Photoelectric conversion element, solar cell module, electronic device, and power supply module

Abstract

A photoelectric conversion element is provided that includes a first substrate, a first electrode including a transparent electrode, a photoelectric conversion layer, a second electrode, a sealing member, and an output terminal on the first substrate. The output terminal includes an end portion of the first electrode exposed from the sealing member and a metal layer on the end portion. A surface of the output terminal where the metal layer is provided has an arithmetic mean height (Ra) of 0.1 μm or more and 0.3 μm or less, and the surface of the output terminal where the metal layer is provided has a ten-point average roughness (Rz) of 0.35 μm or more and 0.75 μm or less.

Description

FN202402483 [DESCRIPTION] [Title of Invention] PHOTOELECTRIC CONVERSION ELEMENT, SOLAR CELL MODULE, ELECTRONIC DEVICE, AND POWER SUPPLY MODULE [Technical Field]

[0001] The present disclosure relates to a photoelectric conversion element, a solar cell module, an electronic device, and a power supply module. [Background Art]

[0002] In recent years, solar cells utilizing photoelectric conversion elements represent a technique with expectations in a wide range of applications, not only as an alternative to fossil fuels and a measure against global warming, but also as an independent power source that does not require battery replacement, power wiring, or the like. Further, solar cells as independent power sources are also attracting attention as an energy harvesting technology required for Internet of Things (IoT) devices and artificial satellites.

[0003] Types of solar cells include inorganic solar cells using silicon or the like, which have been widely used until now, and organic solar cells such as dye-sensitized solar cells, organic thin- film solar cells, and perovskite solar cells. Perovskite solar cells can be manufactured by using printing means of the related art, without using electrolytes containing organic solvents and the like, and thus, are advantageous to improve the safety and reduce the manufacturing costs. Further, in organic thin-film solar cells and perovskite solar cells, it is known that a plurality of spatially divided photoelectric conversion elements are electrically connected to form a series circuit to increase the output voltage (see, for example, PTL 1). [Citation List] [Patent Literature]

[0004] [PTL 1] Japanese Unexamined Patent Application Publication No.2020-053616 [Summary of Invention] [Technical Problem]

[0005] An object of the present disclosure is to provide a photoelectric conversion element in which an output terminal has excellent adhesion and durability and in which the power generation efficiency can be maintained. [Solution to Problem]

[0006] FN202402483 A photoelectric conversion element according to an embodiment of the present disclosure includes a first substrate, a first electrode including a transparent electrode, a photoelectric conversion layer, a second electrode, a sealing member, and an output terminal on the first substrate. The output terminal includes an end portion of the first electrode exposed from the sealing member and a metal layer on the end portion. A surface of the output terminal where the metal layer is provided has an arithmetic mean height (Ra) of 0.1 μm or more and 0.3 μm or less, and the surface of the output terminal where the metal layer is provided has a ten- point average roughness (Rz) of 0.35 μm or more and 0.75 μm or less. [Advantageous Effects of Invention]

[0007] According to embodiments of the present disclosure, a photoelectric conversion element is provided in which an output terminal has excellent adhesion and durability and in which the power generation efficiency can be maintained. [Brief Description of Drawings]

[0008] A more complete appreciation of embodiments of the present disclosure and many of the attendant advantages and features thereof can be readily obtained and understood from the following detailed description with reference to the accompanying drawings. [FIG.1] FIG.1 is a schematic diagram illustrating a solar cell as an embodiment of a photoelectric conversion element. [FIG.2] FIG.2 is an enlarged view of an output terminal of the solar cell illustrated in FIG.1. [FIG.3] FIG.3 is a schematic diagram illustrating a solar cell as an embodiment of a photoelectric conversion element. [FIG.4] FIG.4 is a schematic diagram illustrating a solar cell module. [FIG.5] FIG.5 is a schematic diagram illustrating a solar cell module. [FIG.6] FIG.6 is a schematic diagram illustrating a solar cell module. [FIG.7] FIG.7 is a schematic diagram illustrating a solar cell module. [FIG.8] FIG.8 is a schematic diagram illustrating a solar cell module. [FIG.9] FIG.9 is a schematic diagram illustrating a solar cell module. [FIG.10]FN202402483 FIG.10 is a block diagram of a mouse for a personal computer as an example of an electronic device. [FIG.11] FIG.11 is a schematic external view of the mouse illustrated in FIG.10. [FIG.12] FIG.12 is a block diagram of a keyboard for a personal computer as an example of an electronic device. [FIG.13] FIG.13 is a schematic external view of the keyboard illustrated in FIG.12. [FIG.14] FIG.14 is a schematic external view of the keyboard illustrated in FIG.12. [FIG.15] FIG.15 is a block diagram of a sensor as an example of an electronic device. [FIG.16] FIG.16 is a block diagram of a turntable as an example of an electronic device. [FIG.17] FIG.17 is a block diagram illustrating an electronic device. [FIG.18] FIG.18 is a block diagram illustrating an example in which a power supply IC is further included in the electronic device illustrated in FIG.17. [FIG.19] FIG.19 is a block diagram illustrating an example in which a power storage device is further included in the electronic device illustrated in FIG.18. [FIG.20] FIG.20 is a block diagram illustrating a power supply module. [FIG.21] FIG.21 is a block diagram illustrating an example in which a power storage device is further included in the power supply module illustrated in FIG.20. [FIG.22] FIG.22 is a cross-sectional view of a solar cell in a manufacturing process of Example 1. [FIG.23] FIG.23 is a top view of an end portion of a first electrode in the manufacturing process of Example 1. The accompanying drawings are intended to depict embodiments of the present disclosure and should not be interpreted to limit the scope thereof. The accompanying drawings are not to be considered as drawn to scale unless explicitly noted. Also, identical or similar reference numerals designate identical or similar components throughout the several views. [Description of Embodiments]

[0009] FN202402483 In describing embodiments illustrated in the drawings, specific terminology is employed for the sake of clarity. However, the disclosure of this specification is not intended to be limited to the specific terminology so selected and it is to be understood that each specific element includes all technical equivalents that have a similar function, operate in a similar manner, and achieve a similar result. Referring now to the drawings, embodiments of the present disclosure are described below. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. (Photoelectric Conversion Element) The photoelectric conversion element of the present embodiment includes a first substrate, a first electrode, a photoelectric conversion layer, a second electrode, and a sealing member, and if desired, further includes another member. The first electrode is a transparent electrode. The photoelectric conversion element includes, on the first substrate, an output terminal including an end portion of the first electrode exposed from the sealing member and a metal layer provided on the end portion. The arithmetic mean height (Ra) of the surface of the output terminal where the metal layer is provided is 0.1 μm or more and 0.3 μm or less, and the ten-point average roughness (Rz) of the surface of the output terminal where the metal layer is provided is 0.35 μm or more and 0.75 μm or less.

[0010] The inventors have found that, in an output terminal in which an end portion of a first electrode (a transparent electrode) exposed from a sealing member has unevenness and a metal layer provided on the end portion has a predetermined surface roughness (arithmetic mean height Ra and ten-point average roughness Rz), an area in which the metal layer and a lower end portion of the electrode adhere to each other increases, so that peeling of the metal layer is reduced and the metal layer and the lower end portion of the electrode adhere closely to each other. Therefore, in a photoelectric conversion element having such a configuration, the output terminal has excellent adhesion and durability, and the power generation efficiency can be maintained, even after the photoelectric conversion element is exposed to light having high luminous intensity during a long period of time.

[0011] The photoelectric conversion element refers to an element that can convert light energy into electric energy or convert electric energy into light energy, and is applied to solar cells, photodiodes, and the like. The photoelectric conversion element may be a so-called regular structure-type photoelectric conversion element including a first substrate, a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a second electrode, in this order. Alternatively, the photoelectric conversion element may be a so-called inverted structure-typeFN202402483 photoelectric conversion element including a first substrate, a first electrode, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a second electrode, in this order. The regular structure-type photoelectric conversion element preferably further includes a passivation layer between the photoelectric conversion layer and the hole transport layer. The inverted structure-type photoelectric conversion element preferably further includes a passivation layer between the photoelectric conversion layer and the electron transport layer.

[0012] <Output Terminal> The output terminal includes, on the first substrate, an end portion of the first electrode exposed from the sealing member and a metal layer provided on the end portion. The arithmetic mean height (Ra) of a surface of the output terminal where the metal layer is provided is 0.1 μm or more and 0.3 μm or less. The ten-point average roughness (Rz) of the surface of the output terminal where the metal layer is provided is 0.35 μm or more and 0.75 μm or less.

[0013] The arithmetic mean height (Ra) of the surface of the output terminal where the metal layer is provided is 0.1 μm or more and 0.3 μm or less, and more preferably 0.15 μm or more and 0.25 μm or less. When Ra is 0.1 μm or more, the surface is uneven, and thus, the adhesion to the metal layer improves. Further, when Ra is 0.3 μm or less, the uneven surface shape is stable, and thus, it is possible to maintain power generation efficiency, even after exposure to light having high luminous intensity during a long period of time.

[0014] The ten-point average roughness (Rz) of the surface of the output terminal where the metal layer is provided is 0.35 μm or more and 0.75 μm or less, preferably 0.40 μm or more and 0.70 μm or less, and more preferably 0.45 μm or more and 0.65 μm or less. When Rz is 0.35 μm or more, the discontinuous uneven shape has an effect of improving the adhesion between the metal layer and the transparent electrode. Moreover, Rz is preferably 0.75 μm or less, because in this case, the fragility resulting from a specific protruding shape is unlikely to develop, and the strength of the structure is ensured.

[0015] The arithmetic mean height (Ra) and the ten-point average roughness (Rz) of the surface of the output terminal where the metal layer is provided can be measured by using an optical microscope, a contact-type 3D scanner, an optical 3D scanner, a shape analysis laser microscope, and the like. Specifically, the measurement can be performed by using a shape measurement laser microscope (VK-X100, manufactured by Keyence Corporation) having a 50x objective lens.

[0016] FN202402483 <<End Portion of First Electrode>> The end portion of the first electrode is an end portion of the first electrode exposed from the sealing member. In the end portion of the first electrode, the first electrode is provided on the first substrate. If desired, the end portion of the first electrode may further include other layers such as the hole transport layer, the photoelectric conversion layer, and the electron transport layer. From the viewpoint of charge extraction, the end portion of the first electrode preferably further includes other layers such as the hole transport layer, the photoelectric conversion layer, and the electron transport layer, and is formed with a plurality of micropores extending to the first electrode. The end portion of the first electrode may penetrate the first electrode and extend to the first substrate.

[0017] The end portion of the first electrode has a surface roughness on the side opposite to the surface facing the first substrate. The arithmetic mean height (Ra) of the end portion of the first electrode is preferably 0.1 μm or more and 0.3 μm or less, and the ten-point average roughness (Rz) of the end portion of the first electrode is preferably 0.35 μm or more and 0.75 μm or less. The arithmetic mean height (Ra) and the ten-point average roughness (Rz) of the end portion of the first electrode can also be measured by a method similar to the one described above.

[0018] Examples of a method of forming the end portion of the first electrode include a sand blasting method, a water blasting method, abrasive paper, a chemical etching method, and a laser processing method. Among these methods, the laser processing method is preferred, because fine holes can be formed without using sand, an etchant, a resist, and the like, and thus, the material can be processed cleanly with good reproducibility.

[0019] <<Metal Layer>> The metal layer may be formed in the end portion of the first electrode. The metal layer may generally be a layer similar to the one used in the second electrode. Examples of materials used in the metal layer include, but are not limited to, metals such as platinum, gold, silver, copper, and aluminum; carbon-based compounds such as graphite, fullerene, carbon nanotubes, and graphene; conductive metal oxides such as ITO, FTO, and ATO; conductive polymers such as polythiophene and polyaniline; and conductive pastes containing metal nanomaterials. These materials may be used alone or in combination of two or more types. Among these materials, gold (Au) and silver (Ag) are preferred. The average thickness of the metal layer is not particularly limited and may be appropriately selected, but is preferably 0.02 μm or more and 30 μm or less. To improve the productivity, it is preferable that the metal layer is film-formed simultaneously with the second electrode. In this case, the films are formed at the same time,FN202402483 and thus, the average thickness of the second electrode and the average thickness of the metal layer are the same. Here, "the same" means that the difference between the average thickness of the second electrode and the average thickness of the metal layer is 10 nm or less. In a method of forming the metal layer, conditions described in the method of forming the second electrode can be appropriately selected, and examples of the method include coating, lamination, vapor deposition, CVD, and bonding.

[0020] <First Substrate> The shape, the structure, and the size of the first substrate are not particularly limited and can be appropriately selected according to a purpose. The material of the first substrate is not particularly limited and can be appropriately selected according to a purpose, as long as the material transmits light and has insulating properties. Examples of the material include, but are not limited to, substrates made of glass, plastic films, and ceramics. Among these substrates, when a firing step is included in the formation of the electron transport layer as described below, it is preferable to use a substrate having heat resistance to the firing temperature. Further, it is more preferable that a flexible substrate is used as the first substrate.

[0021] A second substrate may be provided on an outermost portion on a side of the second electrode. The shape, the structure, and the size described for the first substrate can be appropriately selected for the second substrate. Hereinafter, a substrate provided at an outermost portion on a side of the first electrode will be referred to as a first substrate, and a substrate provided at the outermost portion on a side of the second electrode will be referred to as a second substrate. The first substrate and the second substrate will be collectively referred to as a substrate. The average thickness of the substrate is not particularly limited and can be appropriately selected according to a purpose. For example, the average thickness may be 50 μm or more and 5 mm or less.

[0022] <First Electrode> The shape and the size of the first electrode are not particularly limited and can be appropriately selected according to a purpose, as long as the first electrode is a transparent electrode. Hereinafter, an electrode provided on a side of the first substrate will be referred to as a first electrode, and an electrode provided on a side of the second substrate will be referred to as a second electrode. The first electrode and the second electrode will be collectively referred to as an electrode.

[0023] FN202402483 The structure of the first electrode is not particularly limited and can be appropriately selected according to a purpose. The structure may be a single-layer structure or a structure in which a plurality of materials are laminated.

[0024] The material of the first electrode is not particularly limited and can be appropriately selected according to a purpose, as long as the material has conductivity. Examples of the material include, but are not limited to, transparent conductive metal oxides, carbon, and metals.

[0025] Examples of the transparent conductive metal oxides include, but are not limited to, indium tin oxide (hereinafter referred to as "ITO"), fluorine-doped tin oxide (hereinafter referred to as "FTO"), antimony-doped tin oxide (hereinafter referred to as "ATO"), niobium-doped tin oxide (hereinafter referred to as "NTO"), aluminum-doped zinc oxide (hereinafter referred to as "AZO"), indium zinc oxide, and niobium titanium oxide. Examples of the types of carbon include, but are not limited to, carbon black, carbon nanotubes, graphene, and fullerene. Examples of the metals include, but are not limited to, gold, silver, aluminum, nickel, indium, tantalum, and titanium. These metals may be used alone or in combination of two or more types. Among these materials, transparent conductive metal oxides having high transparency are preferred, and ITO, FTO, ATO, NTO, and AZO are more preferred.

[0026] The average thickness of the first electrode is not particularly limited and may be appropriately selected according to a purpose, but is preferably 5 nm or more and 100 μm or less, and more preferably 50 nm or more and 10 μm or less. When the material of the first electrode includes carbon or a metal, the average thickness of the first electrode is preferably set to an average thickness at which it is possible to obtain light transmittance.

[0027] The first electrode can be formed by a known method such as a sputtering method, a vapor deposition method, and a spraying method.

[0028] The first electrode is preferably formed on a substrate, and a commercially available integrally formed product in which the first electrode is formed in advance on a substrate can be used. Examples of the commercially available integrally formed product include, but are not limited to, FTO-coated glass, ITO-coated glass, zinc oxide:aluminum-coated glass, FTO-coated transparent plastic films, and ITO-coated transparent plastic films. Examples of other commercially available integrally formed products include, but are not limited to, transparent electrodes in which tin oxide or indium oxide is doped with cations or anions having differentFN202402483 valence, and glass substrates including metal electrodes having a structure through which light can pass, such as a mesh shape and a stripe pattern. These products may be used alone or two or more types of these products may be mixed or laminated and used together. To reduce the electric resistance value, a metal lead wire or the like may also be used in combination with these products. Further, electrodes in the commercially available integrally formed products may be appropriately processed to manufacture a substrate on which a plurality of first electrodes are formed, to manufacture a photoelectric conversion module, which will be described later.

[0029] As described above, the photoelectric conversion element includes, as the output terminal, an output terminal including an end portion of a first electrode exposed from a sealing member and a metal layer provided on the end portion. The output terminal is integrally formed with the first electrode, and thus, the output terminal has the advantage of having excellent durability.

[0030] <Electron Transport Layer> The electron transport layer refers to a layer that transports electrons generated in a photoelectric conversion layer, which will be described later, to an electrode. Therefore, the electron transport layer is preferably arranged adjacent to the electrode.

[0031] The shape and the size of the electron transport layer are not particularly limited and can be appropriately selected according to a purpose.

[0032] The electron transport layer may have a single layer structure or a multilayer structure in which a plurality of layers are laminated.

[0033] The electron transport layer contains an electron transport material. The electron transport material is not particularly limited and can be appropriately selected according to a purpose. However, the electron transport material is preferably a semiconductor material.

[0034] The semiconductor material is not particularly limited, and any known material can be used as the semiconductor material. Examples of the semiconductor material include, but are not limited to, an elemental semiconductor and a compound including a compound semiconductor. Examples of the elemental semiconductor include, but are not limited to, silicon and germanium. Examples of the compound semiconductor include, but are not limited to, metal chalcogenides.FN202402483

[0035] Examples of the metal chalcogenides include, but are not limited to, metal oxides (oxide semiconductors), metal sulfides, metal selenides, and metal tellurides. Examples of the metal oxides (oxide semiconductors) include, but are not limited to, oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum. Examples of the metal sulfides include, but are not limited to, sulfides of cadmium, zinc, lead, silver, antimony, and bismuth. Examples of the metal selenides include, but are not limited to, selenides of cadmium and lead. Examples of the metal tellurides include, but are not limited to, tellurides of cadmium. Examples of other compound semiconductors include, but are not limited to, phosphides of zinc, gallium, indium, and cadmium, gallium arsenide, copper-indium-selenide, and copper- indium-sulfide.

[0036] Among the semiconductor materials, metal oxides (oxide semiconductors) are preferred, and in particular, at least one of titanium oxide, zinc oxide, tin oxide, and niobium oxide is more preferred, and tin oxide is even more preferred. These materials may be used alone or in combination of two or more types. The crystal type of the semiconductor material is not particularly limited and can be appropriately selected according to a purpose. The semiconductor material may be a single crystal, polycrystalline, or amorphous.

[0037] The electron transport layer preferably contains, on the electron transport material on the surface on a side of the photoelectric conversion layer, at least one compound from among a phosphonic acid compound, a boronic acid compound, a sulfonic acid compound, a halogenated silyl compound, and an alkoxysilyl compound. The electron transport layer contains these compounds on the electron transport material on the surface on the side of the photoelectric conversion layer. If the electron transport layer contains these compounds, it is expected that the physical properties of an interface between the electron transport layer and the photoelectric conversion layer can be controlled. In other words, by applying these compounds onto the electron transport material on the surface of the electron transport layer on the side of the photoelectric conversion layer, it is expected that the interfacial resistance between the electron transport layer and the photoelectric conversion layer decreases, and the electron transfer is made smoother. These compounds may be bonded to the electron transport material. Examples of the bond include, but are not limited to, a covalent bond and an ionic bond.

[0038] FN202402483 The compound is at least one compound among a phosphonic acid compound, a boronic acid compound, a sulfonic acid compound, a halogenated silyl compound, and an alkoxysilyl compound. The compound preferably contains a nitrogen atom to ensure compatibility with the photoelectric conversion layer (perovskite layer) described below.

[0039] The phosphonic acid compound is not particularly limited and can be appropriately selected according to a purpose, as long as the phosphonic acid compound is a compound containing a phosphonic acid group. Specific examples of the phosphonic acid compound will be described later.

[0040] The boronic acid compound is not particularly limited and can be appropriately selected according to a purpose, as long as the boronic acid compound is a compound containing a boronic acid group. Specific examples of the boronic acid compound will be described later.

[0041] The sulfonic acid compound is not particularly limited and can be appropriately selected according to a purpose, as long as the sulfonic acid compound is a compound containing a sulfonic acid group. Specific examples of the sulfonic acid compound will be described later.

[0042] The halogenated silyl compound is not particularly limited and can be appropriately selected according to a purpose, as long as the halogenated silyl compound is a compound containing a halogenated silyl group. Specific examples of the halogenated silyl compound will be described later.

[0043] The alkoxysilyl compound is not particularly limited and can be appropriately selected according to a purpose, as long as the alkoxysilyl compound is a compound containing an alkoxysilyl group. Specific examples of the alkoxysilyl compound will be described later.

[0044] The molecular weight of the compound is not particularly limited and can be appropriately selected according to a purpose. For example, the molecular weight may be 100 or more and 500 or less.

[0045] For example, the compound is represented by General Formula (X) below. [Chem.1]FN202402483 In General Formula (X) above, R1and R2each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocycle, and may be the same or may be different. R3represents a divalent alkylene group, a divalent aryl group, or a divalent heterocycle. R4represents a phosphonic acid group, a boronic acid group, a sulfonic acid group, a halogenated silyl group, or an alkoxysilyl group. R1or R2, R3, and N may be joined together to form a ring structure.

[0046] Examples of the compound include, but are not limited to, Compounds (X-01) to (X-56) below. [Chem.2]

[0047] [Chem.3]FN202402483FN202402483

[0049] [Chem.5]

[0050] It is preferable to coat the surface of the metal oxide on the electron transport layer with a compound including a substituent that reacts with the metal oxide, such as a phosphonic acid, a sulfonic acid, or a halogenated silyl group. Specific examples of the compound used for coating the surface include, but are not limited to, methylphosphonic acid, phenylphosphonic acid, phenethylphosphonic acid, (1- aminoethyl)phosphonic acid, (2-aminoethyl)phosphonic acid, methanesulfonic acid, benzenesulfonic acid, 2-thienylboronic acid, methyltrichlorosilane, and n- hexyltriethoxysilane. However, the compound is not limited thereto.

[0051] The average thickness of the electron transport layer is not particularly limited and may be appropriately selected according to a purpose, but is preferably 5 nm or more and 1 μm or less, and more preferably 10 nm or more and 700 nm or less.

[0052] FN202402483 The surface of the electron transport layer on the side of the photoelectric conversion layer is preferably as smooth as possible. The roughness factor, which serves as an indicator expressing the smoothness, is preferably small. However, in relation to the average thickness of the electron transport layer, the roughness factor of the electron transport layer on the side of the photoelectric conversion layer side is preferably 20 or less, and more preferably 10 or less. A lower limit value of the roughness factor is not particularly limited and can be appropriately selected according to a purpose. For example, the lower limit value may be 1 or more. The roughness factor is the ratio of the actual surface area to the apparent surface area, and is also called the Wenzel roughness factor. The actual surface area can be measured, for example, by measuring the BET specific surface area. The roughness factor can be determined by dividing the value of the BET specific surface area by the apparent surface area.

[0053] A method of preparing a thin film of the electron transport material in the electron transport layer is not particularly limited and can be appropriately selected according to a purpose. Examples of the method include a wet film-forming method and method of forming a thin film of the electron transport material in a vacuum (vacuum film-forming method). Examples of the vacuum film-forming method include, but are not limited to, a sputtering method, a pulsed laser deposition method (PLD method), an ion beam sputtering method, an ion-assisted method, an ion plating method, a vacuum vapor deposition method, an atomic layer deposition method (ALD method), and a chemical vapor deposition method (CVD method). An example of the wet film-forming method includes, but is not limited to, a sol-gel method. The sol-gel method is a method in which a gel is prepared from a solution by a chemical reaction such as hydrolysis and polymerization / condensation, and then, the gel is subjected to a heat treatment to promote densification. When a sol-gel method is used, a method of applying a sol solution is not particularly limited and can be appropriately selected according to a purpose. Examples of the method include a dipping method, a spraying method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, and further, as wet printing methods, letterpress, offset, gravure, intaglio, rubber plate, and screen printing. The temperature during the heat treatment after the application of the sol solution is preferably 80°C or higher, and more preferably 100°C or higher.

[0054] A method of applying the compound onto the electron transport material is not particularly limited and can be appropriately selected according to a purpose. Examples of the method include a method in which a solution containing the compound is applied onto a thin film of the electron transport material and then, the applied solution is dried.FN202402483 The coating method is not particularly limited and may be appropriately selected according to a purpose. Examples of the coating method include a dipping method, a spraying method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, and a gravure coating method. The temperature during the drying process after the solution is applied is preferably 40°C or higher, and more preferably 50°C or higher.

[0055] <Photoelectric Conversion Layer> The photoelectric conversion layer is not particularly limited and can be appropriately selected according to a purpose, as long as the photoelectric conversion layer is a layer that performs photoelectric conversion. Examples of the photoelectric conversion layer include, but are not limited to, a perovskite layer and a bulk heterojunction layer.

[0056] <<Perovskite Layer>> The perovskite layer refers to a layer that contains a perovskite compound and absorbs light to sensitize the electron transport layer. Therefore, the perovskite layer is preferably arranged adjacent to the electron transport layer.

[0057] The shape and the size of the perovskite layer are not particularly limited and can be appropriately selected according to a purpose.

[0058] The perovskite compound is a composite material of an organic compound and an inorganic compound, and is represented by General Formula (5) below. XαYβZγ... General Formula (5) In General Formula (5) above, a ratio of α:β:γ is 3:1:1, β and γ each independently represent an integer greater than 1, X represents a halogen atom, Y represents an organic compound having an amino group, and Z represents a metal ion.

[0059] In General Formula (5) above, X is not particularly limited and can be appropriately selected according to a purpose. Examples of X include, but are not limited to, halogen atoms such as chlorine, bromine, and iodine. These materials may be used alone or in combination of two or more types.

[0060] In General Formula (5) above, Y is not particularly limited and can be appropriately selected according to a purpose, as long as Y is an organic cation. Examples of Y include, but are not limited to, ions of alkylamine compounds such as methylamine, ethylamine, n-butylamine, and formamidine, and inorganic alkali metal cations such as Sb atoms, Cs atoms, Rb atoms, and K atoms. These ions may be used alone or in combination of two or more types, andFN202402483 inorganic alkali metal cations and organic cations may be used in combination. Among these, organic compounds having an amino group are preferred. Further, in the case of a methylammonium lead halide perovskite compound, peak λmax of the optical absorption spectrum shifts to the longer wavelength side in the following order. When the halogen ion is Cl, the peak λmax is about 350 nm, when the halogen ion is Br, the peak λmax is about 410 nm, and when the halogen ion is I, the peak λmax is about 540 nm. Therefore, the usable spectral width (band width) differs.

[0061] In General Formula (5), Z is not particularly limited and can be appropriately selected according to a purpose. Examples of Z include, but are not limited to, ions of metals such as lead, indium, antimony, tin, copper, and bismuth. These materials may be used alone or in combination of two or more types.

[0062] The perovskite layer preferably has a layered perovskite structure obtained by alternately laminating layers including a metal halide and layers in which organic cation molecules are arranged.

[0063] The average thickness of the perovskite layer is preferably 50 nm or more and 2 μm or less, and more preferably 100 nm or more and 600 nm or less.

[0064] A method of forming the perovskite layer is not particularly limited and can be appropriately selected according to a purpose. An example of the method includes a method of applying a solution in which a metal halide, an alkylamine halide, a cesium halide, or the like is dissolved or dispersed, and then, the applied solution is dried. Another example of a method of forming a perovskite layer includes a two-step precipitation method in which a solution obtained by dissolving or dispersing a metal halide is applied and dried, and then, the formed layer is immersed in a solution in which an alkylamine halide is dissolved, to form a perovskite compound. Further, an example of a method of forming a perovskite layer includes a method in which a solution obtained by dissolving or dispersing a metal halide and an alkylamine halide is applied, while a poor solvent (a solvent having low solubility) for the perovskite compound is added to precipitate crystals. In addition, an example of a method of forming a perovskite layer includes a method in which a metal halide is vapor-deposited in a gas filled with methylamine or the like. Among these methods, a preferred method is to apply a solution in which a metal halide and an alkylamine halide are dissolved or dispersed, while adding a poor solvent for the perovskite compound to precipitate crystals.

[0065] FN202402483 A method of applying the solution is not particularly limited and can be appropriately selected according to a purpose. Examples of the method include an immersion method, a spin coating method, a spraying method, a dipping method, a roller method, and an air knife method. An example of a method of applying the solution includes a method of precipitating the solution in a supercritical fluid using carbon dioxide or the like.

[0066] The perovskite layer may also contain a sensitizing dye. A method of forming a perovskite layer containing a sensitizing dye is not particularly limited and can be appropriately selected according to a purpose. Examples of the method include, but are not limited to, a method of mixing a perovskite compound with a sensitizing dye, and a method of forming a perovskite layer and then adsorbing a sensitizing dye.

[0067] The sensitizing dye is not particularly limited and can be appropriately selected according to a purpose, as long as the sensitizing dye is a compound that can be photoexcited by the excitation light being used. Examples of the sensitizing dye include, but are not limited to, metal complex compounds, coumarin compounds, polyene compounds, indoline compounds, thiophene compounds, cyanine dyes, merocyanine dyes, 9-arylxanthene compounds, triarylmethane compounds, phthalocyanine compounds, and porphyrin compounds. Examples of the metal complex compounds include, but are not limited to, metal complex compounds described in Japanese Translation of PCT International Publication No. JP-T-7- 500630, Japanese Unexamined Patent Application Publication No.10-233238, Japanese Unexamined Patent Application Publication No.2000-26487, Japanese Unexamined Patent Application Publication No.2000-323191, and Japanese Unexamined Patent Application Publication No.2001-59062. Examples of the coumarin compounds include, but are not limited to, coumarin compounds described in Japanese Unexamined Patent Application Publication No.10-93118, Japanese Unexamined Patent Application Publication No.2002-164089, Japanese Unexamined Patent Application Publication No.2004-95450, and J. Phys. Chem. C, 7224, Vol.111 (2007). Examples of the polyene compounds include, but are not limited to, the polyene compounds described in Japanese Unexamined Patent Application Publication No.2004-95450 and Chem. Commun., 4887 (2007). Examples of the indoline compounds include, but are not limited to, the indoline compounds described in Japanese Unexamined Patent Application Publication No.2003-264010, Japanese Unexamined Patent Application Publication No.2004-63274, Japanese Unexamined Patent Application Publication No.2004-115636, Japanese Unexamined Patent Application Publication No.2004-200068, Japanese Unexamined Patent Application Publication No. 2004-235052, J. Am. Chem. Soc., 12218, Vol.126 (2004), Chem. Commun., 3036 (2003), and Angew. Chem. Int. Ed., 1923, Vol.47 (2008).FN202402483 Examples of the thiophene compounds include, but are not limited to, the thiophene compounds described in J. Am. Chem. Soc., 16701, Vol.128 (2006) and J. Am. Chem. Soc., 14256, Vol.128 (2006). Examples of the cyanine dyes include, but are not limited to, the cyanine dyes described in Japanese Unexamined Patent Application Publication No.11-86916, Japanese Unexamined Patent Application Publication No.11-214730, Japanese Unexamined Patent Application Publication No.2000-106224, Japanese Unexamined Patent Application Publication No. 2001-76773, and Japanese Unexamined Patent Application Publication No.2003-7359. Examples of the merocyanine dyes include, but are not limited to, merocyanine dyes described in Japanese Unexamined Patent Application Publication No.11-214731, Japanese Unexamined Patent Application Publication No.11-238905, Japanese Unexamined Patent Application Publication No.2001-52766, Japanese Unexamined Patent Application Publication No.2001-76775, and Japanese Unexamined Patent Application Publication No. 2003-7360. Examples of the 9-arylxanthene compounds include, but are not limited to, 9-arylxanthene compounds described in Japanese Unexamined Patent Application Publication No.10-92477, Japanese Unexamined Patent Application Publication No.11-273754, Japanese Unexamined Patent Application Publication No.11-273755, and Japanese Unexamined Patent Application Publication No.2003-31273. Examples of the triarylmethane compounds include, but are not limited to, the triarylmethane compounds described in Japanese Unexamined Patent Application Publication No.10-93118 and Japanese Unexamined Patent Application Publication No.2003-31273. Examples of the phthalocyanine compounds and the porphyrin compounds include, but are not limited to, the phthalocyanine compounds and the porphyrin compounds described in Japanese Unexamined Patent Application Publication No.9-199744, Japanese Unexamined Patent Application Publication No.10-233238, Japanese Unexamined Patent Application Publication No.11-204821, Japanese Unexamined Patent Application Publication No.11- 265738, J. Phys. Chem., 2342, Vol.91 (1987), J. Phys. Chem. B, 6272, Vol.97 (1993), Electroanal. Chem., 31, Vol.537 (2002), Japanese Unexamined Patent Application Publication No.2006-032260, J. Porphyrins Phthalocyanines, 230, Vol.3 (1999), Angew. Chem. Int. Ed., 373, Vol.46 (2007), and Langmuir, 5436, Vol.24 (2008). Among these compounds, metal complex compounds, indoline compounds, thiophene compounds, and porphyrin compounds are preferred.

[0068] <Passivation Layer> The regular structure-type photoelectric conversion element preferably further includes a passivation layer between the photoelectric conversion layer and the hole transport layer. The inverted structure-type photoelectric conversion element preferably further includes a passivation layer between the photoelectric conversion layer and the electron transport layer.FN202402483 The passivation layer preferably contains an amine compound different from the compound contained in the photoelectric conversion layer, and preferably contains a compound represented by General Formula (6) below. A-X ... General Formula (6) In General Formula (6) above, A is at least one compound among an amino cation compound, a pyridinium cation compound, an imidazolinium cation compound, and a pyrrolidinium cation compound represented by any one of General Formula (7) below and General Formula (8) below. X represents a halogen ion. [Chem.6]In General Formula (7) above, R1represents any one among -H, -F, -CF3, and -OCH3, n represents 1 or 2, and X represents any one of Br and I. [Chem.7]In General Formula (8) above, n represents an integer of 3 or more and 12 or less, and X represents any one of Br and I.

[0069] Specific examples of compounds represented by General Formula (7) above include, but are not limited to, (E-1) to (E-12) indicated below. However, the compound is not limited thereto.

[0070] [Chem.8]FN202402483

[0071] Specific examples of compounds represented by General Formula (8) above include, but are not limited to, 5-aminopentanoic acid hydroiodide, 5-aminopentanoic acid hydrobromide, 6- aminohexanoic acid hydroiodide, 6-aminohexanoic acid hydrobromide, 7-aminoheptanoic acid hydroiodide, 7-aminoheptanoic acid hydrobromide, 8-aminoheptanoic acid hydroiodide, 8-aminoheptanoic acid hydrobromide, 9-aminononanoic acid hydroiodide, 9-aminononanoic acid hydrobromide, 10-aminodecanoic acid hydroiodide, 10-aminodecanoic acid hydrobromide, 11-aminoundecanoic acid hydroiodide, 12-aminoundecanoic acid hydrobromide, 12-aminododecanoic acid hydroiodide, and 12-aminododecanoic acid hydrobromide.

[0072] The photoelectric conversion element includes the passivation layer between the photoelectric conversion layer and the hole transport layer, and thus, it is expected that the physical properties of the interface can be controlled. Note that, when the photoelectric conversion layer is a perovskite layer, the compound (organic salt or inorganic salt) represented by General Formula (6) above is preferably a salt different from the salt included in the perovskite layer.

[0073] The salt is not particularly limited and can be appropriately selected according to a purpose. However, in particular when a perovskite compound is used in the photoelectric conversion layer, the salt preferably contains a halogen atom to ensure compatibility. Examples of the halogen atoms include, but are not limited to, chlorine, iodine, and bromine.FN202402483

[0074] In particular, when a perovskite compound is used in the photoelectric conversion layer, the organic salt is preferably a hydrogen halide salt of amine to ensure compatibility. In particular, when a perovskite compound is used in the photoelectric conversion layer, the inorganic salt is preferably a halide of an alkali metal to ensure compatibility. Examples of the alkali metal include, but are not limited to, lithium, sodium, potassium, rubidium, and cesium.

[0075] The above-mentioned A is at least one compound among an amino cation compound, a pyridinium cation compound, an imidazolinium cation compound, and a pyrrolidinium cation compound represented by any one of General Formula (7) below and General Formula (8) below. [Chem.9]In General Formula (7) above, R1represents any one among -H, -F, -CF3, and -OCH3, n represents 1 or 2, and X represents any one of Br and I. [Chem.10]In General Formula (8) above, n represents an integer of 3 or more and 12 or less, and X represents any one of Br and I.

[0076] Examples of X in General Formula (6) above include, but are not limited to, halogen anions such as a bromine (Br) anion and an iodine (I) anion.

[0077] A method of forming the passivation layer between the photoelectric conversion layer and the hole transport layer is not particularly limited and can be appropriately selected according to a purpose. An example of the method includes a method in which a solution containing a compound (an organic salt or an inorganic salt) represented by General Formula (6) above is applied onto the photoelectric conversion layer, the solution is dried, and then, a hole transport layer is further formed thereon. Examples of the solution include, but are not limited to, an aqueous solution and an alcohol.FN202402483 The coating method is not particularly limited and may be appropriately selected according to a purpose. Examples of the coating method include a dipping method, a spraying method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, and a gravure coating method. An example of a method of applying the solution includes a method of precipitating the solution in a supercritical fluid using carbon dioxide or the like. The film thickness of the layer is not limited, and the solution may be adsorbed by single molecules or may be in the form of islands that are not continuous. The temperature during the drying process after the solution is applied is not particularly limited and can be appropriately selected according to a purpose. The average thickness of the passivation layer is preferably 0.5 nm or more and 100 nm or less, and more preferably 1 nm or more and 50 nm or less. The compound (organic salt or inorganic salt) represented by General Formula (6) above does not need to be uniformly distributed at the interface between the photoelectric conversion layer and the hole transport layer, and may be present locally in a plurality of regions (for example, in the form of islands). When the photoelectric conversion layer is a perovskite layer, the perovskite compound may be reacted with the hole transport material of the hole transport layer to distribute the compound represented by General Formula (6) above in the perovskite layer or the hole transport layer. That is, it is only required to provide a region in which the compound (organic salt or inorganic salt) represented by General Formula (6) above is present between the perovskite layer in which the compound (organic salt or inorganic salt) represented by General Formula (6) above is not present and the hole transport layer in which no organic salt or inorganic salt is present.

[0078] <Hole Transport Layer> The hole transport layer refers to a layer that transports holes (positive holes) generated in the photoelectric conversion layer to an electrode. Therefore, the hole transport layer is preferably arranged adjacent to the photoelectric conversion layer, directly or via the above- described salt.

[0079] The hole transport layer contains a compound having the structural unit of General Formula (1) below and a compound represented by General Formula (2) below. By adding a dopant represented by General Formula (2), it is possible to obtain an effect of preventing a hole transport solution from forming a gel and reducing the resistance of a hole transport layer formed as a film by using ink of the hole transport solution.

[0080] [Chem.11]FN202402483In General Formula (1) above, Ar1represents an aryl group. Examples of the aryl group include, but are not limited to, a phenyl group, a 1-naphthyl group, and a 9-anthracenyl group. The aryl group may have a substituent. Examples of the substituent include, but are not limited to, an alkyl group, an alkoxy group, and an aryl group. Ar2and Ar3each independently represent an arylene group, a divalent heterocyclic group, or the like. Examples of the arylene group include, but are not limited to, 1,4-phenylene, 1,1'- biphenylene, and 9,9'-di-n-hexylfluorene. An example of the divalent heterocyclic group includes, but is not limited to, 2,5-thiophene.

[0081] A compound having the structural unit of General Formula (1) above is preferably a compound represented by General Formula (1A). Thus, it is possible to obtain an effect of reducing the resistance of the hole transport layer.

[0082] [Chem.12]In General Formula (1A) above, Ar1represents an aromatic hydrocarbon group which may have a substituent. Ar2and Ar3each independently represent a divalent group of a monocyclic aromatic hydrocarbon group that may have a substituent, a non-condensed polycyclic aromatic hydrocarbon group that may have a substituent, or a condensed polycyclic aromatic hydrocarbon group that may have a substituent. Ar4represents a divalent group of benzene that may have a substituent, thiophene that may have a substituent, biphenyl that may have a substituent, anthracene that may have a substituent, or naphthalene that may have a substituent. n represents an integer of 2 or more. The weight average molecular weight of the polymer represented by General Formula (1A) above is preferably 2,000 or more.

[0083] In General Formula (1A) above, Ar1is an aromatic hydrocarbon group that may have a substituent. For example, Ar1represents an aryl group that may have a substituent.FN202402483 Examples of the aryl group include, but are not limited to, a phenyl group, a 1-naphthyl group, and a 9-anthracenyl group. Examples of the substituent include, but are not limited to, an alkyl group, an alkoxy group, and an aryl group. Ar2and Ar3each independently represent a divalent group of a monocyclic aromatic hydrocarbon group that may have a substituent, a non-condensed polycyclic aromatic hydrocarbon group that may have a substituent, or a condensed polycyclic aromatic hydrocarbon group that may have a substituent. For example, Ar2and Ar3each independently represent an arylene group that may have a substituent, a divalent heterocyclic group that may have a substituent, and the like. Examples of the arylene group include, but are not limited to, 1,4-phenylene, 1,1'-biphenylene, and 9,9'-di-n-hexylfluorene. An example of the divalent heterocyclic group includes, but is not limited to, 2,5-thiophene. Examples of the substituent include, but are not limited to, an alkyl group, an alkoxy group, and an aryl group. Ar4represents a divalent group of benzene, thiophene, biphenyl, anthracene, or naphthalene, which may be substituted with a substituent. Examples of the substituent include, but are not limited to, an alkyl group, an alkoxy group, and an aryl group.

[0084] The compound represented by General Formula (1A) above is preferably a compound represented by General Formula (1B) below.

[0085] [Chem.13]In General Formula (1B) above, R5represents a methyl group or a methoxy group, R6and R7represent an alkoxy group, and n represents an integer of 2 or more.

[0086] The weight average molecular weight of a compound (polymer) represented by General Formula (1) above is preferably 2,000 or more and 150,000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

[0087] Specific examples of the polymer represented by General Formula (1) include, but are not limited to, Compounds (A-01) to (A-31) below.

[0088] FN202402483 [Chem.14][Chem.16]FN202402483[Chem.18]FN202402483In General Formula (2) above, M represents any one element among boron, aluminum, phosphorus, and antimony. R2, R3, and R4each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, an ether bond, or an ester bond.

[0090] Examples of the halogen atom include, but are not limited to, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include, but are not limited to, an alkyl group having 1 to 6 carbon atoms. The alkyl group may be substituted with a halogen atom. Examples of the alkoxy group include, but are not limited to, an alkoxy group having 1 to 6 carbon atoms. Examples of the aryl group include, but are not limited to, a phenyl group.

[0091] FN202402483 Specific examples of a compound represented by General Formula (2) above include, but are not limited to, Compounds (B-1) to (B-17) below.

[0092] [Chem.21]

[0093] FN202402483 In the hole transport layer, the mass ratio [(1):(2)] of a polymer compound (1) having the structural unit of General Formula (1) above to a compound (2) represented by General Formula (2) above is not particularly limited and may be appropriately selected according to a purpose. However, to transport holes, the mass ratio is preferably from 1000:1 to 1000:500, and more preferably from 100:1 to 100:50.

[0094] The hole transport layer may further include, for example, another solid hole transport material, and if desired, may include other materials. The other solid hole transport material (may be simply referred to as "hole transport material" hereinafter) is not particularly limited and can be appropriately selected according to a purpose, as long as the other solid hole transport material is a material having a property by which holes are transported. However, the other solid hole transport material preferably contains an organic compound.

[0095] When an organic compound is used as the hole transport material, the hole transport layer contains, for example, a plurality of types of organic compounds.

[0096] Examples of the organic compound include, but are not limited to, a polymer material. The polymer material used in the hole transport layer is not particularly limited and can be appropriately selected according to a purpose. Examples of the polymer material include, but are not limited to, polythiophene compounds, polyphenylene vinylene compounds, polyfluorene compounds, polyphenylene compounds, polyarylamine compounds, and polythiadiazole compounds. Examples of the polythiophene compounds include, but are not limited to, 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), poly(2,5- bis(3-decylthiophene-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), and poly(3,6-dioctylthieno[3,2-b]thiophene-co- bithiophene). Examples of the polyphenylene vinylene compounds include, but are not limited to, 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 the polyfluorene compounds include, but are not limited to, poly(9,9'- didodecylfluorenyl-2,7-diyl), poly[(9,9-dioctyl-2,7-divinylene fluorene)-alt-co-(9,10- anthracene)], poly[(9,9-dioctyl-2,7-divinylene fluorene)-alt-co-(4,4'-biphenylene)], poly[(9,9- dioctyl-2,7-divinylene fluorene)-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)].FN202402483 Examples of the polyphenylene compounds include, but are not limited to, poly[2,5- dioctyloxy-1,4-phenylene] and poly[2,5-di(2-ethylhexyloxy-1,4-phenylene]. Examples of the polyarylamine compounds include, but are not limited to, poly[(9,9- dioctylfluorenyl-2,7-diyl)-alt-co-(N,N'-diphenyl)-N,N'-di(p-hexylphenyl)-1,4- diaminobenzene], poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(N,N'-bis(4- octyloxyphenyl)benzidine-N,N'-(1,4-diphenylene)], poly[(N,N'-bis(4- octyloxyphenyl)benzidine-N,N'-(1,4-diphenylene)], poly[(N,N'-bis(4-(2- ethylhexyloxy)phenyl)benzidine-N,N'-(1,4-diphenylene)], poly[phenylimino-1,4- phenylenevinylene-2,5-dioctyloxy-1,4-phenylenevinylene-1,4-phenylene], poly[p-tolylimino- 1,4-phenylenevinylene-2,5-di(2-ethylhexyloxy)-1,4-phenylenevinylene-1,4-phenylene], and poly[4-(2-ethylhexyloxy)phenylimino-1,4-biphenylene]. Examples of the polythiadiazole compounds include, but are not limited to, poly[(9,9- dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo(2,1',3)thiadiazole], and poly(3,4- didecylthiophene-co-(1,4-benzo(2,1',3)thiadiazole). Among these compounds, polythiophene compounds and polyarylamine compounds are preferred in consideration of carrier mobility and ionization potential.

[0097] The hole transport layer may contain not only the above-mentioned polymers, but also a compound having low molecular weight alone or a mixture of a compound having low molecular weight and a compound having high molecular weight. An example of a chemical structure of a hole transport material having low molecular weight is not particularly limited. Examples of the hole transport material having low molecular weight include, but are not limited to, oxadiazole compounds, triphenylmethane compounds, pyrazoline compounds, hydrazone compounds, tetraarylbenzidine compounds, stilbene compounds, spirobifluorene compounds, and thiophene oligomers. Examples of the oxadiazole compounds include, but are not limited to, the oxadiazole compounds described in Japanese Examined Patent Publication No.34-5466 and Japanese Unexamined Patent Application Publication No.56-123544. Examples of the triphenylmethane compounds include, but are not limited to, the triphenylmethane compounds described in Japanese Examined Patent Publication No.45-555. Examples of the pyrazoline compounds include, but are not limited to, the pyrazoline compounds described in Japanese Examined Patent Publication No.52-4188. Examples of the hydrazone compounds include, but are not limited to, the hydrazone compounds described in Japanese Examined Patent Publication No.55-42380. Examples of the tetraarylbenzidine compounds include, but are not limited to, the tetraarylbenzidine compounds described in Japanese Unexamined Patent Application Publication No.54-58445.FN202402483 Examples of the stilbene compounds include, but are not limited to, the stilbene compounds described in Japanese Unexamined Patent Application Publication No.58-65440 and Japanese Unexamined Patent Application Publication No.60-98437. Examples of the spirobifluorene compounds include, but are not limited to, the spirobifluorene compounds described in Japanese Unexamined Patent Application Publication No.2007-115665A, Japanese Unexamined Patent Application Publication No.2014-72327, Japanese Unexamined Patent Application Publication No.2001-257012, WO2004 / 063283, WO2011 / 030450, WO2011 / 45321, WO2013 / 042699, and WO2013 / 121835. Examples of the thiophene oligomers include, but are not limited to, the thiophene oligomers described in Japanese Unexamined Patent Application Publication No.2-250881 and Japanese Unexamined Patent Application Publication No.2013-033868.

[0098] When a polymer and a compound having low molecular weight are mixed, the difference in the ionization potentials of the polymer and the compound having low molecular weight is preferably 0.2 eV or less. The ionization potential is the energy required to remove one electron from a molecule, and is expressed in units of electron volts (eV). A method of measuring the ionization potential is not particularly limited. However, the ionization potential is preferably measured by photoelectron spectroscopy.

[0099] Other materials contained in the hole transport layer are not particularly limited and can be appropriately selected according to a purpose. Examples of the other materials include, but are not limited to, additives and oxidizing agents.

[0100] The additives are not particularly limited and can be appropriately selected according to a purpose. Examples of the additives include, but are not limited to, iodine, metal iodides such as lithium iodide, sodium iodide, potassium iodide, cesium iodide, calcium iodide, copper iodide, iron iodide, and silver iodide, quaternary ammonium salts such as tetraalkylammonium iodide and pyridinium iodide, metal bromides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, and calcium bromide, bromide salts of quaternary ammonium compounds such as tetraalkylammonium bromide and pyridinium bromide, metal chlorides such as copper chloride and silver chloride, metal acetates such as copper acetate, silver acetate, and palladium acetate, metal sulfates such as copper sulfate and zinc sulfate, metal complexes such as ferrocyanide-ferricyanide and ferrocene-ferricinium ions, sulfur compounds such as sodium polysulfide and alkylthiol-alkyl disulfide, viologen dyes, hydroquinone, and basic compounds such as pyridine, 4-t-butylpyridine, and benzimidazole.

[0101] Further, an oxidizing agent may be added.FN202402483 The oxidizing agent is not particularly limited and can be appropriately selected according to a purpose. Examples of the oxidizing agent include, but are not limited to, tris(4- bromophenyl)aminium hexachloroantimonate, silver hexafluoroantimonate, nitrosonium tetrafluoroborate, silver nitrate, cobalt complexes, and 4-isopropyl-4'- methyldiphenyliodonium tetrakis(pentafluorophenyl)borate. Note that, not all of the hole transport material needs to be oxidized by the oxidizing agent, and an effect is achieved as long as a part of the hole transport material is oxidized. Further, the oxidizing agent may or may not be removed from the system after the reaction. If the hole transport layer includes an oxidizing agent, a part or all of the hole transport material can be converted into radical cations. Therefore, it is possible to improve the conductivity and increase the durability and the stability of the output characteristics.

[0102] The average thickness of the hole transport layer is not particularly limited and may be appropriately selected according to a purpose. On the photoelectric conversion layer, the average thickness of the hole transport layer is preferably 0.01 μm or more and 20 μm or less, more preferably 0.1 μm or more and 10 μm or less, and even more preferably 0.2 μm or more and 2 μm or less.

[0103] The hole transport layer can be formed directly on the photoelectric conversion layer. A method of preparing the hole transport layer is not particularly limited and may be appropriately selected according to a purpose. Examples of the method include a method of forming a thin film in a vacuum such as by vacuum vapor deposition, and a wet film-forming method. Among these methods, in terms of production costs, the wet film-forming method is particularly preferred, and a method of coating a material on the photoelectric conversion layer to prepare the hole transport layer is more preferred. The wet film-forming method is not particularly limited and may be appropriately selected according to a purpose. Examples of the wet film-forming method include a dipping method, a spraying method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, and a gravure coating method. Examples of wet printing methods include, but are not limited to, methods such as letterpress, offset, gravure, intaglio, rubber plate, and screen printing.

[0104] The hole transport layer may also be prepared by forming a film in a supercritical fluid or a subcritical fluid at a temperature and pressure lower than the critical point, for example. A supercritical fluid is a fluid that exists as a non-aggregating high-density fluid in a temperature and pressure region higher than the limit (critical point) at which gas and liquid can coexist, does not aggregate even when compressed, and is in a state where the temperature is at or higher than the critical temperature and the pressure is at or higher than the critical pressure. The supercritical fluid is not particularly limited and can beFN202402483 appropriately selected according to a purpose. However, it is preferable to use a fluid having a low critical temperature. The subcritical fluid is not particularly limited and can be appropriately selected according to a purpose, as long as the subcritical fluid is a fluid existing as a high-pressure liquid in the temperature and pressure region near the critical point. The fluids mentioned as examples of the supercritical fluid can also be suitably used as the subcritical fluid.

[0105] Examples of the supercritical fluid include, but are not limited to, carbon monoxide, carbon dioxide, ammonia, nitrogen, water, alcohol solvents, hydrocarbon solvents, halogen solvents, and ether solvents. Examples of the alcohol solvents include, but are not limited to, methanol, ethanol, and n- butanol. Examples of the hydrocarbon solvents include, but are not limited to, ethane, propane, 2,3- dimethylbutane, benzene, and toluene. Examples of the halogen solvents include, but are not limited to, methylene chloride and chlorotrifluoromethane. An example of the ether solvents includes, but is not limited to, dimethyl ether. These supercritical fluids may be used alone or in combination of two or more types. Among these supercritical fluids, carbon dioxide is preferred, because carbon dioxide has a critical pressure of 7.3 MPa and a critical temperature of 31°C. Therefore, carbon dioxide can be easily brought into a supercritical state, and is non-flammable and easy to handle.

[0106] The critical temperature and the critical pressure of the supercritical fluid are not particularly limited and can be appropriately selected according to a purpose. The critical temperature of the supercritical fluid is preferably −273°C or higher and 300°C or lower, and more preferably 0°C or higher and 200°C or lower.

[0107] Further, in addition to the supercritical fluid and the subcritical fluid, an organic solvent and an entrainer can also be used. By adding an organic solvent and an entrainer, the solubility in the supercritical fluid can be more easily adjusted. The organic solvent is not particularly limited, can be appropriately selected according to a purpose, and examples thereof include, but are not limited to, ketone solvents, ester solvents, ether solvents, amide solvents, halogenated hydrocarbon solvents, and hydrocarbon solvents. Examples of the ketone solvents include, but are not limited to, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvents include, but are not limited to, ethyl formate, ethyl acetate, and n-butyl acetate. Examples of the ether solvents include, but are not limited to, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, and dioxane.FN202402483 Examples of the amide solvents include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. Examples of the halogenated hydrocarbon solvents include, but are not limited to, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, and 1-chloronaphthalene. Examples of the hydrocarbon solvents include, but are not limited to, n-pentane, n-hexane, n- octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o- xylene, m-xylene, p-xylene, ethylbenzene, and cumene. These solvents may be used alone or in combination of two or more types.

[0108] Further, after laminating the hole transport material on the photoelectric conversion layer, a pressing process step may be implemented. By the pressing process, the hole transport material adheres more closely to the photoelectric conversion layer, and thus, it is possible to improve the power generation efficiency. A method used in the pressing process is not particularly limited and can be appropriately selected according to a purpose. Examples of the method include a press molding method using a flat plate such as an infrared (IR) spectroscopy tablet molding machine, and a roll press method using a roller. The pressure during the pressing process is preferably 10 kgf / cm2or more, and more preferably 30 kgf / cm2or more. The time used for the pressing process is not particularly limited and can be appropriately selected according to a purpose, but is preferably 1 hour or less. Heat may also be applied during the pressing process.

[0109] During the pressing process, a release agent may be sandwiched between the pressing machine and the electrode. The release agent is not particularly limited and can be appropriately selected according to a purpose. Examples of the release agent include, but are not limited to, fluororesins such as polytetrafluoroethylene, polychlorotrifluoroethylene, a tetrafluoroethylene- hexafluoropropylene copolymer, a perfluoroalkoxy fluoride resin, polyvinylidene fluoride, an ethylene-tetrafluoroethylene copolymer, an ethylene-chlorotrifluoroethylene copolymer, and polyvinyl fluoride. These release agents may be used alone or in combination of two or more types.

[0110] -- Film Containing Metal Oxide -- After the pressing process step and before providing the second electrode, a film containing a metal oxide may be provided between the hole transport layer and the second electrode.FN202402483 The metal oxide is not particularly limited and can be appropriately selected according to a purpose. Examples of the metal oxide include, but are not limited to, molybdenum oxide, tungsten oxide, vanadium oxide, and nickel oxide. These metal oxides may be used alone or in combination of two or more types. Among these metal oxides, molybdenum oxide is preferred. A method of providing the film containing a metal oxide on the hole transport layer is not particularly limited and may be appropriately selected according to a purpose. Examples of the method include sputtering, a method of forming a thin film in a vacuum such as by vacuum vapor deposition, and a wet film-forming method.

[0111] A preferred example of a wet film-forming method for forming a film containing a metal oxide includes a method of preparing a paste in which a powder or a sol of the metal oxide is dispersed, and applying the paste or the sol onto the hole transport layer. The wet film-forming method is not particularly limited and may be appropriately selected according to a purpose. Examples of the wet film-forming method include a dipping method, a spraying method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, and a gravure coating method. Examples of wet printing methods include, but are not limited to, methods such as letterpress, offset, gravure, intaglio, rubber plate, and screen printing.

[0112] The average thickness of the film containing a metal oxide is not particularly limited and may be appropriately selected according to a purpose, but is preferably 0.1 nm or more and 50 nm or less, and more preferably 1 nm or more and 10 nm or less.

[0113] <Second Electrode> The second electrode may be formed on the hole transport layer or on a metal oxide in the hole transport layer. An electrode similar to the first transparent electrode can normally be used as the second electrode, and the second electrode does not necessarily require a support body, as long as the strength and the sealability are sufficiently maintained. Examples of materials used in the second electrode include, but are not limited to, metals such as platinum, gold, silver, copper, and aluminum; carbon-based compounds such as graphite, fullerene, carbon nanotubes, and graphene; conductive metal oxides such as ITO, FTO, and ATO; and conductive polymers such as polythiophene and polyaniline. These materials may be used alone or in combination of two or more types. The average thickness of the second electrode is not particularly limited and can be appropriately selected.FN202402483 The second electrode can be appropriately formed on the hole transport layer by coating, lamination, vapor deposition, CVD, bonding, or other techniques, depending on the type of material being used and the type of the hole transport layer.

[0114] <<Sealing Member>> In the photoelectric conversion element, it is possible and effective to use a sealing member that can shield at least the electron transport layer and the hole transport layer from the external environment of the photoelectric conversion element. In other words, in the present embodiment, it is preferable to further provide a sealing member that shields the photoelectric conversion layer from the external environment of the photoelectric conversion element. Any member known in the related art can be used as the sealing member, as long as the member can reduce the intrusion of excess moisture, oxygen, and the like from the external environment into the sealed interior. Further, the sealing member also has an effect of preventing mechanical damage caused when the photoelectric conversion element is pressed from the outside, and any member known in the related art can be used as the sealing member, as long as the member can achieve this effect.

[0115] Sealing methods can be broadly divided into "frame sealing" and "surface sealing". In the "frame sealing", a sealing member is provided in a peripheral edge portion of a power generation region, which is formed by the photoelectric conversion layer of the photoelectric conversion element, and then, the sealing member is adhered to the second substrate. In the "surface sealing", a sealing member is provided on the entire surface of the power generation region and then, adhered to the second substrate. By the former-mentioned "frame sealing", a hollow portion can be formed inside the sealed interior, and thus, it is possible to appropriately adjust the amount of moisture and the amount of oxygen in the sealed interior. Further, the "frame sealing" provides an effect of reducing the impact of electrode peeling, because the second electrode does not contact the sealing member. On the other hand, the latter-mentioned "surface sealing" is highly effective in preventing the intrusion of excess water and oxygen from the outside. The area in which the sealing member and the second substrate adhere to each other is large, and thus, the sealing strength is high, and the "surface sealing" is particularly suitable when a flexible substrate is used as the first substrate.

[0116] The type of the sealing member is not particularly limited and can be appropriately selected according to a purpose. For example, a cured resin or a glass resin having a low melting point can be used as the sealing member. The cured resin is not particularly limited and can be appropriately selected according to a purpose, as long as the cured resin is a resin that is cured by light or heat. However, among these resins, acrylic resins and epoxy resins are preferably used.

[0117] FN202402483 As a cured product of the acrylic resin, any known material can be used, as long as the material is a cured material of a monomer or an oligomer having an acrylic group in the molecule. As a cured product of the epoxy resin, any known material can be used, as long as the material is a cured product of a monomer or an oligomer having an epoxy group in the molecule. Examples of the epoxy resin include, but are not limited to, a water-dispersed resin, a solvent- free resin, a solid resin, a heat-curable resin, a curing agent mixed-type resin, and an ultraviolet-curable resin. Among these resins, the heat-curable resin and the ultraviolet- curable resin are preferred, and the ultraviolet-curable resin is more preferred. Note that, even an ultraviolet-curable resin may be heated, and even after ultraviolet curing, it is preferable to perform heating. Examples of the epoxy resin include, but are not limited to, bisphenol A type resins, bisphenol F type resins, novolak resins, cyclic aliphatic resins, long chain aliphatic resins, glycidyl amine resins, glycidyl ether resins, and glycidyl ester resins. These resins may be used alone or in combination of two or more types.

[0118] The epoxy resin is preferably mixed with a curing agent and various types of additives, if desired. The curing agents are classified into amine-based curing agents, acid anhydride-based curing agents, polyamide-based curing agents, and other types of curing agents. The curing agent is appropriately selected according to a purpose. Examples of the amine-based curing agents include, but are not limited to, aliphatic polyamines such as diethylenetriamine and triethylenetetramine, and aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Examples of the acid anhydride-based curing agents include, but are not limited to, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, HET acid anhydride, and dodecenylsuccinic anhydride. Examples of the other curing agents include, but are not limited to, imidazoles and polymercaptans. These curing agents may be used alone or in combination of two or more types.

[0119] Examples of the additives include, but are not limited to, a filling material (filler), a gap agent, a polymerization initiator, a drying agent (moisture absorbent), a curing promoter, a coupling agent, a flexibilizing agent, a colorant, a flame retardant auxiliary, an antioxidant, and an organic solvent. Among these additives, the filling material, the gap agent, the curing promoter, the polymerization initiator, and the drying agent (moisture absorbent) are preferred, and the filling material and the polymerization initiator are more preferred.FN202402483

[0120] The filling material is effective in suppressing the intrusion of moisture and oxygen. In addition, by using the filling material, it is possible to obtain effects including reducing the volumetric shrinkage during curing, reducing the amount of outgassing during curing or heating, improving the mechanical strength, and controlling the thermal conductivity and fluidity. Thus, stable output can be efficiently maintained in various environments. In particular, the output characteristics and the durability of photoelectric conversion elements are not only affected by the simple intrusion of moisture and oxygen, but also by the outgassing that occurs when a sealing member is cured or heated, which is an effect that cannot be ignored. In particular, the outgassing that occurs during heating has a significant effect on the output characteristics when a photoelectric conversion element is stored in a high-temperature environment. In this case, if the sealing member includes a filling material, a gap agent, and a drying agent, these materials can suppress the intrusion of moisture and oxygen. Further, by reducing the amount of material being used in the sealing member, it is possible to obtain an effect of reducing outgassing. This is effective not only during curing, but also when the photoelectric conversion element is stored in a high-temperature environment.

[0121] The filling material is not particularly limited and can be appropriately selected according to a purpose. Preferable examples of the filling material include, but are not limited to, inorganic filling materials such as crystalline or amorphous silica, talc, alumina, aluminum nitride, silicon nitride, calcium silicate, and calcium carbonate. These filling materials may be used alone or in combination of two or more types. The average primary particle diameter of the filling material is preferably 0.1 μm or more and 10 μm or less, and more preferably 1 μm or more and 5 μm or less. When the amount of the filling material being added is within a preferred range, an effect of suppressing the intrusion of moisture and oxygen can be sufficiently obtained, an appropriate viscosity is obtained. Further, an effect of improving the adhesion to the substrate and the degassing properties, controlling the width of the sealing member, and increasing the workability can be obtained.

[0122] The content of the filling material is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 20 parts by mass or more and 70 parts by mass or less, with respect to 100 parts by mass of the total amount of the sealing member. When the content of the filling material is within the above-mentioned ranges, the effect of suppressing the intrusion of moisture and oxygen is sufficiently obtained, an appropriate viscosity is obtained, and the adhesion and workability are also good.

[0123] FN202402483 The gap agent is also referred to as a gap control agent or a spacer agent, and by using the gap agent, it is possible to control a gap of the sealing member. For example, when a sealing member is applied onto the first substrate or the first electrode, and then, a second substrate is placed on the sealing member to perform sealing, the gap of the sealing member can be easily controlled, because the gap agent is mixed into the epoxy resin, so that the gap of the sealing member is aligned with the size of the gap agent. Any known material can be used as the gap agent, as long as the material is granular, has a uniform particle diameter, and has high solvent resistance and heat resistance. The material of the gap agent preferably has high affinity to the epoxy resin and a spherical particle shape. Specific examples of the material of the gap agent include, but are not limited to, glass beads, fine silica particles, and fine organic resin particles. These materials may be used alone or in combination of two or more types. The average particle diameter of the gap agent can be selected in accordance with the gap of the sealing member to be set. However, the average particle diameter is preferably 1 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less.

[0124] Examples of the polymerization initiator include, but are not limited to, a thermal polymerization initiator that uses heat to initiate polymerization, and a photopolymerization initiator that uses light to initiate polymerization. The thermal polymerization initiator is a compound that uses heat to generate active species such as radicals and cations. Specific examples of the thermal polymerization initiator include, but are not limited to, azo compounds such as 2,2'-azobisbutyronitrile (AIBN) and peroxides such as benzoyl peroxide (BPO). Examples of a thermal cationic polymerization initiator include, but are not limited to, benzenesulfonate esters and alkylsulfonium salts. On the other hand, in the case of an epoxy resin, a cationic photopolymerization initiator is preferably used as the photopolymerization initiator. When an epoxy resin is mixed with a cationic photopolymerization initiator and irradiated with light, the cationic photopolymerization initiator decomposes to generate a strong acid. The acid induces polymerization of the epoxy resin and thus, the curing reaction progresses. The cationic photopolymerization initiator has little volumetric shrinkage during curing, is not inhibited by oxygen, and has high storage stability. Examples of the cationic photopolymerization initiator include, but are not limited to, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, metallocene compounds, and silanol-aluminum complexes.

[0125] Further, a photoacid generator having a function of generating an acid by irradiation with light can also be used. The photoacid generator acts as an acid that initiates cationic polymerization. Examples of the photoacid generator include, but are not limited to, onium salts such as ionic sulfonium salts and iodonium salts that include a cationic moiety and anFN202402483 anionic moiety. These photoacid generators may be used alone or in combination of two or more types. The amount of the polymerization initiator to be added may vary depending on the material used. However, the amount of the polymerization initiator is preferably 0.5 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less, with respect to the total amount of 100 parts by mass of the sealing member. When the amount of the polymerization initiator being added is within the above-mentioned ranges, the curing proceeds appropriately, the remaining amount of uncured material can be reduced, and excessive outgassing can be prevented, which is effective.

[0126] The drying agent is also referred to as a moisture absorbent, and is a material having a function of physically or chemically adsorbing moisture. If the sealing member includes a drying agent, the moisture resistance may be further increased and the impact of outgassing may be reduced, which is effective. The drying agent is preferably in particulate form, and examples thereof include, but are not limited to, inorganic water-absorbing materials such as calcium oxide, barium oxide, magnesium oxide, magnesium sulfate, sodium sulfate, calcium chloride, silica gel, molecular sieves, and zeolite. Among these drying agents, zeolite and calcium oxide, which have a large moisture absorption capacity, are preferable. These drying agents may be used alone or in combination of two or more types.

[0127] The curing promoter is also referred to as a curing catalyst, is used for the purpose of accelerating the curing speed, and is mainly used for thermosetting epoxy resins. Examples of the curing promoter include, but are not limited to, tertiary amines or tertiary amine salts such as 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU) and 1,5-diazabicyclo(4,3,0)- nonene-5 (DBN); imidazoles such as 1-cyanoethyl-2-ethyl-4-methylimidazole and 2-ethyl-4- methylimidazole; and phosphines or phosphonium salts such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate. These curing promoters may be used alone or in combination of two or more types.

[0128] The coupling agent has an effect of increasing the molecular bonding strength. Examples of the coupling agent include, but are not limited to, silane coupling agents. Examples of the silane coupling agents include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4- epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-(2- aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3- aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-FN202402483 aminopropyltrimethoxysilane hydrochloride, and 3-methacryloxypropyltrimethoxysilane. These coupling agents may be used alone or in combination of two or more types.

[0129] Further, known epoxy resin compositions that are commercially available as sealing materials or adhesives, can also be effectively used as the sealing member in the present embodiment. Some of these known epoxy resin compositions have been developed and are commercially available for use in solar cells and organic EL devices. Examples of such epoxy resin compositions include, but are not limited to, TB3118, TB3114, TB3124, and TB3125F (all manufactured by ThreeBond Co., Ltd.), WORLD ROCK 5910, WORLD ROCK 5920, and WORLD ROCK 8723 (all manufactured by Kyoritsu Chemical Co., Ltd.), and WB90US(P) (manufactured by Moresco Corporation). Examples of commercially available acrylic resins include, but are not limited to, products by the trade names of TB3035B and TB3035C (both manufactured by ThreeBond Co., Ltd.) and NICHIBAN UM (manufactured by Nichiban Co., Ltd.). These sealing members can be cured by irradiation with ultraviolet light or the like and then subjected to a heat treatment, which is effective in the present embodiment. By performing the heat treatment, the amount of uncured components may be reduced, the amount of outgassing that impacts the output characteristics is reduced, and the sealing performance is improved, which is effective in improving the output characteristics and the durability of the output characteristics.

[0130] On the other hand, the glass resin having a low melting point is fired after application to decompose the resin components, and then, melted with an infrared laser or the like to cause the product to closely adhere to the glass substrate to perform sealing. At this time, glass components having a low melting point diffuse into the metal oxide layer and are physically bonded, and thus, high sealing performance can be obtained. Further, when the resin components are eliminated, outgassing does not occur as in the case of an ultraviolet curable resin, which is effective in increasing the durability of the photoelectric conversion element. Generally, glass resins are commercially available as glass frit or glass paste, and these can be effectively used. In one embodiment, a resin having a lower melting point is preferred.

[0131] The temperature in the heat treatment is not particularly limited and can be freely set in accordance with the sealing member being used. However, the temperature is preferably 50°C or higher and 200°C or lower, more preferably 60°C or higher and 150°C or lower, and even more preferably 70°C or higher and 100°C or lower. The time of the heat treatment is not particularly limited and can be freely set in accordance with the sealing member being used. However, the time is preferably 10 minutes or longer and 10 hours or shorter, more preferably 20 minutes or longer and 5 hours or shorter, and even more preferably 30 minutes or longer and 3 hours or shorter.FN202402483

[0132] In one embodiment, a sheet-shaped sealing material can also be effectively used. The sheet-shaped sealing material is obtained by forming in advance a resin layer on a sheet. The sheet includes glass, a film having high gas barrier properties, or the like, and the sheet corresponds to the second substrate. The sheet-shaped sealing material is attached onto the second electrode of the photoelectric conversion element and then cured, so that the sealing member and the substrate can be formed in one process. If the resin layer formed on the sheet is formed over the entire surface of the sheet, the type of sealing is "surface sealing". However, depending on the formation pattern of the resin layer, the type of sealing may be "frame sealing", in which a hollow portion is provided inside the photoelectric conversion element. If the hollow portion inside the sealed interior contains oxygen, it is possible to stably maintain the hole transport function of the hole transport layer during a long period of time, which may be effective in improving the durability of the photoelectric conversion element. Such an effect can be obtained, as long as the oxygen concentration in the hollow portion in the sealed interior formed in the sealing process exceeds 0 vol%. However, the oxygen concentration is preferably 5.0 vol% or more and 21.0 vol% or less, and more preferably 10.0 vol% or more and 21.0 vol% or less.

[0133] The oxygen concentration in the hollow portion can be controlled by performing the sealing process in a glove box in which the oxygen concentration is adjusted. The oxygen concentration can be adjusted by a method of using a gas cylinder having a determined oxygen concentration or by a method of using a nitrogen gas generator. The oxygen concentration in the glove box can be measured by using a commercially available oxygen concentration meter or an oxygen monitor. For example, the oxygen concentration in the hollow portion formed by the sealing process can be measured by an in-package moisture and residual gas analysis (IVA) or an atmospheric pressure ionization mass spectrometer (API-MS). Specifically, the photoelectric conversion element is placed in a chamber under high vacuum or a chamber filled with an inert gas. The sealing is released inside the chamber, and the gas and the moisture inside the chamber are subjected to mass analysis to quantify all components in the gas contained in the hollow portion. The ratio of oxygen to the sum of all the components is calculated to determine the oxygen concentration.

[0134] A gas other than oxygen contained inside the sealed interior is preferably an inert gas, and examples of preferred gases include, but are not limited to, nitrogen and argon. When the sealing process is performed, it is preferable to control the dew point, together with the oxygen concentration inside the glove box, which is effective in improving the output andFN202402483 the durability of the output. The dew point is defined as the temperature at which condensation starts when a gas containing water vapor is cooled. The dew point is not particularly limited, but is preferably 0°C or lower, and more preferably −20°C or lower. The lower limit of the dew point is preferably −50°C or higher.

[0135] A method of forming the sealing member is not particularly limited and the sealing member can be formed in accordance with a known method. For example, various methods may be used, such as a dispense method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, a letterpress method, an offset method, an intaglio method, a rubber plate method, and a screen printing method.

[0136] Further, a passivation layer may be provided between the sealing member and the second electrode. The passivation layer is not particularly limited and can be appropriately selected according to a purpose, as long as the passivation layer is arranged so that the sealing member does not contact the second electrode. However, aluminum oxide, silicon nitride, silicon oxide, and the like are preferably used in the passivation layer.

[0137] <Other Members> Other members are not particularly limited and can be appropriately selected according to a purpose.

[0138] An example of the photoelectric conversion element of the present embodiment will be described below with reference to the drawings. However, the present disclosure is not limited to these examples. For example, the number, the position, the shape, and the like of the constituent members described below that are not described in the present embodiment are also included in the scope of the present disclosure.

[0139] <First Embodiment> FIG.1 is a schematic diagram illustrating an example of a solar cell as an embodiment of a photoelectric conversion element. FIG.2 is an enlarged view of an output terminal of the solar cell illustrated in FIG.1. A solar cell 50 in FIG.1 includes a first substrate 1, a first electrode 2, a dense electron transport layer 3, a perovskite layer 5 serving as a photoelectric conversion layer, a hole transport layer 7, a second electrode 8, and a sealing member 10 sealing the laminated body including these layers. The first electrode 2 contacts the dense electron transport layer 3. The dense electron transport layer 3 contacts the perovskite layer 5. The perovskite layer 5 may contact the hole transport layer 7, but a passivation layer 6 is preferably provided between the perovskite layer 5 and the hole transport layer 7. Further, anFN202402483 electrode protection layer 9 may be provided on the second electrode 8. In the solar cell 50, the electrode protection layer 9 is provided between the second electrode 8 and the second substrate 11, and thus, peeling or damage of the second electrode 8 can be prevented. The second substrate 11 may be provided on the sealing member 10, or a sealing member and a second substrate may be integrally formed. The hole transport layer 7 contacts the second electrode 8.

[0140] The solar cell 50 includes an output terminal 20 that is integrally formed with the solar cell 50. The output terminal 20 includes an end portion 21 of the first electrode 2 exposed from the sealing member 10 and a metal layer 22 provided on the end portion 21, as illustrated in FIGs.1 and 2. The end portion 21 of the first electrode 2 has an uneven shape, and the metal layer 22 provided on the end portion 21 also has an uneven shape. The arithmetic mean height (Ra) of a surface of the output terminal 20 where the metal layer 22 is provided is 0.1 μm or more and 0.3 μm or less, and the ten-point average roughness (Rz) of the surface of the output terminal 20 where the metal layer 22 is provided is 0.35 μm or more and 0.75 μm or less.

[0141] <Second Embodiment> FIG.3 is a schematic diagram illustrating another example of a solar cell as an embodiment of a photoelectric conversion element. A solar cell 60 in FIG.3 includes the output terminal 20 that is integrally formed with the solar cell 60. The output terminal 20 further includes, on the end portion 21 of the first electrode 2 exposed from the sealing member 10, an electron transport layer 23 exposed from the sealing member 10, and a perovskite layer 25 exposed from the sealing member 10, and further includes the metal layer 22 provided thereon. This configuration is advantageous in that the arithmetic mean height (Ra) and the ten-point average roughness (Rz) are larger than those of the output terminal 20 illustrated in FIGs.1 and 2, the electrode adhesion is improved, and the charge extraction is excellent.

[0142] (Photoelectric Conversion Module) In a photoelectric conversion module of the present embodiment, a plurality of the photoelectric conversion elements of the present embodiment are electrically connected to each other in series or in parallel. For example, the photoelectric conversion module includes a plurality of the photoelectric conversion elements of the present embodiment on a substrate, and preferably further includes a second substrate different from the substrate mentioned above, a sealing member, and if desired, includes another member. An example of the photoelectric conversion module includes, but is not limited to, a photoelectric conversion module.FN202402483

[0143] In the photoelectric conversion module, a plurality of the photoelectric conversion elements are provided on a substrate. In the photoelectric conversion module, it is preferable that, in at least two photoelectric conversion elements adjacent to each other, the hole transport layers are continuous with each other, and the first electrodes, the electron transport layers, and the photoelectric conversion layers in the at least two photoelectric conversion elements adjacent to each other are separated by the hole transport layers. In such a photoelectric conversion module, the electron transport layer and the photoelectric conversion layer are disconnected, so that the recombination of electrons due to diffusion is reduced, and thus, it possible to maintain power generation efficiency, even after the photoelectric conversion module is exposed to light having high luminous intensity during a long period of time.

[0144] If the photoelectric conversion module is combined with a circuit board and the like that controls the generated current, the photoelectric conversion module can be applied to a power supply device. Examples of appliances that utilize power supply devices include, but are not limited to, electronic desk calculators and wristwatches. Moreover, the power supply device including the photoelectric conversion module can be applied to mobile phones, electronic notebooks, electronic paper, and the like. Further, a power supply device including the photoelectric conversion module of the present disclosure can be used as an auxiliary power source to extend the continuous operating time of a rechargeable electric device or an electric device using a dry battery, or as a power source that can be utilized at night and the like by combining the power source with a secondary battery and the like. Further, the power supply device can be used as an independent power source that does not require battery replacement, power wiring, or the like in IoT devices and artificial satellites.

[0145] (Solar Cell Module) In a solar cell module of the present embodiment, a plurality of the photoelectric conversion elements of the present embodiment are electrically connected in series or in parallel. The solar cell module is similar to the photoelectric conversion module.

[0146] An example of the photoelectric conversion module of the present embodiment will be described below with reference to the drawings. However, the present disclosure is not limited to these examples. For example, the number, the position, the shape, and the like of the constituent members described below that are not described in the present embodiment are also included in the scope of the present disclosure.

[0147] FIG.4 is a cross-sectional diagram illustrating an example of the solar cell module of the present embodiment. As illustrated in FIG.4, a solar cell module 90 includes three of the solar cells 50 illustrated in FIG.1, and adjacent ones of the solar cells 50 are electricallyFN202402483 connected in series. The solar cells 50 located at the two ends each include the output terminal 20 that is integrally formed with the solar cell 50. The output terminal 20 includes the end portion 21 of the first electrode 2 exposed from the sealing member 10 and the metal layer 22 provided on the end portion 21, as illustrated in FIGs.1 and 2. The end portion 21 of the first electrode 2 has an uneven shape, and the metal layer 22 provided on the end portion 21 also has an uneven shape. The arithmetic mean height (Ra) of the surface of the output terminal 20 where the metal layer 22 is provided is 0.1 μm or more and 0.3 μm or less, and the ten-point average roughness (Rz) of the surface of the output terminal 20 where the metal layer 22 is provided is 0.35 μm or more and 0.75 μm or less.

[0148] FIG.5 is a cross-sectional diagram illustrating another example of the solar cell module of the present embodiment. As illustrated in FIG.5, a solar cell module 100 includes, on the first substrate 1, photoelectric conversion elements a and b including respective first electrodes 2a and 2b (may be collectively referred to as the first electrode 2), the dense electron transport layer (dense layer) 3, a porous electron transport layer (porous layer) 4, the perovskite layer 5, the passivation layer 6, the hole transport layer 7, and respective second electrodes 8a and 8b (may be collectively referred to as the second electrode 8). The first electrode 2 and the second electrode 8 have a conductive path leading to the output terminal 20. Further, in the solar cell module 100, the second substrate 11 is arranged facing the first substrate 1, to sandwich the photoelectric conversion elements a and b therebetween, and the sealing member 10 is arranged between the first substrate 1 and the second substrate 11. In the solar cell module 100, the first electrodes 2a and 2b, the dense layers 3, the porous layers 4, the perovskite layers 5, and the passivation layers 6 in the photoelectric conversion element a and the photoelectric conversion element b are separated from each other by the hole transport layers 7 that form a continuous layer extending between the photoelectric conversion element a and the photoelectric conversion element b.

[0149] FIG.6 is a cross-sectional diagram illustrating an example of the cross-sectional structure of a solar cell module of the present embodiment. As illustrated in FIG.6, a solar cell module 101 includes, on the first substrate 1, photoelectric conversion elements a and b including respective first electrodes 2a and 2b, the dense electron transport layer (dense layer) 3, the perovskite layer 5, the passivation layer 6, the hole transport layer 7, and respective second electrodes 8a and 8b. The first electrode 2 and the second electrode 8 have a conductive path leading to the output terminal 20. Further, in the solar cell module 101, the second substrate 11 is arranged facing the first substrate 1, to sandwich the photoelectric conversion elements a and b therebetween, and the sealing member 10 is arranged between the first substrate 1 and the second substrate 11. In the solar cell module 101, the first electrodes 2a and 2b, the dense layers 3, the perovskite layers 5, and the passivation layers 6 in the photoelectric conversion element a and theFN202402483 photoelectric conversion element b are separated from each other by the hole transport layers 7 forming a continuous layer that extends between the photoelectric conversion element a and the photoelectric conversion element b.

[0150] FIG.7 is a cross-sectional diagram illustrating an example of the cross-sectional structure of a solar cell module of the present embodiment. As illustrated in FIG.7, a solar cell module 102 includes, on the first substrate 1, photoelectric conversion elements a and b including respective first electrodes 2a and 2b, the dense electron transport layer (dense layer) 3, the porous electron transport layer (porous layer) 4, the perovskite layer 5, the passivation layer 6, the hole transport layer 7, and respective second electrodes 8a and 8b. The first electrode 2 and the second electrode 8 have a conductive path leading to the output terminal 20. Further, in the solar cell module 102, the second substrate 11 is arranged facing the first substrate 1, to sandwich the photoelectric conversion elements a and b therebetween, and the sealing member 10 is arranged between the first substrate 1 and the second substrate 11. In the solar cell module 102, the first electrodes 2a and 2b and the dense layers 3 in the photoelectric conversion element a and the photoelectric conversion element b are separated from each other by the porous layer 4, the perovskite layer 5, the passivation layer 6, and the hole transport layer 7, which form a continuous layer extending between the photoelectric conversion element a and the photoelectric conversion element b.

[0151] FIG.8 is a cross-sectional diagram illustrating an example of the cross-sectional structure of a solar cell module of the present embodiment. As illustrated in FIG.8, a solar cell module 103 includes, on the first substrate 1, photoelectric conversion elements a and b including respective first electrodes 2a and 2b, the dense electron transport layer (dense layer) 3, the porous electron transport layer (porous layer) 4, the perovskite layer 5, the passivation layer 6, the hole transport layer 7, and respective second electrodes 8a and 8b. The first electrode 2 and the second electrode 8 have a conductive path leading to the output terminal 20. Further, in the solar cell module 103, the second substrate 11 is arranged facing the first substrate 1, to sandwich the photoelectric conversion elements a and b therebetween, and the sealing member 10 is arranged between the first substrate 1 and the second substrate 11. In the solar cell module 103, the first electrodes 2a and 2b, the dense layers 3, the porous layers 4, and the passivation layers 6 in the photoelectric conversion element a and the photoelectric conversion element b are separated from each other by the perovskite layer 5 and the hole transport layer 7, which form a continuous layer extending between the photoelectric conversion element a and the photoelectric conversion element b.

[0152] FIG.9 is a cross-sectional diagram illustrating an example of the cross-sectional structure of a solar cell module of the present embodiment. As illustrated in FIG.9, a solar cell module 104 includes, on the first substrate 1, photoelectric conversion elements a and b includingFN202402483 respective first electrodes 2a and 2b, the dense electron transport layer (dense layer) 3, the perovskite layer 5, the passivation layer 6, the hole transport layer 7, and respective second electrodes 8a and 8b. The first electrode 2 and the second electrode 8 have a conductive path leading to the output terminal 20. Further, in the solar cell module 104, the second substrate 11 is arranged facing the first substrate 1, to sandwich the photoelectric conversion elements a and b therebetween, and the sealing member 10 is arranged between the first substrate 1 and the second substrate 11.

[0153] In the solar cell module 104, the first electrodes 2a and 2b and the dense layers 3 in the photoelectric conversion element a and the photoelectric conversion element b are separated from each other by the perovskite layer 5, the passivation layer 6, and the hole transport layer 7, which form a continuous layer extending between the photoelectric conversion element a and the photoelectric conversion element b.

[0154] The solar cell modules 90 and 100 to 104 are sealed by the first substrate 1, the sealing member 10, and the second substrate 11. Therefore, it is possible to control the amount of moisture and the oxygen concentration in a hollow portion present between the second electrode 8 and the second substrate 11. By controlling the amount of moisture and the oxygen concentration in the hollow portion of the solar cell modules 90 and 100 to 104, the power generation performance and the durability can be improved. That is, if the solar cell module further includes a second substrate arranged facing the first substrate to sandwich the photoelectric conversion element therebetween, and a sealing member arranged between the first substrate and the second substrate to seal the photoelectric conversion element, the amount of moisture and the oxygen concentration in the hollow portion can be controlled, and thus, it is possible to improve the power generation performance and the durability. The oxygen concentration in the hollow portion is not particularly limited and can be appropriately selected according to a purpose. However, the oxygen concentration is preferably 0% or more and 21% or less, more preferably 0.05% or more and 10% or less, and even more preferably 0.1% or more and 5% or less.

[0155] In the solar cell modules 100 to 104, the second electrode 8 and the second substrate 11 do not contact each other, so that peeling or damage of the second electrode 8 can be prevented.

[0156] Further, the solar cell modules 100 to 104 include a through portion 15 that electrically connects the photoelectric conversion element a and the photoelectric conversion element b. In the solar cell modules 100 to 104, the second electrode 8a of the photoelectric conversion element a and the first electrode 2b of the photoelectric conversion element b are electrically connected by the through portion 15 penetrating the hole transport layer 7, so that the photoelectric conversion element a and the photoelectric conversion element b are connectedFN202402483 in series. Thus, by connecting a plurality of photoelectric conversion elements in series, the open circuit voltage of the solar cell module can be increased.

[0157] Note that the through portion 15 may penetrate the first electrode 2 and extend to the first substrate 1, or the processing for providing the through portion 15 may be stopped inside the first electrode 2 and the through portion 15 may not extend to the first substrate 1. When the through portion 15 has the shape of micropores that penetrate the first electrode 2 and extend to the first substrate 1, if the total opening area of the micropores relative to the area of the through portion 15 is too large, the cross-sectional film area of the first electrode 2 decreases. Therefore, the resistance value increases, which may cause a decrease in the photoelectric conversion efficiency. Thus, the ratio of the total opening area of the micropores to the area of the through portion 15 is preferably 5 / 100 or more and 60 / 100 or less.

[0158] A method of forming the through portion is not particularly limited and can be appropriately selected according to a purpose. Examples of the method include a sand blasting method, a water blasting method, a chemical etching method, a laser processing method, and a method using abrasive paper. Among these methods, the laser processing method is preferred, because fine holes can be formed without using sand, etching, a resist, and the like, and thus, the material can be processed cleanly with good reproducibility. Further, the laser processing method is also preferable because, when forming the through portion 15, at least one of the dense layer 3, the porous layer 4, the perovskite layer 5, the passivation layer 6, the hole transport layer 7, and the second electrode 8 can be removed by impact peeling using the laser processing method. Thus, it is not necessary to provide a mask during lamination. Further, it is possible to easily remove the material forming the photoelectric conversion element and form the through portion in one process.

[0159] Here, the perovskite layer in the photoelectric conversion element a and the perovskite layer in the photoelectric conversion element b may extended one after the other or may be separated. When the perovskite layers are separated, the distance between the perovskite layers is preferably 1 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less. When the distance between the perovskite layer in the photoelectric conversion element a and the perovskite layer in the photoelectric conversion element b is 1 μm or more and 100 μm or less, a porous titanium oxide layer and the perovskite layer are discontinuous and the recombination of electrons due to diffusion is reduced. Thus, it is possible to maintain power generation efficiency even after exposure to light having high luminous intensity during a long period of time. That is, in at least two photoelectric conversion elements that are adjacent to each other, the distance between the electron transport layer and the perovskite layer in one photoelectric conversion element and theFN202402483 electron transport layer and the perovskite layer in the other photoelectric conversion element is 1 μm or more and 100 μm or less. Therefore, it is possible to maintain the power generation efficiency even after exposure to light having high luminous intensity during a long period of time. In at least two photoelectric conversion elements that are adjacent to each other, the distance between the electron transport layer and the perovskite layer in one photoelectric conversion element and the electron transport layer and the perovskite layer in the other photoelectric conversion element refers to the distance of the shortest portion between outer peripheral portions (end portions) of the electron transport layers and the perovskite layers in the photoelectric conversion elements.

[0160] If the solar cell module of the present embodiment is combined with a circuit board and the like that controls the generated current, the solar cell module can be applied to a power supply device. Examples of appliances that utilize power supply devices include, but are not limited to, electronic desk calculators and wristwatches. The power supply device including the photoelectric conversion element of the present embodiment can be applied to mobile phones, electronic notebooks, electronic paper, and the like. Further, a power supply device including the photoelectric conversion element of the present embodiment can be used as an auxiliary power source to extend the continuous operating time of a rechargeable electric device or an electric device using a dry battery, or as a power source that can be utilized at night and the like by combining the power source with a secondary battery and the like. Moreover, the power supply device can be used as an independent power source that does not require battery replacement, power wiring, or the like in IoT devices and artificial satellites.

[0161] (Electronic Device) An electronic device of the present embodiment includes at least any one of the photoelectric conversion element and the photoelectric conversion module of the present embodiment, and a device that operates by using electric power generated by photoelectric conversion by at least any one of the photoelectric conversion element and the photoelectric conversion module. If desired, the electronic device of the present embodiment further includes another device. The electronic device of the present embodiment includes at least any one of the photoelectric conversion element and the photoelectric conversion module of the present embodiment, a storage battery that can store electric power generated by photoelectric conversion by at least any one of the photoelectric conversion element and the photoelectric conversion module, and a device that operates by using the electric power stored in the storage battery. If desired, the electronic device of the present embodiment further includes another device.

[0162] (Power Supply Module)FN202402483 A power supply module of the present embodiment includes at least any one of the photoelectric conversion element and the photoelectric conversion module of the present embodiment, and a power supply integrated circuit (power supply IC, integrated circuit), and if desired, further includes another device.

[0163] Next, a specific embodiment of an electronic device including at least any one of the photoelectric conversion module of the present embodiment and the solar cell module of the present embodiment, and a device that operates by using electric power generated by the at least any one of the photoelectric conversion module of the present embodiment and the solar cell module of the present embodiment will be described.

[0164] FIG.10 is a block diagram of a mouse for a personal computer as an example of the electronic device of the present embodiment. As illustrated in FIG.10, a photoelectric conversion element 201, a photoelectric conversion module, a power supply IC 202, and a power storage device 203 are combined, and the supplied electric power is connected to the power supply of a control circuit 204 of the mouse. Thus, the power storage device 203 can be charged when the mouse is not being used, and the mouse can be operated by using the electric power, so that it possible to obtain a mouse that does not require wiring or battery replacement. Further, no battery is required, and thus, the device can be made lighter, which is effective.

[0165] FIG.11 is a schematic external view illustrating an example of the mouse illustrated in FIG. 10. As illustrated in FIG.11, the photoelectric conversion element 201, the power supply IC 202, and the power storage device 203 are mounted inside the mouse. However, an upper portion of the photoelectric conversion element 201 is covered with a transparent housing, so that light can reach the photoelectric conversion element 201. It is also possible to mold the entire housing of the mouse from a transparent resin. The arrangement of the photoelectric conversion element 201 is not limited thereto, and it is possible and may be preferable to arrange the photoelectric conversion element 201 at a position where the photoelectric conversion element 201 is irradiated with light, even when the mouse is covered by a hand.

[0166] Next, another embodiment of the electronic device including the photoelectric conversion module of the present embodiment and a device that operates by using electric power generated by the photoelectric conversion module will be described.

[0167] FIG.12 is a block diagram of a keyboard for a personal computer as an example of the electronic device of the present embodiment.FN202402483 As illustrated in FIG.12, the photoelectric conversion element 201, the power supply IC 202, and the power storage device 203 are combined, and the supplied electric power is connected to the power supply of a control circuit 205 of the keyboard. Thus, the power storage device 203 can be charged when the keyboard is not being used, and the keyboard can be operated by using the electric power, so that it possible to obtain a keyboard that does not require wiring or battery replacement. Further, no battery is required, and thus, the device can be made lighter, which is effective.

[0168] FIG.13 is a schematic external view illustrating an example of the keyboard illustrated in FIG.12. As illustrated in FIG.13, the photoelectric conversion element 201, the power supply IC 202, and the power storage device 203 are mounted inside the keyboard. However, an upper portion of the photoelectric conversion element 201 is covered with a transparent housing, so that light can reach the photoelectric conversion element 201. It is also possible to mold the entire housing of the keyboard from a transparent resin. Note that the arrangement of the photoelectric conversion element 201 is not limited thereto. In the case of a small keyboard having little space for mounting a photoelectric conversion element, it is possible and effective to embed a small photoelectric conversion element in a part of a key, as illustrated in FIG.14.

[0169] Next, another embodiment of the electronic device including the photoelectric conversion module of the present embodiment and a device that operates by using electric power generated by the photoelectric conversion module will be described.

[0170] FIG.15 is a block diagram of a sensor as an example of an electronic device of the present embodiment. As illustrated in FIG.15, the photoelectric conversion element 201, the power supply IC 202, and the power storage device 203 are combined, and the supplied electric power is connected to the power supply of a sensor circuit 206. Thus, it possible to obtain a sensor module A that does not need to be connected to an external power supply and does not need battery replacement. The sensor module A can be effectively applied to a variety of sensors, and sensing targets include temperature and humidity, illuminance, human presence, CO2concentration, acceleration, UV intensity, noise, geomagnetism, and air pressure. As illustrated in FIG.15, the sensor module is configured to periodically sense a measurement target and transmit the read data by radio communication to a device 207 such as a PC or a smartphone. With the development of Internet of Things (IoT) technology, the number of sensors is expected to increase rapidly. Replacing the batteries in these countless sensors one by one would be a lot of work and is not practical. Further, the sensors are often located in placesFN202402483 such as a ceiling and a wall, where it is difficult to replace batteries, which also reduces the workability. It is possible to supply electric power by using the photoelectric conversion element, which is also very beneficial. Further, the photoelectric conversion module of the present disclosure also has the advantage of providing high output, even at low luminous intensity, and the output is not strongly dependent on the incident angle of light, so that the freedom in installation is high.

[0171] Next, another embodiment of the electronic device including the photoelectric conversion module of the present embodiment and a device that operates by using electric power generated by the photoelectric conversion module will be described.

[0172] FIG.16 is a block diagram of a turntable as an example of the electronic device of the present embodiment. As illustrated in FIG.16, the photoelectric conversion element 201, the power supply IC 202, and the power storage device 203 are combined, and the supplied electric power is connected to a power supply of a turntable control circuit 208. Thus, it possible to obtain a turntable that does not need to be connected to an external power supply and in which the battery does not need to be replaced. For example, turntables are used in showcases for displaying products. However, the wiring of the power supply does not have good appearance, and during battery replacement, the displayed items need to be removed, which is a lot of work. By using the photoelectric conversion module of the present disclosure, such problems can be eliminated, which is effective.

[0173] Above, an electronic device and a power supply module, which include the photoelectric conversion module of the present embodiment and a device that operates by using electric power generated by the photoelectric conversion module are described. However, these are only some of the applications, and the photoelectric conversion module of the present embodiment is not limited to these applications.

[0174] <Applications> The photoelectric conversion module of the present embodiment can function as a standalone power supply, and can cause a device to operate by using electric power generated by photoelectric conversion. The photoelectric conversion module of the present embodiment can generate electricity when irradiated with light, and thus, the electronic device does not need to be connected to a power source and does not need battery replacement. Therefore, it is possible to operate an electronic device even in a place without power supply facilities, to attach a device to the body and move together with the device, and to operate an electronic device without changing a battery, for example in a place where it is difficult to change theFN202402483 battery. Further, when a dry battery is used, the weight and the size of the electronic device increase by the weight and the size of the dry battery, and thus, it may be difficult to install the electronic device on a wall or a ceiling or to carry the electronic device. However, the photoelectric conversion module of the present embodiment is light and thin, and thus has advantages such as a high freedom in installation and the possibility to be worn and carried.

[0175] As described above, the photoelectric conversion module of the present embodiment can be used as a standalone power source and can be combined with various electronic devices. For example, the photoelectric conversion module can be used in combination with many electronic devices, including display devices such as electronic desk calculators, wristwatches, mobile phones, electronic notebooks, and electronic paper, computer accessories such as a mouse and a keyboard, various types of sensor devices such as temperature and humidity sensors and sensors detecting human presence, transmitters such as beacons and GPS devices, auxiliary lights, and remote controls. Further, by imparting flexibility to the photoelectric conversion element or the photoelectric conversion module, the photoelectric conversion element or the photoelectric conversion module can also be applied to flexible devices.

[0176] In particular, the photoelectric conversion module of the present embodiment can generate electricity even with light of low luminous intensity, and thus can generate power even indoors and in dimly lit places in the shadow, so that the photoelectric conversion module has a wide range of applications. In the photoelectric conversion module, there is no leakage such as in dry batteries, and the photoelectric conversion module does not present the risk of being swallowed such as button batteries. Therefore, the photoelectric conversion module is very safe. Moreover, the photoelectric conversion module can also be used as an auxiliary power supply for extending the continuous operating time of a rechargeable electric device or an electric device using a dry battery. As described above, by combining the photoelectric conversion module of the present embodiment with a device that operates by using electric power generated by photoelectric conversion by the photoelectric conversion module, it is possible to obtain an electronic device that is light, easy to use, has a high degree of freedom in installation, does not require replacement, has excellent safety, and is also effective in reducing the environmental impact.

[0177] FIG.17 illustrates a general configuration of an electronic device obtained by combining the photoelectric conversion element 201 of the present embodiment and a device 209 that operates by using electric power generated by photoelectric conversion in the photoelectric conversion element 201. When the photoelectric conversion element 201 is irradiated with light, electricity is generated and electric power can be extracted. The circuit of the device can operate by using the generated electric power.FN202402483

[0178] The output of the photoelectric conversion element of the photoelectric conversion module changes depending on the surrounding illuminance, and thus, the electronic device illustrated in FIG.17 may not operate stably. In this case, as illustrated in FIG.18, it is possible and effective to incorporate a power supply IC 202 for a photoelectric conversion element between the photoelectric conversion element 201 and a circuit of the device 209, to supply a stable voltage to the circuit side. The photoelectric conversion element of the photoelectric conversion module can generate electricity when being irradiated with light having sufficient luminous intensity. However, if the luminous intensity is insufficient to generate electricity, the desired electric power is not obtained, which is a drawback of the photoelectric conversion element. In this case, as illustrated in FIG.19, by mounting a power storage device 203 such as a capacitor between the power supply IC 202 and the circuit of the device 209, it is possible to charge the power storage device with excess electric power from the photoelectric conversion element. Even when the luminous intensity is too low or no light is incident on the photoelectric conversion element, it is possible to supply electric power stored in the power storage device to the device circuit, so that stable operation is possible.

[0179] Thus, in an electronic device in which the photoelectric conversion module of the present embodiment and a device circuit are combined, by combining a power supply IC and a power storage device, it is possible to operate the electronic device even in an environment without a power source, and it is possible to operate the electronic device stably without replacing the battery, so that the benefits of the photoelectric conversion element are maximized.

[0180] On the other hand, the photoelectric conversion module of the present embodiment can also be effectively used as a power supply module. For example, as illustrated in FIG.20, by connecting the photoelectric conversion element 201 of the present embodiment to a power supply IC 202 for a photoelectric conversion element, a DC power supply module can be obtained that can supply electric power generated by photoelectric conversion in the photoelectric conversion element of the photoelectric conversion module, at a constant voltage level via the power supply IC. Further, as illustrated in FIG.21, by adding a power storage device 203 to the power supply IC 202, it is possible to charge the power storage device with electric power generated by the photoelectric conversion element of the photoelectric conversion module, and thus, it is possible to obtain a power supply module that can supply electric power, even when the luminous intensity is too low or when no light is incident on the photoelectric conversion element.FN202402483 The power supply module of the present embodiment illustrated in FIGs.20 and 21 can be used as a power supply module without the need for battery replacement, such as in conventional primary batteries. [Examples]

[0181] The present disclosure will be described below with reference to Examples and Comparative Examples. Note that the present disclosure is not limited to the Examples described herein.

[0182] (Manufacturing Example 1) <Synthesis of Polymer Compound (A-17)> Polymer Compound (A-17) serving as a hole transport material was synthesized by the reaction indicated by the reaction formula below.

[0183] [Chem.23]

[0184] A four-neck flask having a volume of 100 ml was used and 0.66 g (2.0 mmol) of a dialdehyde compound indicated by the reaction formula above and 1.02 g (2.0 mmol) of diphosphonate were placed into the flask. The atmosphere was replaced with nitrogen, and then, 75 ml of tetrahydrofuran were added to the flask. 6.75 ml (6.75 mmol) of a 1.0 mol*dm−3tetrahydrofuran solution of potassium t-butoxide was added dropwise to the obtained solution and the mixture was stirred at room temperature for 2 hours. Subsequently, diethyl benzylphosphonate and benzaldehyde were added consecutively and the mixture was stirred again for 2 hours. The reaction was terminated by adding about 1 ml of acetic acid, and the solution was washed with water. The solvent was removed by distillation under reduced pressure, and then, the obtained product was purified by reprecipitation using tetrahydrofuran and methanol, to obtain 0.95 g of Polymer Compound (A-17). The number average molecular weight, in terms of polystyrene, measured by gel permeation chromatography (GPC) was 8,500 and the weight average molecular weight was 20,000. The ionizationFN202402483 potential was measured by using a photoelectron spectrometer AC-2 manufactured by Riken Keiki and was found to be 5.20 eV. All the ionization potentials mentioned below are values measured by using the AC-2.

[0185] (Example 1) <Manufacturing of Solar Cell Module 1> First, 3 g of a 15 mass% aqueous dispersion of tin (IV) oxide (manufactured by Alfa Aesar) was dissolved in 7 g of ultrapure water to obtain a liquid. The obtained liquid was applied onto an ITO glass substrate by using a spin coating method and dried at 100°C for 30 minutes to prepare, on a first substrate, a first electrode and a dense electron transport layer containing tin oxide. The conditions were chosen so that the average thickness of the dense layer was 10 nm to 40 nm.

[0186] Afterwards, the laminated body including the glass substrate / ITO / electron transport layer was divided into three cells by laser processing.

[0187] Next, lead(II) iodide (0.5306 g), lead(II) bromide (0.0736 g), methylamine bromide (0.0224 g), and formamidine iodide (0.1876 g) were added to N,N-dimethylformamide (0.8 ml) and dimethylsulfoxide (0.2 ml), and the mixture was stirred and heated at 60°C. The obtained solution was applied onto the porous layer by using a spin coating method, while adding chlorobenzene (0.3 ml) to form a perovskite film. Subsequently, the perovskite film was dried at 150°C during 30 minutes to prepare a perovskite layer. The conditions were chosen so that the average thickness of the perovskite layer was 200 nm to 350 nm.

[0188] Further, a 1 mM solution obtained by dissolving 5-aminopentanoic acid hydroiodide as a compound represented by General Formula (8) in isopropyl alcohol, was applied by using a spin coating method onto the formed perovskite layer to form a passivation layer containing the compound represented by General Formula (8) above.

[0189] Next, 73.6 mg of Polymer Compound (A-17) serving as a hole transport material and 7.4 mg of an additive represented by (B-1) serving as an additive were weighed and dissolved in 3.0 ml of chlorobenzene. The obtained solution was applied by using a spin coating method onto the laminated product obtained in the above-described process to prepare a hole transport layer. The conditions were chosen so that the average thickness of the hole transport layer was 50 nm to 120 nm.

[0190] Next, prior to the formation of the second electrode, laser processing was used to form a through portion a (see reference numeral a in FIG.22) for connection to the ITO layer servingFN202402483 as the first electrode. In addition, laser processing was used to form a through portion for connecting the cells in series. In addition, a through portion b (see reference numeral b in FIG.22) was also formed at an end portion of the first electrode by the procedure described below. FIG.22 is a cross-sectional view of a solar cell in a manufacturing process of Example 1, and the reference numerals and members are similar to the reference numerals and members described in FIG.1.

[0191] <<Formation of Surface Roughness at End Portion of First Electrode>> The glass substrate formed on the ITO until a position where the hole transport layer is formed was mounted on a stage that can move in the in-plane direction. A pulsed laser having a laser wavelength λ = 349 nm was adjusted to have an energy per pulse of 8.0 μJ and a pulse pitch of 50 μm, and light from the laser was perpendicularly incident on the glass substrate on the stage. The area processed in the laser processing was 10 mm x 10 mm. Micropores obtained under these conditions had an average diameter of 35 μm and an average pitch of 50 μm. FIG.23 illustrates a schematic diagram of a pitch and a hole diameter of circular micropores 30. FIG.23 is a top view of an end portion of the first electrode in the manufacturing process of Example 1. In FIG.23, reference numeral 31 indicates the pitch of the circular micropores 30 and reference numeral 32 indicates the diameter of the circular micropores 30.

[0192] Next, a mask was attached to the end portion of the first electrode and to an area positioned between cells when cells are connected. Subsequently, gold was deposited by vacuum vapor deposition onto the hole transport layer and the through portion a to form a second electrode having an average thickness of approximately 60 nm. Simultaneously, gold was also deposited by vacuum vapor deposition on the end portion of the first electrode and a part of the plurality of through portions b to form a metal layer having an average thickness of about 60 nm, to obtain an output terminal.

[0193] Next, as an electrode protection layer, a fluorine compound having a silane structure (manufactured by Harves Co., Ltd., product name: DURASURF DS-5935F130) was applied by spin coating onto the second electrode to form a film having an average thickness of 10 nm, and thus, an electrode protection layer was formed.

[0194] Afterwards, to provide a sealing member, a mask having a width of 1.0 mm from the end portion of the ITO glass substrate and a mask between the cells were subjected to an etching treatment (deletion treatment) by laser processing to form a portion where the sealing member contacts the glass substrate.

[0195] FN202402483 An aluminum PET sheet having a sealing member (manufactured by TESA, pressure- sensitive adhesive A, moisture capture ability: 60 mg / 100 mm2, peeling strength: 5 N / 1 cm or more, drying agent: calcium oxide) in which the sealing member and a second substrate are integrally formed was prepared. The sheet was bonded to the entire surface of the glass substrate by using a vacuum bonding device (manufactured by JOYO ENGINEERING CO., LTD., device name: airbag-type vacuum laminator). The bonded product was heated to 80°C by using a heating laminator and pressed to form a sealing member and a second substrate. Three solar cells 1 having the configuration illustrated in FIG.1 were manufactured. The three obtained solar cells 1 were electrically connected in series to obtain a solar cell module 1 having the configuration illustrated in FIG.3.

[0196] <Evaluation> In the obtained solar cell module 1, the thickness of the metal layer, the surface roughness of the output terminal (arithmetic mean height (Ra) and ten-point average roughness (Rz)), the adhesion of the output terminal, the conversion efficiency, and the maintenance factor after a light resistance test were measured by the procedures described below.

[0197] <Thickness of Metal Layer> To measure the thickness of the metal layer, a shape measurement laser microscope (VK- X100, manufactured by Keyence Corporation) was used. The thickness of the metal layer was measured at any 10 points by using an objective lens at a magnification of 50 times, and the average of the measurements was determined as the thickness of the metal layer.

[0198] <Surface Roughness of Output Terminal> The surface roughness of the surface of the output terminal where the metal layer is provided was measured by using a stylus-type profiling system (DEKTAK XT-E, Bruker Japan).

[0199] <Adhesion of Output Terminal> The adhesion of the output terminal was evaluated by a peeling test described below. Each sample was subjected 10 times to a tape test using cellophane tape. A piece of cellophane tape (manufactured by Nichiban Co., Ltd., "CELLOTAPE" (registered trademark), 24 mm wide, for industrial use) was attached to the surface of the output terminal where the metal layer was provided, and an operation of peeling the cellophane tape off (cellophane tape peeling) was repeated from 1 to 10 times. The samples were evaluated according to the evaluation criteria mentioned below. - Evaluation Criteria - A: The metal layer did not peel off, even after 10 repetitions of the cellophane tape peeling operation.FN202402483 B: The metal layer peeled off after 6 to 10 repetitions of the cellophane tape peeling operation. F: The metal layer peeled off after 1 to 5 repetitions of the cellophane tape peeling operation.

[0200] <Conversion Efficiency (Evaluation of Solar Cell Characteristics)> First, the obtained solar cell module 1 was irradiated with light under conditions including AM 1.5G and 100 mW / cm2by using a solar simulator (SS-80XIL, manufactured by EKO INSTRUMENTS CO., LTD.), and the current-voltage characteristics were measured by using a source meter (KEYSIGHT B2921BL) as an evaluation device. A conversion efficiency η (%) in the solar cell characteristics (initial characteristics) was calculated and evaluated from the obtained current-voltage curve. The results are illustrated in Table 1. Note that a conversion efficiency η of 15% or more is within a range usable in practice, 17% or more is an excellent evaluation result of the conversion efficiency η, 18% or more is an even better evaluation result, and less than 15% is outside the range usable in practice.

[0201] <<Durability (Maintenance Factor of Conversion Efficiency after Light Resistance Test)>> The durability of the obtained solar cell module 1 was evaluated from the maintenance factor of the conversion efficiency after a light resistance test. The conversion efficiency in the initial characteristics is defined as η (%). The solar cell module 1 was subjected to a light resistance test including 500 hours of continuous irradiation (AM 1.5G, 100 mW / cm2), to measure a conversion efficiency ηx (%) after the light resistance test. The maintenance factor of the conversion efficiency was calculated by the following formula: ηx / η (%). Note that a maintenance factor of the conversion efficiency after the light resistance test of 60% or more is within a range usable in practice, 70% or more is an excellent evaluation result, 80% or more is an even better evaluation result, and less than 60% is outside the range usable in practice.

[0202] (Examples 2 to 20) Solar cell modules of Examples 2 to 20 were manufactured and evaluated similarly as in Example 1, except that the arithmetic mean height (Ra), the ten-point average roughness (Rz), the thickness of the metal layer, and the material of the metal layer of the output terminal in Example 1 were changed to the values and materials indicated in Table 1. The results of the evaluation are illustrated in Table 1. Ra and Rz were controlled by choosing the laser output conditions indicated in Table 1.

[0203] (Comparative Examples 1 and 2) Solar cell modules of Comparative Examples 1 and 2 were manufactured and evaluated similarly as in Example 1, except that the arithmetic mean height (Ra), the ten-point averageFN202402483 roughness (Rz), the thickness of the metal layer, and the material of the metal layer of the output terminal in Example 1 were changed to the values and materials indicated in Table 1. The results of the evaluation are illustrated in Table 2.

[0204] (Comparative Example 3) A solar cell module of Comparative Examples 3 was manufactured and evaluated similarly as in Example 1, except that the output terminal in Example 1 did not include a metal layer, and in the end portion of the first electrode in the output terminal, the arithmetic mean height (Ra) was changed to 0.3 [μm] and the ten-point average roughness (Rz) was changed to 0.5 μm. The results of the evaluation are illustrated in Table 2.

[0205] [Table 1] Output terminal Evaluation results Arithmetic Ten-point Maintenance average Thic Material mean height kness of Laser Dot Conversion factor after light (Ra) height metal layer of metal output pitch Adhesion efficiency resistance [μm] (Rz) [μm] [%] [μm] [%] test [μm] layer [%] Example 1 0.15 0.4 0.06 Au 100 50 A 19.0 90 Example 2 0.15 0.55 0.12 Ag 138 50 A 18.7 88 Example 3 0.15 0.45 0.65 Au 113 50 A 19.1 91 Example 4 0.15 0.7 0.15 Ag 175 50 A 18.3 87 Example 5 0.1 0.5 0.06 Au 125 53 A 19.5 93 Example 6 0.25 0.5 0.1 Ag 125 43 A 18.5 85 Example 7 0.3 0.5 0.75 Au 125 40 A 19.2 89 Example 8 0.15 0.5 0.12 Ag 125 50 A 18.2 83 Example 9 0.1 0.4 0.8 Au 100 53 A 19.0 89 Example 10 0.25 0.55 0.1 Ag 138 43 A 18.6 88 Example 11 0.3 0.45 0.8 Au 113 40 A 18.9 90 Example 12 0.15 0.7 0.9 Ag 175 50 A 18.4 86 Example 13 0.1 0.4 0.08 Al 100 5 A 16.2 69 Example 14 0.12 0.45 0.1 Cu 113 52 A 15.9 68 Example 15 0.3 0.75 0.08 Au 188 40 B 17.0 78 Example 16 0.15 0.5 60 Solder 125 50 B 14.9 60FN202402483 Example 17 0.15 0.5 0.01 Al 125 50 A 15.1 63 Example 18 0.15 0.5 0.015 Ag 125 50 A 15.9 65 Example 19 0.15 0.5 30 Ag 125 50 B 15.6 68 Example 20 0.15 0.5 80 Ag 125 50 B 15.2 62

[0206] [Table 2] Output terminal Evaluation results Arithmetic Ten-point Maintenance av Material mean height erage Thickness of Laser Dot Conversion factor after light (Ra) height metal layer of output pitch Adhesion efficiency resistan [μm] ) [μm] m ce (Rz etal layer [%] [μm] [%] test [μm] [%] Comparative Example 1 0.05 0.2 0.08 Au 50 56 F 13.0 53 Comparative Example 2 0.4 0.8 0.12 Ag 200 33 B 12.4 43 Comparative Example 3 - - - - - - - 12.2 33

[0207] As can be seen from Examples 1 to 20 and Comparative Examples 1 to 3, the surface of the output terminal where the metal layer is provided has a surface roughness including an average arithmetic height (Ra) of 0.1 μm or more and 0.3 μm or less and a ten-point average roughness (Rz) of 0.40 μm or more and 0.75 μm or less. Therefore, the metal layer in the output terminal adheres tightly without peeling off, and it was found that a photoelectric conversion element having such a configuration can maintain power generation efficiency even after being exposed to light of high luminous intensity during a long period of time.

[0208] Aspects of the present disclosure include the following, for example. According to a first aspect, a photoelectric conversion element includes a first substrate, a first electrode including a transparent electrode, a photoelectric conversion layer, a second electrode, a sealing member, and an output terminal on the first substrate, in which the output terminal includes an end portion of the first electrode exposed from the sealing member and a metal layer provided on the end portion, a surface of the output terminal where the metal layer is provided has an arithmetic mean height (Ra) of 0.1 μm or more and 0.3 μm or less, and the surface of the output terminal where the metal layer is provided has a ten-point average roughness (Rz) of 0.35 μm or more and 0.75 μm or less. According to a second aspect, in the photoelectric conversion element according to the first aspect, the metal layer has an average thickness of 0.02 μm or more and 30 μm or less.FN202402483 According to a third aspect, in the photoelectric conversion element according to the first aspect or the second aspect, the metal layer includes any one of Au and Ag. According to a fourth aspect, in the photoelectric conversion element according to any one of the first aspect to the third aspect, an average thickness of the second electrode and an average thickness of the metal layer are the same. According to a fifth aspect, in the photoelectric conversion element according to any one of the first aspect to the fourth aspect, the photoelectric conversion layer includes a perovskite compound represented by General Formula (5) below: XαYβZγ... General Formula (5) where, in General Formula (5), a ratio of α:β:γ is 3:1:1, β and γ each independently represent an integer greater than 1, X represents a halogen atom, Y represents an organic compound having an amino group, and Z represents a metal ion. According to a sixth aspect, in the photoelectric conversion element according to any one of the first aspect to the fifth aspect, the photoelectric conversion layer includes at least any one of Sb atoms, Cs atoms, Rb atoms, and K atoms. According to a seventh aspect, the photoelectric conversion element according to any one of the first aspect to the sixth aspect further includes a passivation layer between the photoelectric conversion layer and the second electrode and a hole transport layer between the photoelectric conversion layer and the second electrode, and the passivation layer includes an amine compound different from a compound included in the photoelectric conversion layer. According to an eighth aspect, the photoelectric conversion element according to any one of the first aspect to the seventh aspect further includes an electron transport layer between the first electrode and the photoelectric conversion layer, and the electron transport layer includes at least tin oxide. According to a ninth aspect, a solar cell module includes a plurality of the photoelectric conversion elements according to any one of the first aspect to the eighth aspect that are adjacent to each other, and adjacent ones of the photoelectric conversion elements are electrically connected in series or in parallel. According to a tenth aspect, an electronic device includes the solar cell module according to the ninth aspect, and a device that operates by using electric power generated by photoelectric conversion in the solar cell module. According to an eleventh aspect, a power supply module includes the solar cell module according to the ninth aspect and a power supply integrated circuit.

[0209] According to the photoelectric conversion element according to any one of the first aspect to the eighth aspect, the photoelectric conversion module according to the ninth aspect, theFN202402483 electronic device according to the tenth aspect, and the power supply module according to the eleventh aspect, it is possible to solve the above-described problems in the related art and achieve the object of the present disclosure.

[0210] The above-described embodiments are illustrative and do not limit the present invention. Thus, numerous additional modifications and variations are possible in light of the above teachings. For example, elements and / or features of different illustrative embodiments may be combined with each other and / or substituted for each other within the scope of the present invention.

[0211] This patent application is based on and claims priority to Japanese Patent Application Nos. 2024-032012 and 2024-197893, filed on March 4, 2024 and November 13, 2024, respectively, in the Japan Patent Office, the entire disclosure of each of which is hereby incorporated by reference herein. [Reference Signs List]

[0212] 1 First substrate 2 First electrode 3 Dense electron transport layer (Dense layer) 4 Porous electron transport layer (Porous layer) 5 Perovskite layer 6 Passivation layer 7 Hole transport layer 8 Second electrode 9 Electrode protection layer 10 Sealing Member 11 Second substrate 20 Output terminal 21 End portion of first electrode 22 Metal layer 50, 60 Solar Cell 90, 100 to 104 Solar cell module

Claims

FN202402483 [CLAIMS]

1. A photoelectric conversion element, comprising: a first substrate; a first electrode including a transparent electrode; a photoelectric conversion layer; a second electrode; a sealing member; and an output terminal on the first substrate, the output terminal including: an end portion of the first electrode exposed from the sealing member; and a metal layer on the end portion, wherein a surface of the output terminal where the metal layer is provided has an arithmetic mean height (Ra) of 0.1 μm or more and 0.3 μm or less, and the surface of the output terminal where the metal layer is provided has a ten-point average roughness (Rz) of 0.35 μm or more and 0.75 μm or less.

2. The photoelectric conversion element according to claim 1, wherein the metal layer has an average thickness of 0.02 μm or more and 30 μm or less.

3. The photoelectric conversion element according to claim 1 or 2, wherein the metal layer comprises any one of Au and Ag.

4. The photoelectric conversion element according to any one of claims 1 to 3, wherein an average thickness of the second electrode and an average thickness of the metal layer are the same.

5. The photoelectric conversion element according to any one of claims 1 to 4, wherein the photoelectric conversion layer includes a perovskite compound represented by General Formula (5) below: XαYβZγ... General Formula (5) where, in General Formula (5), a ratio of α:β:γ is 3:1:1, β and γ each independently represent an integer greater than 1, X represents a halogen atom, Y represents an organic compound having an amino group, and Z represents a metal ion.

6. The photoelectric conversion element according to any one of claims 1 to 5, wherein the photoelectric conversion layer includes at least any one of Sb atoms, Cs atoms, Rb atoms, and K atoms.

7. FN202402483 The photoelectric conversion element according to any one of claims 1 to 6, further comprising: a passivation layer between the photoelectric conversion layer and the second electrode, the passivation layer including an amine compound different from a compound included in the photoelectric conversion layer; and a hole transport layer between the photoelectric conversion layer and the second electrode.

8. The photoelectric conversion element according to any one of claims 1 to 7, further comprising: an electron transport layer between the first electrode and the photoelectric conversion layer, the electron transport layer including at least tin oxide.

9. A solar cell module, comprising: a plurality of the photoelectric conversion elements according to any one of claims 1 to 8 that are adjacent to each other, wherein adjacent ones of the photoelectric conversion elements are electrically connected in series or in parallel.

10. An electronic device, comprising: the solar cell module according to claim 9; and a device that operates by using electric power generated by photoelectric conversion in the solar cell module.

11. A power supply module, comprising: the solar cell module according to claim 9; and a power supply integrated circuit.

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