversion layer coating liquid I- 15 mg of the above-mentioned exemplary compound 1 and 10 mg of the above-mentioned exemplary compound 2 were dissolved in 1 mL of chloroform to prepare photoelectric conversion layer coating solution I.

[0223] Example 17 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution J described below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0224] -Photoelectric conversion layer coating liquid J- 15 mg of the above-mentioned exemplary compound 9 and 10 mg of the above-mentioned exemplary compound 2 were dissolved in 1 mL of chloroform to prepare a photoelectric conversion layer coating solution J.

[0225] Example 18 <Fabrication of photoelectric conversion modules (Fabrication of organic thin-film solar cells)> A photoelectric conversion module was produced in the same manner as in Example 1, except that photoelectric conversion layer coating solution A was changed to photoelectric conversion layer coating solution K described below. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0226] -Photoelectric conversion layer coating solution K- 15 mg of the above-mentioned exemplary compound 10 and 10 mg of the above-mentioned exemplary compound 2 were dissolved in 1 mL of chloroform to prepare a photoelectric conversion layer coating solution K.

[0227] Example 19 <Fabrication of photoelectric conversion modules (Fabrication of dye-sensitized solar cells)> Indium-doped tin oxide (ITO) and niobium-doped tin oxide (NTO) were sequentially sputtered onto a flexible glass substrate as the first electrode, followed by a dense titanium oxide layer (average thickness 20 nm) as the hole-blocking layer, which was then reactively sputtered with oxygen gas. Next, a titanium dioxide (Greatcell Solar Materials, 18NR-T) paste was applied to the hole-blocking layer by screen printing to an average thickness of approximately 1.3 μm. After drying at 120°C, the substrate was sintered in air at 550°C for 30 minutes to form a porous electron transport region. The ITO / NTO layer, hole-blocking layer, and electron transport region were then divided into eight cells by laser processing. Next, the glass substrate on which the electron transport part was formed was immersed in a stirred solution prepared by adding a photosensitizing compound (0.2 mM) represented by Exemplary Compound 11 to a mixed solution of acetonitrile / t-butanol (volume ratio 1:1), and left to stand in a dark place for 1 hour to allow the photosensitizing compound to be adsorbed onto the surface of the electron transport part. Next, 70.2 mM of lithium bis(fluorosulfonyl)(trifluoromethanesulfonyl)imide (LiFTFSI) (Kishida Chemical Co., Ltd.), 145.8 mM of the pyridine compound represented by exemplary compound 12, 162.0 mM of the organic hole transport material (HTM) represented by exemplary compound 13 (SHT-263, Merck) and 12.6 mM of the cobalt complex represented by exemplary compound 14 (Greatcell Solar Materials) were dissolved in the chlorobenzene solution to prepare a hole transport coating solution. The molar ratio A / B of the pyridine compound (A) to the lithium salt (B) was 2.08. Next, a hole transport region of approximately 550 nm was formed on the electron transport region with the photosensitizing compound adsorbed thereon by die coating using a hole transport region coating solution. After that, the edge of the glass substrate where the sealing member was to be provided was etched by laser processing, and through holes for connecting to the ITO / NTO layer as terminal extraction points were further formed by laser processing, and through holes for connecting the cells in series were also formed by laser processing. Next, a mask was attached to the edge of the flexible glass substrate and between the cells, and silver was then vacuum-deposited to form a second electrode having a thickness of about 70 nm. Next, a surface protective layer material consisting of a fluorine-based silane compound (DURASURF DS-5935F130, manufactured by Harves Co., Ltd., a compound satisfying general formula (A)) was spin-coated onto the second electrode to form a surface protective layer with an average thickness of 50 nm. The formed surface protective layer covered the entire exposed surface of the second electrode. Next, the photovoltaic conversion module was covered with a sealing film with an adhesive layer made of aluminum PET as a sealing member (manufactured by Tesa Tape Co., Ltd.), and a pressure of 5.0 × 10 was applied using a laminator. 5 The lamination was performed under the conditions of 1.0 m / min at a temperature of 70°C and a pressure of 1.0 Pa. The water vapor permeation rate of the gas barrier material of the sealing member per day was 10 g / m 2 It was as follows. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0228] [ka]

[0229] [ka]

[0230] [ka]

[0231] [ka]

[0232] Example 20 <Fabrication of photovoltaic conversion modules (Fabrication of perovskite solar cells)> First, 0.36 g of titanium diisopropoxide bis(acetylacetone) isopropyl alcohol solution (B3395, 75% by mass, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 10 mL of isopropyl alcohol to obtain a solution, which was then applied by spin coating to an FTO flexible glass substrate manufactured by Nippon Sheet Glass Co., Ltd., dried at 120°C for 3 minutes, and then baked at 450°C for 30 minutes to form a first electrode and a dense electron transport layer (dense layer) on the substrate. The average thickness of the dense layer was set to 10 μm to 40 μm. Next, a dispersion of titanium oxide paste (manufactured by Great Cell Solar, product name: MPT-20) diluted with α-terpineol (manufactured by Kanto Chemical Co., Ltd.) was applied onto the dense layer by spin coating, dried at 120°C for 3 minutes, and then baked at 550°C for 30 minutes. Next, lithium bis(trifluoromethanesulfonyl)imide (Kanto Chemical Co., Ltd., product number: 38103) was dissolved in acetonitrile (Kanto Chemical Co., Ltd.) at 0.1 M (M: mol / dm 3A solution of the above-mentioned compound (meaning 'CuO') was applied onto the above-mentioned film by spin coating and baked at 450°C for 30 minutes to prepare a porous electron transport layer (porous layer). The average thickness of the porous layer was set to 150 nm. Next, lead(II) iodide (Tokyo Chemical Industry Co., Ltd., L0279, 0.5306 g), lead(II) bromide (Tokyo Chemical Industry Co., Ltd., L0288, 0.0736 g), methylamine bromide (Tokyo Chemical Industry Co., Ltd., M2589, 0.0224 g), formamidine iodide (Tokyo Chemical Industry Co., Ltd., F0974, 0.1876 g), and potassium iodide (Kanto Chemical Industry Co., Ltd., 32351, 0.0112 g) were added to N,N-dimethylformamide (Kanto Chemical Industry Co., Ltd., 0.8 ml) and dimethyl sulfoxide (Kanto Chemical Industry Co., Ltd., 0.2 ml). The mixture was heated and stirred at 60°C. The resulting solution was spin-coated onto the porous layer, while chlorobenzene (Kanto Chemical Industry Co., Ltd., 0.3 ml) was added to form a perovskite film. The resulting solution was then dried at 150°C for 30 minutes to form a perovskite layer. The average thickness of the perovskite layer was set to 200 nm or more and 350 nm or less. The laminate obtained by the above process was then subjected to laser processing to form grooves so that the distance between adjacent laminates was 10 μm. Next, 36.8 mg of the polymer represented by Exemplary Compound 15 (weight average molecular weight = 20,000, ionization potential = 5.22 eV), 36.8 mg of 2,2(7,7(-tetrakis-(N,N-di-p-methoxyphenylamine)9,9(-spirobifluorene))) (hereinafter referred to as "spiro-OMeTAD", manufactured by Merck, molecular weight = 1225.4, ionization potential = 5.09 eV), 4.9 mg of lithium bis(trifluoromethanesulfonyl)imide, 6.8 mg of 4-t-butylpyridine (manufactured by Tokyo Chemical Industry Co., Ltd., B0388), tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(III) hexafluorophosphate (Greatcell 0.1 mg of a compound (MS210205, manufactured by Solar Co., Ltd.) was weighed and dissolved in 1.5 mL of chlorobenzene (manufactured by Kanto Chemical Co., Ltd.). The resulting solution was applied by spin coating to the laminate obtained by the above process to prepare a hole transport layer. The average thickness of the hole transport layer (the portion above the perovskite layer) was adjusted to 100 nm to 200 nm. The difference in ionization potential between the above two types of hole transport materials was 0.13 eV. Furthermore, gold (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) was vacuum-deposited onto the above laminate to a thickness of 100 nm. The edges where the sealing material would be installed were then etched using a laser, and through-holes (conductive portions) for connecting the photoelectric conversion elements in series were further formed using a laser. Next, silver was vacuum-deposited on the laminate to form second electrodes with a thickness of approximately 100 nm. Mask deposition was used to set the distance between adjacent second electrodes to 200 μm. Silver was also deposited on the inner walls of the through-holes, confirming that adjacent photoelectric conversion elements were connected in series. Next, a surface protective layer material consisting of a fluorine-based silane compound (DURASURF DS-5935F130, manufactured by Harves Co., Ltd., a compound satisfying general formula (A)) was spin-coated onto the second electrode to form a surface protective layer with an average thickness of 50 nm. The formed surface protective layer covered the entire exposed surface of the second electrode. Next, the photovoltaic conversion module was covered with a sealing film with an adhesive layer made of aluminum PET as a sealing member (manufactured by Tesa Tape Co., Ltd.), and a pressure of 5.0 × 10 was applied using a laminator. 5 The lamination was performed under the conditions of 1.0 m / min at a temperature of 70°C and a pressure of 1.0 Pa. The water vapor permeation rate of the gas barrier material of the sealing member per day was 10 g / m 2 It was as follows. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0233] [ka]

[0234] (Comparative Example 1) <Fabrication of photoelectric conversion module> In the preparation of the photoelectric conversion module of Example 5, the material of the surface protection part was changed to an aluminum oxide nanoparticle dispersion liquid (manufactured by Sigma-Aldrich), and the average thickness of the formed surface protection part was changed to 10 μm. The photoelectric conversion module was prepared in the same manner as in Example 5. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0235] (Comparative Example 2) <Fabrication of photoelectric conversion module> In the preparation of the photoelectric conversion module of Example 5, the material of the surface protection part was changed to a zirconium oxide nanoparticle dispersion liquid (manufactured by Taki Chemical Co., Ltd.), and the average thickness of the formed surface protection part was changed to 10 μm. The photoelectric conversion module was prepared in the same manner as in Example 5. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0236] (Comparative Example 3) <Fabrication of photoelectric conversion module> In the preparation of the photovoltaic conversion module of Example 5, the material of the surface protection part was changed to a fluororesin (manufactured by Fluoro Technology Co., Ltd.), and the average thickness of the formed surface protection part was changed to 10 μm. A photovoltaic conversion module was prepared in the same manner as in Example 5. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0237] Comparative Example 4 <Fabrication of photoelectric conversion module> A photoelectric conversion module was produced in the same manner as in Example 5, except that no surface protective portion was formed in the production of the photoelectric conversion module of Example 5. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0238] (Comparative Example 5) <Fabrication of photoelectric conversion module> In the preparation of the photoelectric conversion module of Example 19, the material of the surface protection part was changed to an aluminum oxide nanoparticle dispersion liquid (manufactured by Sigma-Aldrich), and the average thickness of the formed surface protection part was changed to 10 μm. The photoelectric conversion module was prepared in the same manner as in Example 19. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0239] (Comparative Example 6) <Fabrication of photoelectric conversion module> A photoelectric conversion module was produced in the same manner as in Example 19, except that no surface protective portion was formed. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0240] (Comparative Example 7) <Fabrication of photoelectric conversion module> In the preparation of the photoelectric conversion module of Example 20, the material of the surface protection part was changed to an aluminum oxide nanoparticle dispersion liquid (manufactured by Sigma-Aldrich), and the average thickness of the formed surface protection part was changed to 10 μm. The photoelectric conversion module was prepared in the same manner as in Example 20. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0241] (Comparative Example 8) <Fabrication of photoelectric conversion module> A photoelectric conversion module was produced in the same manner as in Example 20, except that no surface protective portion was formed. The solar cell characteristics were evaluated in the same manner as in Example 1, and further, the electrode peelability, storage durability (at normal temperature and humidity), and storage durability (at high temperature and humidity) were evaluated. The results are shown in Table 1.

[0242] [Table 1]

[0243] The results in Table 1 show that the photoelectric conversion element of the present disclosure has a surface protective part adjacent to the surface of one of the electrodes selected from the first electrode and the second electrode that does not face the photoelectric conversion layer, and that the surface protective part contains a fluorine silane compound, thereby suppressing peeling of the electrode and a decrease in storage durability even when the photoelectric conversion element is bent. [Explanation of symbols]

[0244] 1 Photoelectric conversion element 2 Photoelectric conversion region 3 Sealing area 4 Other materials 11 UV protection layer 12 Base material 13 First electrode 14 First electron transport layer 15 Second electron transport layer (intermediate layer) 16 Photoelectric conversion layer 17 Hole transport layer 18 Second electrode 19 Surface protection part 20 Sealing member 21 Adhesive material 22 Gas barrier materials 30 Adhesive area [Prior art documents] [Patent documents]

[0245] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-220333 [Non-patent literature]

[0246] [Non-Patent Document 1] Applied Physics letters 108,253301 (2016) [Non-patent document 2] Japanese Journal of Applied Physics 54,071602 (2015)

Claims

1. A photoelectric conversion element having, in order, a first electrode, a photoelectric conversion layer, a second electrode, a surface protection part, an adhesive member, and a gas barrier member, the surface protective part is adjacent to a surface of the second electrode that does not face the photoelectric conversion layer, and contains a compound derived from a fluorine-based silane compound; The adhesive member is adjacent to the surface of the surface protection part that does not face the second electrode, and contains a pressure-sensitive adhesive resin.

2. 2. The photoelectric conversion element according to claim 1, wherein the surface protection portion has an average thickness of 1 [mu]m or less.

3. The photoelectric conversion element according to claim 1 , wherein the surface protection portion covers the entire exposed surface of the second electrode.

4. The fluorine-containing silane compound is a compound represented by the following general formula (A):

4. The photoelectric conversion element according to claim 1, wherein the molecular weight of the fluorine-containing silane compound is 1,000 or less. 【Chemical 1】 (In the general formula (A), R １ and R ２ each independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, a represents an integer of 2 to 3, p represents an integer of 1 to 2, q represents an integer of 0 to 5, m represents an integer of 1 to 3, n represents an integer of 2 to 4, and p+q+2m+n is an integer of 5 to 14.

5. a substrate on a surface of the first electrode that does not face the photoelectric conversion layer; The substrate is a resin film or glass, The photoelectric conversion element according to claim 1 , wherein the thickness of the substrate is 200 μm or less.

6. The water vapor permeation rate of the substrate per day is 10 g / m ２ The photoelectric conversion element according to claim 5, wherein:

7. The photoelectric conversion element according to claim 1 , wherein the adhesive member encapsulates the photoelectric conversion layer, the second electrode, and the surface protection portion, and is adhered to the surface protection portion and the first electrode.

8. The photoelectric conversion element according to claim 1 , comprising the first electrode, an electron transport layer, the photoelectric conversion layer, a hole transport layer, and the second electrode in that order.

9. 9. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer contains an organic material having a highest occupied molecular orbital (HOMO) level of 5.1 eV or more and 5.5 eV or less and a number average molecular weight (Mn) of 10,000 or less.

10. 10. The photoelectric conversion element according to claim 9, wherein the photoelectric conversion layer further contains an organic material having a highest occupied molecular orbital (HOMO) level of 5.2 eV to 5.6 eV and a number average molecular weight (Mn) of 10,000 or more.

11. The photoelectric conversion element according to claim 1 , wherein the photoelectric conversion layer contains a compound represented by the following general formula (1): 【Chemistry 2】 (In the general formula (1), R １ represents an alkyl group having 2 or more and 8 or less carbon atoms, n represents an integer of 1 or more and 3 or less, X is represented by the following general formula (2) or (3) below, Y represents a halogen atom, and m represents an integer of 0 or more and 4 or less. 【Chemistry 3】 (In the general formula (2), R ２ represents a linear or branched alkyl group. 【Chemistry 4】 (In the general formula (3), R ３ represents a linear or branched alkyl group.

12. The photoelectric conversion element according to claim 1 , wherein the photoelectric conversion layer contains an organic material that is a fullerene derivative.

13. the electron transport layer includes a first electron transport layer and a second electron transport layer provided between the first electron transport layer and the photoelectric conversion layer, the first electron transport layer contains metal oxide particles; 9. The photoelectric conversion element according to claim 8, wherein the second electron transport layer contains an amine compound represented by the following general formula (4): 【Chemistry 5】 (In the general formula (4), R ４ and R ５ is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or R ４ and R ５ represents a ring structure to which X is bonded, X represents a divalent aromatic group having 6 to 14 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and A represents any of the substituents represented by the following structural formulas (1) to (3): 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】

14. A photoelectric conversion module comprising a plurality of the photoelectric conversion elements according to claim 1 .

15. An electronic device comprising: the photoelectric conversion element according to claim 1 ; and a device electrically connected to the photoelectric conversion element.

16. 14. An electronic device comprising: the photoelectric conversion element according to claim 1; a storage battery electrically connected to the photoelectric conversion element; and a device electrically connected to the photoelectric conversion element and the storage battery.

17. A power supply module comprising: the photoelectric conversion element according to claim 1; and a power supply IC electrically connected to the photoelectric conversion element.

Images