Photoelectric conversion module

Abstract

The purpose of the present invention is to provide a photoelectric conversion element that has a bypass diode function and does not lose flexibility. In order to achieve this purpose, this photoelectric conversion module (10) is characterized by comprising a power generation unit and a bypass unit, each of which comprises a first electrode (12), a photoelectric conversion layer (14), and a second electrode (16), the first electrode (12), the photoelectric conversion layer (14), and the second electrode (16) being laminated in this order, and the first electrode (12), the photoelectric conversion layer (14), and the second electrode (16) being laminated in this order. The power generation unit and the bypass unit each have a diode function, and the directions of the diodes of the power generation unit and the bypass unit are opposite to each other in a plane parallel to a light receiving surface.

Description

Technical Field

[0001] The invention relates to a photoelectric conversion component. Background Art

[0002] In recent years, solar power generation has attracted much attention as a clean energy source, and the development of solar cells is being promoted. As one of them, solar cells using perovskite materials in the light absorption layer are rapidly gaining attention as the next generation of solar cells that can be manufactured at low cost. For example, in non-patent document 1, a solution-type solar cell using perovskite materials in the light absorption layer is reported. In addition, non-patent document 2 also reports that solid-type perovskite solar cells show high efficiency. As a component structure of amorphous silicon solar cells, dye-sensitized solar cells, organic thin-film solar cells, and perovskite solar cells, there are many reports on the shape of connecting cells in series.

[0003] Prior art literature Non-patent literature Non-patent document 1: Journal of the American Chemical Society, 2009, 131, 6050-6051. Non-patent document 2: Science, 2012, 388, 643-647. Patent Literature Patent Document 1: Japanese Patent Application Laid-Open No. 2000-277785 Summary of the invention

[0004] Technical problem to be solved by the invention However, when a portion of a solar cell is shaded, a difference in the generated current occurs, and in the case of a series connection, the amount of power generated is severely reduced. In addition, since a large reverse bias voltage is applied to the shaded portion of the cell based on the load state of the solar cell module, the cell overheats due to a phenomenon called a hot spot. When a hot spot occurs, it may cause damage to the cell depending on the circumstances. Therefore, in order to avoid the hot spot phenomenon, a method of providing a bypass diode to prevent the cell from overheating has been proposed (Patent Document 1). However, when a conventional bypass diode is installed on a solar cell, the thickness of the solar cell increases, hindering the flexibility that is a characteristic of a thin-film solar cell.

[0005] Therefore, an object of the present invention is to provide a photoelectric conversion component having a bypass diode function without losing flexibility.

[0006] Technical solutions for solving technical problems In order to achieve the above object, the photoelectric conversion component of the present invention is characterized in that: It includes power generation section and bypass section. The power generation unit and the bypass unit respectively include a first electrode, a photoelectric conversion layer, and a second electrode, wherein the first electrode, the photoelectric conversion layer, and the second electrode are sequentially stacked. The power generation unit and the bypass unit each have a diode function. In a plane parallel to the light receiving surface, the diodes of the power generation section and the diodes of the bypass section are oriented in opposite directions to each other.

[0007] Effects of the Invention According to the present invention, it is possible to provide a photoelectric conversion element having a bypass diode function without losing flexibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 This is a cross-sectional view showing an example of a forward-type structure of the photoelectric conversion element of the present invention.

[0009] Figure 2 This is a cross-sectional view showing an example of an inverted structure of the photoelectric conversion element of the present invention.

[0010] Figure 3A This is a pattern diagram of the photoelectric conversion element in Example 1 of the present invention as viewed from the opposite side of the support.

[0011] Figure 3B This is a pattern diagram of the photoelectric conversion element in Example 1 of the present invention as viewed from the support surface.

[0012] Figure 4 3 is a cross-sectional view taken along line AA of FIG. 3 showing the connection of the bypass portion according to the embodiment of the present invention.

[0013] Figure 5 3 is a BB cross-sectional view showing the connection of the power generation section according to the embodiment of the present invention.

[0014] Figure 6 An equivalent circuit of an embodiment of the present invention is shown.

[0015] Figure 7 1 is a diagram showing a pattern of a first electrode according to Example 1 of the present invention.

[0016] Figure 8 1 is a diagram showing a pattern of a photoelectric conversion layer on a first electrode according to Example 1 of the present invention.

[0017] Fig. 9 1 is a diagram showing a pattern of a second electrode on a photoelectric conversion layer according to Example 1 of the present invention.

[0018] Fig.10 This is a diagram showing a mask mounted on the light-receiving surface of the photoelectric conversion element according to Example 1 of the present invention.

[0019] Fig.11 This is a diagram showing a state where one cell of the photoelectric conversion module according to Example 1 of the present invention is shielded from light.

[0020] Fig.12 2 is a diagram showing a pattern of a first electrode of a comparative example.

[0021] Fig.13 1 is a diagram showing a pattern of a photoelectric conversion layer on a first electrode of a comparative example.

[0022] Fig.14 1 is a diagram showing a pattern of a second electrode on a photoelectric conversion layer of a comparative example.

[0023] Fig.15 This is a diagram showing a photoelectric conversion element of a comparative example in which a mask is attached to the light-receiving surface.

[0024] Fig.16 This is a diagram showing a state where one cell of a photoelectric conversion module of a comparative example is shielded from light.

[0025] Fig.17 This is a diagram showing a pattern of a first electrode according to Example 2 of the present invention.

[0026] Fig.18 This is a diagram showing a pattern of a photoelectric conversion layer according to Example 2 of the present invention.

[0027] Fig.19 1 is a diagram showing a pattern of a second electrode according to Example 2 of the present invention.

[0028] Fig. 20 This is a diagram showing a photoelectric conversion element according to Example 2 of the present invention in which a mask is mounted on the light-receiving surface.

[0029] Fig.21 This is a diagram showing a state where one cell of the photoelectric conversion module according to Example 2 of the present invention is shielded from light. DETAILED DESCRIPTION

[0030] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following description.

[0031] In the present invention, unless otherwise specified, "mass %" and "weight %" may be interchanged, and "mass parts" and "weight parts" may be interchanged.

[0032] In the present invention, “on” or “on the surface of” may be a state of being in direct contact with on or on the surface of, or may be a state of sandwiching other components or the like.

[0033] The photoelectric conversion component of the present invention (hereinafter, sometimes referred to as the "component"), as described above, includes, for example, a power generation section and a bypass section, and the power generation section and the bypass section respectively include a first electrode, a photoelectric conversion layer, and a second electrode, and the first electrode, the photoelectric conversion layer, and the second electrode are stacked in the above order. In the photoelectric conversion component of the present invention, for example, the power generation section and the bypass section may each further include a support body. Here, other components other than the first electrode, the photoelectric conversion layer, the second electrode, and the support body may also be included between the first electrode and the photoelectric conversion layer (hereinafter, referred to as "other components"). In addition, other components may also be included between the photoelectric conversion layer and the second electrode. Examples of the above-mentioned other components include an electron transport layer, a hole transport layer, and the like. The photoelectric conversion component of the present invention may, for example, be Figure 1 The forward structure described in Figure 2 Any of the reverse structures described in the . The forward structure is composed of a support, a first electrode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a second electrode in order from the side of the support on which light is incident. On the other hand, the reverse structure is composed of a support, a first electrode, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a second electrode in order from the side of the support on which light is incident.

[0034] Furthermore, in the photoelectric conversion component of the present invention, for example, in the power generation section and the bypass section, at least one of the first electrode, the photoelectric conversion layer, and the second electrode may be formed of the same material as each other. That is, the power generation section and the bypass section may share at least one of the first electrode, the photoelectric conversion layer, and the second electrode with each other. Furthermore, in the case where the photoelectric conversion component of the present invention includes the support body, for example, in the power generation section and the bypass section, at least one of the support body, the first electrode, the photoelectric conversion layer, and the second electrode may be formed of the same material as each other. That is, the power generation section and the bypass section may share at least one of the support body, the first electrode, the photoelectric conversion layer, and the second electrode with each other. For example, Figure 8 As shown in FIG. 1 , the photoelectric conversion layer 14 in the power generation section and the bypass section can be formed of the same material. Fig. 9 As shown, the second electrodes in the power generation section and the bypass section may be formed of the same material.

[0035] <About Series Components> The existing photoelectric conversion components are connected in series to suppress the current density flowing through the transparent electrode to a low level, thereby reducing the influence of the resistance of the transparent electrode. In the existing photoelectric conversion components, if a shadow appears on a part of the component during power generation, an imbalance in the generated current occurs, and sometimes the output reduction ratio is greater than the area ratio of the shadow. In addition, when the system is connected in parallel, depending on the load state, the battery that becomes the shadow is sometimes applied with a reverse bias. In this case, if there are a few defects, it is possible to produce a so-called hot spot, causing greater damage to the photoelectric conversion component. As a solution to date, a method of clamping an element such as an ohmic resistor in parallel in each battery has been proposed. However, in this case, if the resistance is small, the leakage becomes larger, and the original output is reduced; if the resistance is large, there is a technical problem that the battery that becomes the shadow is applied with a reverse bias voltage. In order to solve this problem, a method of installing a bypass diode has been studied. The commonly used bypass diode refers to a diode assembled in the photoelectric conversion component, which is connected in parallel with the series circuit of the battery to bypass the circuit that cannot generate electricity due to the influence of shadows, failures, etc. In the present invention, in each battery, a diode in the opposite direction to the current flowing through the battery is provided on the same plane where the battery exists. That is, in the photoelectric conversion component of the present invention, in a plane parallel to the light receiving surface, the diodes of the power generation part and the bypass part are oriented in opposite directions to each other. In addition, in the process of studying the present invention, the inventor of the present invention has obtained an invention having the same function as the bypass diode by changing the pattern shape of the component without the need for additional materials and processes.

[0036] In the present invention, the pattern shape of the bypass portion needs to have a diode in the opposite direction to the power generation portion. A diode is a semiconductor that allows current to flow in the forward direction of an applied voltage but does not allow current to flow in the reverse direction. In the present invention, the bypass portion (a portion having a bypass diode function) allows current to flow in the opposite direction to the power generation portion (a portion that contributes to power generation). In addition, the bypass portion in the present invention allows current to flow in the reverse direction by incident light and generates electricity. Figure 4 and Figure 5 2 shows the flow of current in the bypass section and the power generation section. When light is incident on the bypass section, Figure 4 and Figure 5 As shown, in the bypass section, the current flows in the opposite direction to the power generation section, and the current of the battery is offset. Therefore, it is preferred that the area of ​​the bypass section is smaller than that of the power generation section. In addition, a more preferred state is to shield the bypass section so that light does not enter. Therefore, the bypass section can be arranged in a frame supporting the photoelectric conversion component of the present invention to stably shield light.

[0037] The photoelectric conversion element of the present invention has the same function as a conventional semiconductor pn diode (to be precise, a pin diode) by sandwiching a semiconductor layer such as perovskite with an electron transport layer and a hole transport layer. In a dark place, the electrode connected to the electron transport layer side is set to zero potential, and the diode becomes as follows: if a positive voltage is applied to the electrode connected to the hole transport layer side, it becomes a forward direction and current flows; if a negative voltage is applied, it becomes a reverse direction and current is difficult to flow.

[0038] The larger the cell area in the photoelectric conversion module is, the more conducive it is to power generation, but excessive heat caused by the current flowing into the bypass section must be avoided. Therefore, the area ratio S (Sb / Sp) of the entire area of ​​the surface parallel to the light-receiving surface in the power generation section (Sp) and the entire area of ​​the surface parallel to the light-receiving surface in the bypass section (Sb) is preferably 0.001 to 0.2, and more preferably 0.01 to 0.15.

[0039] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[0040] [Photoelectric conversion components] The photoelectric conversion component of the present invention is as described above, for example, it can be a forward structure in which the first electrode, the electron transport layer, the photoelectric conversion layer, the hole transport layer and the second electrode are stacked in sequence, or any of the reverse structures in which the first electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer and the second electrode are stacked in sequence. The photoelectric conversion component of the present invention may, for example, include or not include other constituent elements other than the first electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer and the second electrode. For example, between the first electrode and the electron transport layer or the hole transport layer, there may be no other constituent elements and they are directly stacked, or there may be other constituent elements between them. Similarly, between the electron transport layer or the hole transport layer and the photoelectric conversion layer, there may be no other constituent elements and they are directly stacked, or there may be other constituent elements between them. Similarly, between the photoelectric conversion layer and the hole transport layer or the electron transport layer, there may be no other constituent elements and they are directly stacked, or there may be other constituent elements between them. Similarly, the hole transport layer or the electron transport layer and the second electrode may be directly stacked without any other components being present, or may have any other components present therebetween.

[0041] The following is a more specific description of the configuration and components of the photoelectric conversion module of the present invention by way of example. However, the photoelectric conversion module of the present invention is not limited to the following examples. It should be noted that the following description is mainly based on the case where the photoelectric conversion module of the present invention is a solar cell.

[0042] Figure 1 and Figure 2 Each shows an example of the structure of the photoelectric conversion module of the present invention. In addition, for the convenience of description, Figure 1 and Figure 2 The description is schematically presented with appropriate omissions, exaggerations, etc. Figure 1 As shown, in the photoelectric conversion element 10, a first electrode 12, an electron transport layer 13, a photoelectric conversion layer 14, a hole transport layer 15, and a second electrode 16 are sequentially stacked on a support (also called a substrate, base material, etc.) 11. Figure 2 As shown, in the photoelectric conversion element 20 , a first electrode 22 , an electron transport layer 23 , a photoelectric conversion layer 24 , a hole transport layer 25 and a second electrode 26 are sequentially stacked on a support (also called a substrate, base material, etc.) 21 .

[0043] [Supporting bodies 11, 21] The supports 11 and 21 are not particularly limited, and for example, a substrate that can be used for a conventional photovoltaic cell or other photovoltaic conversion component can be appropriately used. Examples of the substrate include glass, a plastic plate including a plastic film, a plastic film, an inorganic crystal, and the like. The thickness of the substrate is not particularly limited, and for example, it is a thickness that does not hinder the flexibility of the photovoltaic conversion component of the present invention. In the present invention, "flexibility" means being soft to the extent that, for example, after stress is applied to the photovoltaic conversion component of the present invention, no breakage or cracking occurs, and the performance of the photovoltaic conversion component is not affected. When the substrate is glass, for example, the thickness is preferably 0.5 to 1.1 mm. When the substrate is a plastic film, for example, the thickness is preferably 50 to 60 mm. μ m~125 μ m. In addition, substrates having at least one of a metal film, a semiconductor film, a conductive film, and an insulating film formed on a part or all of the surface of these substrates can also be suitably used as the support 11, 21. The size, thickness, etc. of the support 11, 21 are not particularly limited, and for example, may be the same as or based on a conventional photoelectric conversion component such as a solar cell.

[0044] [First electrodes 12, 22] The first electrodes 12 and 22 are layers that support the electron transport layer 13 and the hole transport layer 25 and have the function of extracting electrons or holes from the photoelectric conversion layers 14 and 24. The first electrode 12 is a layer that functions as an anode (negative electrode), and the electrode 22 is a layer that functions as a cathode (positive electrode).

[0045] The first electrodes 12 and 22 can be formed directly on the support bodies 11 and 21, for example. The first electrodes 12 and 22 can be transparent electrodes formed by a conductor, for example. As the transparent electrode, there is no particular limitation, for example, tin-doped indium oxide (ITO) film, impurity-doped indium oxide (In2O3) film, impurity-doped zinc oxide (ZnO) film, fluorine-doped tin dioxide (FTO) film, a laminated film formed by laminating two or more of them, gold, silver, copper, aluminum, tungsten, titanium, chromium, nickel and cobalt, etc. They can be used alone or in a mixture of two or more, and can be a single layer or a laminate. In addition, these films can also be films that function as diffusion prevention layers, for example. The thickness of the first electrodes 12 and 22 is not particularly limited, for example, it is preferably adjusted in a manner that the sheet resistance is 5 to 15Ω / □ (per unit area). The method for forming the first electrodes 12 and 22 is not particularly limited, for example, it can be obtained by a known film forming method according to the forming material. In addition, the shape of the first electrodes 12 and 22 is not particularly limited, for example, it can be a film or a grid-like shape such as a mesh. The method for forming the first electrodes 12 and 22 on the support 11 and 21 is not particularly limited, for example, it can be a known method, for example, preferably vacuum film forming such as vacuum evaporation and sputtering. In addition, the first electrodes 12 and 22 can use patterned electrodes. As a patterning method, there is no particular limitation, for example, a method of laser immersion in an etching solution, a method of patterning using a mask during vacuum film forming, etc., can be any method in the present invention. In addition, for the purpose of reducing the resistance value, the first electrodes 12 and 22 can also be used in combination with metal wiring, etc. As the material of the metal wiring (metal wire), there is no particular limitation, for example, aluminum, copper, silver, gold, platinum, nickel, etc. can be cited. The metal wire can be formed on the first substrate, for example, by evaporation, sputtering, crimping, etc., and a layer of ITO or FTO is set thereon, or it can be set on ITO and FTO and used in combination.

[0046] [Hole transport layers 15, 25] The hole transport layer 15, 25 is a layer having the function of transporting charges. The hole transport layer 15, 25 can use, for example, a conductor, a semiconductor, an organic hole transport material, etc. The organic hole transport material can function as a hole transport material that receives holes from the perovskite layer (photoelectric conversion layer) 14, 24 and transports holes. As the conductor and the semiconductor, an inorganic hole transport material or the organic hole transport material is used. As the inorganic hole transport material, for example, compound semiconductors containing monovalent copper such as CuI, CuInSe2, and CuS; compounds containing metals other than copper such as GaP, NiO, CiO, FeO, Bi2O3, MoO3, and Cr2O. Among them, from the viewpoint of more effectively receiving only holes and obtaining a higher hole mobility, a semiconductor containing monovalent copper is preferred, and CuI or CuSCN is more preferred. Examples of the organic hole transport material include polythiophene derivatives such as poly-3-hexylthiophene (P3HT) and polyethylene dioxythiophene (PEDOT); fluorene derivatives such as 2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamino)-9,9′-spirobifluorene (Spiro-OMeTAD); carbazole derivatives such as polyvinylcarbazole; triphenylamine derivatives such as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA); diphenylamine derivatives; polysilane derivatives; polyaniline derivatives, etc. Among them, from the viewpoint of more effectively receiving only holes and obtaining higher hole mobility, triphenylamine derivatives, fluorene derivatives, etc. are preferred, and PTAA, Spiro-OMeTAD, etc. are more preferred.

[0047] Furthermore, in order to further improve the hole transport properties, the organic hole transport material may also include, for example, lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), silver bis(trifluoromethylsulfonyl)imide, zinc bis(trifluoromethylsulfonyl)imide, ammonium bis(trifluoromethanesulfonyl)imide, lithium bis(nonafluorobutanesulfonyl)imide, sodium bis(nonafluorobutanesulfonyl)imide, lithium nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide, nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide, Oxidants such as potassium fluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide, nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonamide, lithium N,N-hexafluoro-1,3-disulfonylimide, sodium N,N-hexafluoro-1,3-disulfonylimide, trifluoromethylsulfonyloxysilver, NOSbF6, SbCl5, SbF5, tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridinium)cobalt(III)tris[bis(trifluoromethane)sulfonylimide]. In addition, the hole transport layers 15 and 25 may also contain basic compounds such as tert-butylpyridine (TBP), 2-methylpyridine, and 2,6-lutidine. The contents of the oxidant and the basic compound may be, for example, the amounts conventionally used. From the viewpoint of more effectively receiving only holes and obtaining a higher hole mobility, the thickness of the hole transport layer 15, 25 is preferably 1 to 500 nm, and more preferably 2 to 300 nm. The method of forming the hole transport layer 15, 25 is preferably carried out in a dry atmosphere. For example, it is preferred to apply (spin coating, etc.) a solution containing an organic hole transport material on the perovskite layer (light absorption layer) in a dry atmosphere and heat it at 30 to 180°C, particularly 100 to 150°C.

[0048] In addition, as the hole transport layer 25 in the inverted structure, for example, a hole transport compound that forms a monomolecular layer (hereinafter also referred to as a "monomolecule hole transport compound") can also be used. As the monomolecule hole transport compound, for example, it is preferred to have an anchor that is chemically bonded to ITO or the like as a transparent electrode in the inverted structure. As the anchor, for example, a phosphonic acid group (-P=O(OH)2), a carboxyl group (-COOH), a sulfonic group (-SO3H), a boric acid group (-B(OH)2), a trihalide silicon group (-SiX3, wherein X is a halogen atom), or a trialkoxy silicon group (-Si(OR)3, wherein R is an alkyl group) can be cited. Among them, a phosphonic acid group, a trihalide silicon group, and a trialkoxy silicon group are particularly preferred.

[0049] There is no particular limitation on the method for forming the hole transport layer 25 using the monomolecular hole transport material. For example, the hole transport layer 25 can be formed by adsorbing the monomolecular hole transport compound on the first electrode 22 to form a monomolecular layer. There is no particular limitation on the method for adsorbing the monomolecular hole transport compound on the first electrode 22 to form a monomolecular layer. For example, the monomolecular hole transport compound is dissolved in a solvent and brought into contact with the first electrode 22 to bond. There is no particular limitation on the bonding between the monomolecular hole transport compound and the first electrode 22. It can be a physical bond or a chemical bond. There is no particular limitation on the type of the bond. For example, it can be any one of a hydrogen bond, an ester bond, a chelate bond, etc. There is no particular limitation on the solvent used to dissolve the monomolecular hole transport compound. For example, it can be one of water and an organic solvent, or both. More specifically, as the solvent, for example, water; alcohols such as methanol, ethanol, and 2-propanol; ethers such as diethyl ether and diisopropyl ether; ketones such as acetone and methyl isobutyl ketone; ethyl acetate, isobutyl acetate, γ -Butyrolactone and other esters; tetrahydrofuran, thiophene and other heterocyclics; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and other amides; dimethyl sulfoxide and other sulfoxides; diethyl sulfone, cyclopentane and other sulfones; acetonitrile, 3-methoxypropionitrile and other nitriles; benzene, toluene, chlorobenzene and other aromatic compounds; dichloromethane, chloroform and other halogenated solvents; chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons and other fluorinated solvents, which can be used alone or in combination of two or more.

[0050] There is no particular limitation on the specific method for adsorbing the monomolecular hole transport compound on the first electrode 22 to form a monolayer, and examples thereof include known methods such as dipping, spraying, spin coating, and bar coating. The temperature during adsorption is not particularly limited, and is preferably -20°C to 100°C, and more preferably 0°C to 50°C. The adsorption time is not particularly limited, and is preferably 1 second to 48 hours, and more preferably 10 seconds to 1 hour. In addition, after the adsorption treatment, for example, washing may be performed or may not be performed. The washing method is not particularly limited, and for example, a known method may be used appropriately.

[0051] After the adsorption treatment or the cleaning, a heat treatment may or may not be performed. The temperature of the heat treatment is preferably 50° C. to 150° C., more preferably 70° C. to 120° C. The heat treatment time is preferably 1 second to 48 hours, more preferably 10 seconds to 1 hour. In addition, the heat treatment may be performed, for example, in the atmosphere or in a vacuum.

[0052] When the monomolecular hole transport compound is adsorbed on the first electrode 22, for example, a co-adsorbent may be used or not. The co-adsorbent may be added when the monomolecular hole transport compound alone cannot completely cover the electrode surface, or may be added for the purpose of inhibiting the interaction between the monomolecular hole transport compounds.

[0053] The co-adsorbent is not particularly limited, and examples thereof include phosphonic acid compounds such as n-butylphosphonic acid, n-hexylphosphonic acid, n-decylphosphonic acid, n-octadecylphosphonic acid, 2-ethylhexylphosphonic acid, methoxymethylphosphonic acid, 3-acryloyloxypropylphosphonic acid, 11-hydroxyundecylphosphonic acid, 1H,1H,2H,2H-perfluorophosphonic acid, acetic acid, propionic acid, isobutyric acid, nonanoic acid, fluoroacetic acid, α -chloropropionic acid, glyoxylic acid, chenodeoxycholic acid and the like, and these may be used alone or in combination of two or more.

[0054] The method for adsorbing the co-adsorbent on the first electrode 22 is not particularly limited, and it is preferably a method of adsorbing after being dissolved in a solvent, similarly to the monomolecular hole transport compound. The solvent is also not particularly limited, and for example, it may be the same as the solvent exemplified for the monomolecular hole transport compound. In addition, after the monomolecular hole transport compound is adsorbed on the substrate once, the first electrode 22 may be immersed in a solvent in which the co-adsorbent is dissolved to adsorb the co-adsorbent, or a substance obtained by mixing the co-adsorbent and the monomolecular hole transport compound and dissolving them in an organic solvent may be used.

[0055] [Electron transport layer 13, 23] The material used for the electron transport layers 13 and 23 is not particularly limited and can be appropriately selected according to the purpose, but is preferably a semiconductor material. The semiconductor material is not particularly limited and a known semiconductor material can be used, for example, a single semiconductor, a compound semiconductor, an organic n-type semiconductor, etc.

[0056] The single semiconductor is not particularly limited, and examples thereof include silicon and germanium.

[0057] The compound semiconductor is not particularly limited, and examples thereof include metal chalcogenides, specifically oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum, etc.; sulfides of cadmium, zinc, lead, silver, antimony, bismuth, etc.; selenides of cadmium, lead, etc.; tellurides of cadmium, etc.; and other compound semiconductors include phosphides of zinc, gallium, indium, cadmium, etc., gallium arsenide, copper-indium-selenide, copper-indium-sulfide, etc.

[0058] The organic n-type semiconductor is not particularly limited, and examples thereof include perylene tetracarboxylic anhydride, perylene tetracarboxylic imide compounds, naphthalene diimide-bithiophene copolymers, benzodiimidazolebenzophenanthroline polymers, C 60 , C 70 、PCBM([6,6]-phenyl-C 61 -Butyric acid methyl ester) and other fullerene compounds (Japanese: フレーラン compounds), carbonyl bridge-bithiazole compounds, ALq3 (tris (8-hydroxyquinoline) aluminum), triphenylene bipyridine compounds, silole compounds, oxadiazole compounds, etc.

[0059] Among the materials described for the electron transport layers 13, 23, organic n-type semiconductors are particularly preferred.

[0060] The materials used to form the electron transport layers 13 and 23 may be used alone or in combination of two or more. The crystal form of the semiconductor material is not particularly limited and can be appropriately selected according to the purpose, and may be single crystal, polycrystalline, or amorphous.

[0061] The film thickness of the electron transport layers 13 and 23 is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 nm to 1000 nm, and more preferably 10 nm to 700 nm.

[0062] There is no particular limitation on the method for forming the electron transport layers 13 and 23, and it can be appropriately selected according to the purpose. For example, a method of forming a thin film in a vacuum (vacuum film forming method), a wet film forming method, etc. can be cited. As a vacuum film forming method, for example, sputtering, pulsed laser deposition (PLD method), ion beam sputtering, ion assisted method, ion plating method, vacuum evaporation method, atomic layer deposition (ALD method), chemical vapor deposition (CVD method), etc. can be cited. As a wet film forming method, a method of forming by coating a solvent in which an electron transport material is dissolved, and a sol-gel method in the case of an oxide semiconductor can be cited. The sol-gel method is a method in which a solution is subjected to chemical reactions such as hydrolysis, polymerization, and condensation to produce a gel, and then densification is promoted by heat treatment. When the sol-gel method is used, the coating method of the sol solution is not particularly limited and can be appropriately selected according to the purpose. For example, dipping, spraying, wire rod, spin coating, roll coating, knife coating, and gravure coating can be mentioned. In addition, as a wet printing method, relief printing, offset printing, gravure, gravure, rubber printing, screen printing, etc. can be mentioned. In addition, the temperature during the heat treatment after applying the sol solution is preferably 80° C. or more, and more preferably 100° C. or more.

[0063] In the case of the inverted structure, after the electron transport layer 23 is formed, an electron injection layer (hole blocking layer) may be formed between the electron transport layer 23 and the second electrode 26. As a material for the electron injection layer, BCP (bathocuproine) may be cited, and cesium may also be doped. The electron injection layer is preferably 1 nm to 100 nm, and more preferably 3 nm to 20 nm.

[0064] [Photoelectric conversion layers 14, 24] The photoelectric conversion layers 14 and 24 are not particularly limited, and may be the same as those used in conventional photoelectric conversion components such as solar cells. The photoelectric conversion layers 14 and 24 may include, for example, a perovskite compound. The perovskite compound may be, for example, a compound represented by the following chemical formula (I).

[0065] X α Y β Z γ (I) In the chemical formula (I), α : β : γ The ratio is, for example, 3:1:1, X represents a halogen ion, Y represents a monovalent cation, and Z represents a divalent cation. The perovskite layer is preferably arranged adjacent to the electron transport layer. α : β : γ The ratio is, for example, 3:1.05:0.95, 3:0.95:1.05, and is not necessarily 3:1:1. α : β : γ The ratio is, for example, 3:(0.95-1.05):(0.95-1.05).

[0066] X in the chemical formula (I) is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include halogen ions such as chlorine, bromine, and iodine. These may be used alone or in combination of two or more.

[0067] As Y in the chemical formula (I), for example, alkylamine compound ions (organic compounds having amino groups) such as methylammonium cations, ethylammonium cations, n-butylammonium cations, and formamidine cations, and alkali metal ions such as cesium cations, potassium cations, and rubidium cations, but not limited to organic ions, can be cited. Alkylamine compound ions and alkali metal ions can be used alone or in combination of two or more. In addition, organic (alkylamine compound ions) and inorganic (alkali metal ions) can also be used in combination, for example, cesium ions and formamidine can be used in combination.

[0068] There is no particular limitation on Z in the chemical formula (I), and Z can be appropriately selected according to the purpose, and examples thereof include divalent metal ions such as lead, indium, antimony, tin, copper, bismuth, and germanium. These may be used alone or in combination of two or more. Lead is particularly preferred, and a combination of lead and tin is particularly preferred.

[0069] As described above, the photoelectric conversion layers 14 and 24 may be formed of a perovskite compound. The method for forming such a perovskite layer is not particularly limited and can be appropriately selected according to the purpose, for example, a method of applying a solution in which a metal halide and an alkylamine halide are dissolved or dispersed and then drying the solution.

[0070] Examples of methods for forming a perovskite layer include a two-step precipitation method in which a solution in which a metal halide is dissolved or dispersed is applied and dried, and then the solution is immersed in a solution in which an alkylamine halide is dissolved to form a perovskite compound.

[0071] As a method for forming a perovskite layer, in addition to the above, for example, a method of applying a solution in which a metal halide and an alkylamine halide are dissolved or dispersed, and adding a poor solvent (solvent with low solubility) for the perovskite compound to cause crystallization, etc. Also, as a method for forming a perovskite layer, in addition to the above, for example, a method of vapor-depositing a metal halide in a gas filled with methylamine, etc., etc. can be mentioned.

[0072] As a method for forming a perovskite layer, a method in which a solution in which a metal halide and an alkylamine halide are dissolved or dispersed is applied while a poor solvent for the perovskite compound is added to cause crystallization. The method for applying these solutions is not particularly limited and can be appropriately selected according to the purpose. For example, there can be immersion method, spin coating method, spray coating method, dip method, roller method, air knife method, etc. In addition, as a method for applying the solution, for example, it can be a method of precipitating it in a supercritical fluid such as carbon dioxide. As the above-mentioned method of adding a poor solvent to cause crystallization, the poor solvent used can be, for example, hydrocarbons such as n-hexane and n-octane; alcohols such as methanol, ethanol, and 2-propanol; ethers such as diethyl ether and diisopropyl ether; ketones such as acetone and methyl isobutyl ketone; ethyl acetate, isobutyl acetate, γ -Butyrolactone and other esters; acetonitrile, 3-methoxypropionitrile and other nitriles; benzene, toluene, chlorobenzene and other aromatic hydrocarbon compounds; dichloromethane, chloroform and other halogenated solvents; chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons and other fluorinated solvents.

[0073] As a method for forming a perovskite layer, for example, a process for removing the solvent after forming the perovskite layer (solvent removal process) or a process for configuring perovskite crystals can be further performed. As the solvent removal process and the crystal configuration process, for example, a method of blowing dry air, a method of heating using a hot plate, an oven, etc., a method of vacuum drying, etc. can be cited. As the heating temperature, for example, it is preferably 50 to 200°C, and more preferably 70 to 180°C. As the heating time, for example, it is preferably 1 to 150 minutes, and more preferably 5 to 60 minutes. In addition, the thickness of the photoelectric conversion layers 14 and 24 is not particularly limited. From the viewpoint of further suppressing performance degradation caused by defects or peeling, for example, it is preferably 50 to 1500nm, and more preferably 200 to 1000nm.

[0074] The method for forming the perovskite layer may include, for example, a surface treatment step using a salt formed of one or more cations and one or more anions. Examples of the cation include inorganic cations such as lithium, sodium, potassium, rubidium, cesium, magnesium, and calcium; ammonium cations; methylamine, ethylamine, n-butylamine, isopentylamine, neopentylamine, formamidine, acetamidine, benzylamine, 2-phenylethylamine, 2-(4-methoxyphenyl)ethylamine, 4-fluorobenzylamine, 2-(4-fluorophenyl)ethylamine, 1,4-phenylenediamine, 5-aminopentanoic acid, methylamine (methamine), ethylenediamine, p-phenylenediamine, m-phenylenediamine, 1,2-adamantanediamine, 1 ,3-adamantanediamine, N,N-dimethylethylenediamine, 1,3-diaminopropane, 1,4-diazabicyclo[2.2.2]octane, guanidine, aniline, pyrrole, imidazole, 1-ethylimidazole, 2-ethylimidazole, benzimidazole, morpholine, pyrrolidine, pyrazole, triazole, carbazole and other organic compounds having amino groups; pyridine, pyrazine, pyridazine, pyrimidine, quinoline, isoquinoline, phenanthroline, 2,2′-bipyridine, 4,4′-bipyridine and other nitrogen-containing heterocyclic rings. Examples of the anions include halogen ions such as fluoride ion, chloride ion, bromide ion, iodide ion, carboxylate ions such as formate ion and acetate ion, isocyanate ion, thiocyanate ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonimide ion, and the like.

[0075] The salt composed of the cation and the anion is preferably dissolved in one or more solvents. Examples of the solvent include alcohols such as isopropyl alcohol (2-propanol), ethanol (EtOH), methanol (MeOH), and butanol; nitriles such as acetonitrile and propionitrile; aromatic solvents such as toluene, chlorobenzene, and 1,2-dichlorobenzene. The solvents may be used alone or in combination of two or more.

[0076] The surface treatment process is carried out by applying a solution in which the salt is dissolved on the formed perovskite layer and drying it. There is no particular limitation on the method for applying the solution, and it can be appropriately selected according to the purpose, for example, dipping method, spin coating method, spray coating method, dip method, roller method, air knife method, etc. can be cited. In addition, heat treatment can also be performed after coating. In the case of heating, the heating temperature is preferably 50 to 200°C, and more preferably 70 to 180°C. As for the heating time, for example, it is preferably 1 to 150 minutes, and more preferably 5 to 60 minutes. There is no particular limitation on the film thickness of the solution applied.

[0077] [Second electrodes 16, 26] The second electrode 16 , 26 (which may be a back electrode, for example) is, for example, a layer having a function of extracting holes or electrons from the photoelectric conversion layer 14 , 24 via a hole transport layer or an electron transport layer.

[0078] The second electrode 16, 26 can be formed directly on the hole transport layer 15 in the case of the forward structure, or directly on the electron transport layer 23 in the case of the reverse structure. In addition, the material of the second electrodes 16, 26 is not particularly limited, for example, the same material as the first electrodes 12, 22 can be used. As the second electrodes 16, 26, there are no particular restrictions on their shape, structure, and size, and they can be appropriately selected according to the purpose. As the material of the second electrodes 16, 26, for example, metals, carbon compounds, conductive metal oxides, conductive polymers, etc. can be cited. As the metal, for example, platinum, gold, silver, copper, aluminum, etc. can be cited. As the carbon compound, for example, graphite, fullerene, carbon nanotubes, graphene, etc. can be cited. As the conductive metal oxide, for example, ITO, IZO, FTO, ATO, etc. can be cited. As the conductive polymer, for example, polythiophene, polyaniline, etc. can be cited. In addition, the material used to form the second electrodes 16, 26 can be used alone, or two or more can be used in combination.

[0079] The second electrodes 16 and 26 can be formed by appropriately applying coating, lamination, vacuum deposition, CVD, sputtering, lamination or the like on the hole transport layer 15 or the electron transport layer 23 depending on the type of material used and the type of the hole transport layer 15 or the electron transport layer 23 .

[0080] In addition, in the photoelectric conversion component of the present invention, it is preferred that at least one of the first electrode 12 or 22 and the second electrode 16 or 26 is substantially transparent. When using the photoelectric conversion component of the present invention, it is preferred to make the electrode transparent so that the incident light is incident from the electrode side. In this case, the back electrode (the electrode on the opposite side of the transparent electrode, such as the second electrode) is preferably made of a material that reflects light, preferably glass, plastic, metal film, etc., on which a metal or conductive oxide is evaporated. In addition, it is also an effective means to provide an anti-reflection layer on the electrode on the incident light side.

[0081] Furthermore, the structure of the photoelectric conversion element of the present invention is not limited to Figure 1 or Figure 2 For example, the support body 11 can be arranged at Figure 1 The opposite side ( Figure 1 On the upper side of the second electrode 16 in the support 11), the second electrode 16, the electron transport layer 15, the photoelectric conversion layer 14, the hole transport layer 13 and the first electrode 12 are stacked in sequence on the support 11. In addition, for example, as described above, other components may or may not exist between the layers of the support 11, the first electrode 12, the hole transport layer 13, the photoelectric conversion layer 14, the electron transport layer 15 and the second electrode 16. In addition, an example in which the first electrode 12 is a transparent electrode and the second electrode 16 is a back electrode is described, but the photoelectric conversion component of the present invention is not limited to this. For example, in the photoelectric conversion component of the present invention, on the contrary, the first electrode may be a back electrode and the second electrode may be a transparent electrode.

[0082] The total thickness of the photoelectric conversion element of the present invention can be appropriately changed according to the thickness of the support used.

[0083] [seal] The photoelectric conversion component (e.g., solar cell) of the present invention is preferably sealed to protect the device from water and oxygen. The sealing structure is not particularly limited, and can be the same as that of a conventional photoelectric conversion component (e.g., solar cell). Specifically, for example, a sealing material can be applied only to the periphery of the photoelectric conversion component of the present invention and covered with glass or a film, or a sealing material can be applied to the entire surface of the photoelectric conversion component of the present invention and covered with glass or a film, or a sealing material can be applied only to the entire surface of the photoelectric conversion component of the present invention.

[0084] The material of the sealing member is not particularly limited and can be appropriately selected depending on the purpose. For example, epoxy resin or acrylic resin is used. It is preferably cured, but it may not be cured or may be only partially cured.

[0085] The epoxy resin is not particularly limited, for example, water dispersion system, solvent-free system, solid system, heat curing type, curing agent mixed type, ultraviolet curing type, etc., wherein preferably heat curing type and ultraviolet curing type, more preferably ultraviolet curing type. It should be noted that even if it is ultraviolet curing type, it can be heated, preferably even after ultraviolet curing. As a specific example of epoxy resin, bisphenol A type, bisphenol F type, novolac type, cyclic aliphatic type, long-chain aliphatic type, glycidylamine type, glycidyl ether type, glycidyl ester type, etc. can be cited, they can be used alone, and more than two kinds can also be used in combination. In addition, it is preferred to mix curing agent and various additives in epoxy resin as needed. Commercially available epoxy resin compositions can be used in the present invention. Among them, there are also commercially available epoxy resin compositions developed for solar cells and organic EL elements, which can be used particularly effectively in the present invention. Examples of commercially available epoxy resin compositions include TB3118, TB3114, TB3124, and TB3125F (manufactured by ThreeBond Co., Ltd.), WorldRock5910, WorldRock5920, and WorldRock8723 (manufactured by Kyoritsu Chemical Industry Co., Ltd.), and WB90US(P) and WB90US-HV (manufactured by Moresco).

[0086] The acrylic resin is not particularly limited, and for example, commercially available acrylic resins developed for solar cells and organic EL devices can be effectively used. Examples of commercially available acrylic resin compositions include TB3035B and TB3035C (manufactured by ThreeBond Co., Ltd.).

[0087] As the curing agent, there is no particular limitation, and it can be appropriately selected according to the purpose, for example, amine system, anhydride system, polyamide system, other curing agents, etc. can be enumerated. As amine curing agent, aliphatic polyamines such as diethylenetriamine, triethylenetetramine, aromatic polyamines such as m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, etc. can be enumerated, and as anhydride curing agent, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, chlorobridged anhydride, dodecenyl succinic anhydride, etc. can be enumerated. As other curing agents, imidazoles, polymercaptan, etc. can be enumerated. They can be used alone, or two or more can be used in combination.

[0088] As the additive, there is no particular limitation, and it can be appropriately selected according to the purpose, for example, fillers (fillers), interstitials, polymerization initiators, desiccants (moisture absorbers), curing accelerators, coupling agents, toughening agents, colorants, flame retardants, antioxidants and organic solvents can be cited. Among them, fillers, interstitials, curing accelerators, polymerization initiators, desiccants (moisture absorbers) are preferred, and fillers and polymerization initiators are more preferred. By containing fillers as additives, it is possible to inhibit the intrusion of moisture and oxygen, and then it is possible to obtain the effects of reducing volume shrinkage during curing, reducing exhaust volume during curing or heating, improving mechanical strength, and controlling thermal conductivity and fluidity. Therefore, in terms of maintaining stable output under various environments, it is very effective to include fillers as additives.

[0089] In addition, regarding the output characteristics and durability of the photoelectric conversion component, not only the influence of the intruding moisture and oxygen cannot be ignored, but also the influence of the exhaust gas generated when the sealing component is cured or heated. In particular, the influence of the exhaust gas generated during heating has a greater impact on the output characteristics during storage in a high-temperature environment. By including fillers, gap agents, and desiccants in the sealing component, in addition to being able to inhibit the intrusion of moisture and oxygen themselves, they can also reduce the amount of sealing components used, thereby achieving the effect of reducing exhaust gas. The inclusion of fillers, gap agents, and desiccants in the sealing component is not only effective during curing, but also effective when storing the photoelectric conversion component in a high-temperature environment.

[0090] As the filler, there is no particular restriction, and it can be appropriately selected according to the purpose, for example, inorganic fillers such as silicate minerals such as crystalline or amorphous silicon dioxide, talc, aluminum oxide, aluminum nitride, silicon nitride, calcium silicate, calcium carbonate, etc. can be cited. Among them, hydrotalcite is particularly preferred. In addition, they can be used alone or in combination of two or more.

[0091] The average primary particle size of the filler is not particularly limited, but is preferably 0.1 μ m or more and 10 μ m or less, more preferably 1 μ m or more and 5 μ When the average primary particle size of the filler is within the preferred range, the effect of suppressing the intrusion of moisture and oxygen can be fully obtained, the viscosity becomes appropriate, the adhesion with the substrate and the degassing property are improved, and the width of the sealing portion can be effectively controlled and the operability is also effective.

[0092] The content of the filler 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, relative to the entire sealing member (100 parts by mass). By making the content of the filler within the above preferred range, the effect of suppressing the intrusion of moisture and oxygen can be fully obtained, the viscosity becomes appropriate, and the adhesion and operability also become good.

[0093] The gap agent is also called a gap control agent or a spacer agent. By including a gap material as an additive, the gap of the sealing portion can be controlled. For example, a sealing member is provided on the first substrate or the first electrode, and in the case where a second substrate is placed thereon for sealing, the sealing member is mixed with the gap agent, whereby the gap of the sealing portion is consistent with the size of the gap agent, and thus the gap of the sealing portion can be easily controlled.

[0094] There is no particular limitation on the interstitial agent, and for example, it is preferably a granular interstitial agent with uniform particle size, high solvent resistance and heat resistance, and can be appropriately selected according to the purpose. As the interstitial agent, it is preferred that the interstitial agent has high affinity with epoxy resin and spherical particle shape. Specifically, glass beads, silica particles, organic resin particles, etc. are preferred. They can be used alone or in combination of two or more. The particle size of the interstitial agent can be selected according to the gap of the set sealing part, preferably 1 μ m or more and 100 μ m or less, more preferably 5 μ m and above and 50 μ m or less.

[0095] The polymerization initiator is not particularly limited, and for example, a polymerization initiator that uses heat or light to initiate polymerization can be cited. It can be appropriately selected according to the purpose, for example, a thermal polymerization initiator, a photopolymerization initiator, etc. can be cited. A thermal polymerization initiator is a compound that generates active species such as free radicals and cations by heating, and examples include azo compounds such as 2,2'-azobisbutyronitrile (AIBN), peroxides such as benzoyl peroxide (BPO), etc. As a thermal cationic polymerization initiator, benzene sulfonate, alkyl sulfonium salt, etc. can be used. In the case of epoxy resin, a photocationic polymerization initiator is preferably used as a photopolymerization initiator. When a photocationic polymerization initiator is mixed with an epoxy resin and irradiated with light, the photocationic polymerization initiator decomposes to generate an acid, and the acid causes polymerization of the epoxy resin to perform a curing reaction. The photocationic polymerization initiator has the effects of less volume shrinkage during curing, no hindrance from oxygen, and high storage stability.

[0096] As the photocationic polymerization initiator, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, metallocene compounds, silanol aluminum complexes, etc. can be mentioned. In addition, as a polymerization initiator, a photoacid generator having a function of generating an acid by irradiating light can also be used. The photoacid generator acts as an acid that initiates cationic polymerization, and onium salts such as ionic sulfonium salts or iodonium salts containing a cationic part and an anionic part can be mentioned. They can be used alone or in combination of two or more.

[0097] The amount of the polymerization initiator added is not particularly limited, and sometimes varies depending on the material used. It is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, relative to the entire sealing member (100 parts by mass). By making the amount added within the above preferred range, curing is properly performed, the residue of uncured material can be reduced, and excessive exhaust can be prevented.

[0098] The desiccant (also called a hygroscopic agent) is a material that physically or chemically absorbs moisture and has a hygroscopic function. By making the sealing component contain the desiccant, the moisture resistance can be further improved and the influence of exhaust gas can be reduced. There is no particular limitation on the desiccant, and it can be appropriately selected according to the purpose. It is preferably a granular desiccant, for example, inorganic water-absorbing materials such as calcium oxide, barium oxide, magnesium oxide, magnesium sulfate, sodium sulfate, calcium chloride, silica gel, molecular sieves, and zeolites can be cited. Among them, zeolites with a large amount of hygroscopicity are preferred. They can be used alone or in combination of two or more.

[0099] The curing accelerator (also called curing catalyst) is a material that accelerates the curing speed and is mainly used for thermosetting epoxy resins. The curing accelerator is not particularly limited and can be appropriately selected according to the purpose. For example, tertiary amines or tertiary amine salts such as DBU (1,8-diazabicyclo (5,4,0)-undecene-7) and DBN (1,5-diazabicyclo (4,3,0)-nonene-5), imidazoles such as 1-cyanoethyl-2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole, phosphines or phosphonium salts such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate can be used alone or in combination of two or more.

[0100] The coupling agent is not particularly limited as long as it has the effect of improving the molecular bonding force, and can be appropriately selected according to the purpose, and examples thereof include silane coupling agents, etc. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl- γSilane coupling agents such as -aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, and 3-methacryloxypropyltrimethoxysilane. These may be used alone or in combination of two or more.

[0101] In the present invention, for example, a sheet-like adhesive can be used. The sheet-like adhesive refers to an adhesive having a resin layer formed in advance on a sheet, and the sheet can be made of glass, a film with high gas barrier properties, etc. In addition, the sheet can be formed only from a sealing resin. The sheet-like adhesive can also be pasted on a sealing film. It is also possible to form a structure in which a hollow portion is provided on the sealing film and then bonded to the device.

[0102] When the sealing film is used for sealing, it is arranged opposite to the support body in a manner of clamping the photoelectric conversion device. The shape, structure, size, and type of the substrate of the sealing film are not particularly limited, and can be appropriately selected according to the purpose. The sealing film forms a barrier layer on the surface of the substrate to prevent moisture and oxygen from passing through, and can be formed only on one side of the substrate or on both sides.

[0103] The barrier layer may be composed of a material mainly composed of metal oxides, metals, a mixture of a polymer and a metal alkoxide, etc. Examples of the metal oxides include aluminum oxide, silicon oxide, aluminum, etc. Examples of the polymers include polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose, etc. Examples of the metal alkoxides include tetraethoxysilane, triisopropoxyaluminum, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc.

[0104] The barrier layer may be transparent or opaque. In addition, the barrier layer may be a single layer composed of the above materials or a multi-layer laminated structure. The barrier layer may be formed by a known method, such as vacuum film forming such as sputtering, dipping, roll coating, screen printing, spraying, gravure printing, and other coating methods.

[0105] [Wiring] In order to effectively extract the current generated by light, the photoelectric conversion component (such as a solar cell) of the present invention preferably connects a wire (wiring) to the electrode and the back electrode. The wire is connected to the first electrode and the second electrode using a conductive material such as solder, silver paste, or graphite. The conductive material can be used alone or in a mixed or laminated structure of two or more. In addition, from the perspective of physical protection, the part where the wire is installed can also be covered with an acrylic resin or an epoxy resin.

[0106] The term "conducting wire" is a general term for electric wires used to electrically connect power supplies, electronic components, and the like in an electric circuit, and examples thereof include vinyl wires and enameled wires.

[0107] [application] The purpose and method of use of the photoelectric conversion component of the present invention are not particularly limited, and for example, it can be widely used for the same purposes as conventional photoelectric conversion components (such as conventional solar cells). The photoelectric conversion component of the present invention (such as a solar cell) can be applied to a power supply device by, for example, combining it with a circuit substrate that controls the generated current. As a type of equipment that utilizes a power supply device, for example, electronic desktop computers, solar radio watches, etc. can be cited. In addition, the photoelectric conversion component of the present invention can also be applied to mobile phones, electronic paper, thermometers and hygrometers as a power supply device. In addition, it can also be used as an auxiliary power supply for the purpose of extending the continuous use time of rechargeable and dry battery-type electrical appliances, or can be used for nighttime use by combining it with a secondary battery. In addition, it can also be used as an independent power supply that does not require battery replacement, power wiring, etc.

[0108] Example Hereinafter, examples of the present invention will be described, but the present invention is not limited to the following examples.

[0109] [Example 1] The first electrode is patterned in advance as Figure 7On an ITO glass substrate of the shape shown (a first electrode is formed on a glass substrate (thickness: 0.7 mm) as a support), a colloidal SnO2 aqueous solution (manufactured by Alfa Aesar) is applied by spin coating and dried at 100°C to obtain an electron transport layer (not shown). It should be noted that a glass substrate is used in this embodiment, but other substrates, such as substrates such as plastic films described in the embodiments, can also be used. Even if the above-mentioned substrate is changed, there is no difference in the performance of the photoelectric conversion component of the present invention. Next, cesium iodide (0.738 g), formamidine iodide (7.512 g), methylamine bromide (0.905 g), lead iodide (23.888 g), and lead bromide (1.022 g) are dissolved in N,N-dimethylformamide (DMF, 40.0 mL) and dimethyl sulfoxide (DMSO, 12.0 mL), and the dissolved solution is spin-coated on the substrate to form a film. The spin coating was performed at a rotation speed of 3000 rpm, and 30 seconds after the start of spin coating, chlorobenzene (0.3 mL) was dropped onto the coating layer of the substrate. Then, the substrate was heated at 150°C for 10 minutes to obtain a perovskite layer (Cs 0.05 FA 0.80 MA 0.15 PbI 2.49 Br 0.51 ) as a photoelectric conversion layer.

[0110] Next, spiro-OMeTAD (72.3 mg), [tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridinium)cobalt(III)tris(bis(trifluoromethylsulfonyl)imide)] (FK209, Fujifilm Wako Pure Chemical Industries, Ltd., 13.5 mg), 4-tert-butylpyridine (28.8 μ L) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI, 9.1 mg) were dissolved in chlorobenzene (1 mL), and a layer of the dissolved solution was formed on the photoelectric conversion layer by spin coating, and then heated and dried at 70°C for 30 minutes to obtain a hole transport layer (not shown). Then, the photoelectric conversion layer (perovskite layer) was etched (removed) using a laser processing device to form a layer such as Figure 8 The pattern of the photoelectric conversion layer (perovskite layer) is shown.

[0111] Finally, 80 nm of gold was formed by vacuum evaporation, and the second electrode was etched (removed) using a laser processing device to obtain the following Fig. 9 The photoelectric conversion module (perovskite solar cell module) of the shape shown in the figure is obtained. The thickness of the layer of the components of the obtained photoelectric conversion module other than the glass substrate is 1.1 μ m. In addition, the area ratio S is 0.2.

[0112] like Fig.10 As shown, for the obtained photoelectric conversion component, only the bypass portion (the reverse diode portion) is hidden. Fig. 9 A mask is installed on the light-receiving side in the manner of the upper part in the image.

[0113] The photoelectric conversion element manufactured according to the above steps was irradiated with a solar simulator (SMO-250III manufactured by Spectrometer Co., Ltd., light intensity 100 mW / cm 2 ), the voltage and current were measured using a source meter (Keithley 2400 model). As a result, a voltage of 6.62 V and a current of 27.8 mA were obtained (Table 1).

[0114] Then, if Fig.11 As shown, one cell portion of the manufactured module was shielded from light by a light shielding member (shade) S, and the voltage and current were measured by irradiating light under the same conditions as above. As a result, a voltage of 5.51 V and a current of 27.7 mA were obtained (Table 1).

[0115] [Example 2] The first electrode, the electron transport layer, the photoelectric conversion layer, the hole transport layer and the second electrode are patterned as follows Figure 17 to Figure 19 As shown, the shape of the component with two bypass diode functions can be made (for example, Fig.19 The upper and lower parts of the circuit are bypass parts), except that the photoelectric conversion component is formed by the same method as in Example 1. Fig. 20 As shown, a mask was attached to the light-receiving surface of the obtained photoelectric conversion element, and the voltage and current were measured in the same manner as in Example 1. As a result, a voltage of 6.67 V and a current of 24.4 mA were obtained (Table 1).

[0116] Then, if Fig.21 As shown, one battery unit was shielded from light, and the voltage and current were measured in the same manner as in Example 1. As a result, a voltage of 5.53 V and a current of 24.3 mA were obtained (Table 1).

[0117] [Comparative Example 1] The first electrode, the electron transport layer, the photoelectric conversion layer, the hole transport layer and the second electrode are patterned as follows Figure 12 to Figure 14 The photoelectric conversion element is formed by the same method as in Example 1 except that the shape of the element is changed to one without the bypass diode function. Fig.15 As shown, a mask was attached to the light-receiving surface of the obtained photoelectric conversion element, and the voltage and current were measured in the same manner as in Example 1. As a result, a voltage of 6.61 V and a current of 30.2 mA were obtained (Table 1).

[0118] Then, if Fig.16As shown, one battery unit was shielded from light, and the voltage and current were measured in the same manner as in Example 1. As a result, a voltage of 4.63 V and a current of 0.002 mA were obtained (Table 1).

[0119] [Comparative Example 2] A photoelectric conversion element was produced in the same manner as in Example 1 except that the area ratio S was set to 1.0.

[0120] [Table 1]

[0121] Regarding Example 1, if the voltage before and after the light shielding is compared, it can be seen that although the voltage is reduced by the equivalent of one battery, the current value is almost unchanged, and it can be seen that the bypass part (the reverse diode part) produced this time functions as a bypass diode. In addition, since the bypass diode function is present in the plane parallel to the light receiving surface, the photoelectric conversion component as a whole has few unevenness, and there are few parts that become obstacles when pasted on a wall, etc., so it is flexible and practical.

[0122] Regarding Example 2, if the voltage before and after the light shielding is compared, it can be seen that although the voltage is reduced by the equivalent of one battery, the current value is almost unchanged, and it can be seen that the two bypass parts (diode parts in the opposite direction) made this time function as bypass diodes. As in Example 1, since the bypass diode function is present in the plane parallel to the light-receiving surface, the photoelectric conversion component as a whole has few unevenness, and there are few parts that become obstacles when pasted on a wall, etc., which is flexible and practical.

[0123] On the other hand, in Comparative Example 1, if the voltage and current before and after the light shielding are compared, the voltage decrease is slightly more than the voltage equivalent to one battery, and the current value is almost not obtained. This is a phenomenon caused by the one battery existing as a resistor due to the light shielding. Therefore, although Comparative Example 1 is flexible, depending on the system set, when excessive voltage is applied to the component from the peripheral circuit and this state is maintained, hot spots may occur.

[0124] In addition, in Comparative Example 2, the area of ​​the power generation section was too small compared to the area of ​​the entire module, and thus the output obtained was low, which was not preferable.

[0125] As described above, this embodiment confirms that the photoelectric conversion module of the present invention has a bypass diode function and does not lose flexibility. That is, it has flexibility and does not generate hot spots even when the battery is shielded from light, and a photoelectric conversion module with stable performance can be obtained, so that, for example, the long-term reliability of the photoelectric conversion module can be ensured. In addition, since there is no need to set up a bypass diode as in the previous photoelectric conversion module, for example, the photoelectric conversion module can also be made lightweight.

[0126] The present invention has been described above using the embodiments and examples. However, the present invention is not limited to the embodiments and examples described above, and any and appropriate combinations, changes or selections can be adopted as needed without departing from the gist of the present invention.

[0127] <Note> A part or all of the above-mentioned embodiments and examples can also be described as the following supplementary notes, but are not limited to the following.

[0128] (Note 1) A photoelectric conversion component, characterized in that the photoelectric conversion component comprises a power generation part and a bypass part, The power generation unit and the bypass unit respectively include a first electrode, a photoelectric conversion layer, and a second electrode, wherein the first electrode, the photoelectric conversion layer, and the second electrode are sequentially stacked. The power generation unit and the bypass unit each have a diode function. In a plane parallel to the light receiving surface, the diodes of the power generation section and the diodes of the bypass section are oriented in opposite directions to each other.

[0129] (Note 2) The photoelectric conversion element according to Supplementary Note 1, wherein in the power generation section and the bypass section, at least one of the first electrode, the photoelectric conversion layer, and the second electrode is formed of the same material as each other.

[0130] (Note 3) The photoelectric conversion element according to Supplementary Note 1 or 2, wherein the power generation section and the bypass section each further include a support.

[0131] (Note 4) The photoelectric conversion element according to Supplementary Note 3, wherein in the power generation section and the bypass section, at least one of the support, the first electrode, the photoelectric conversion layer, and the second electrode is formed of the same material.

[0132] (Note 5) The photoelectric conversion element according to any one of appendices 1 to 4, wherein an area ratio S (Sb / Sp) of an overall area (Sp) of a surface in the power generation section parallel to the light receiving surface and an overall area (Sb) of a surface in the bypass section parallel to the light receiving surface is 0.2 or less.

[0133] (Note 6) The photoelectric conversion element according to any one of Supplementary Notes 1 to 5, wherein at least a portion of the bypass portion is shielded from light.

[0134] (Note 7) The photoelectric conversion element according to any one of Supplementary Notes 1 to 6, wherein the photoelectric conversion layer comprises a compound having a perovskite structure represented by the following chemical formula (I).

[0135] X α Y β Z γ (I) In the chemical formula (I), X is a halogen ion, Y is a monovalent cation, and Z is a divalent cation. α : β : γ The ratio is 3:(0.95~1.05):(0.95~1.05).

[0136] (Note 8) The photoelectric conversion element according to Supplementary Note 7, wherein in the chemical formula (I), the monovalent cation represented by Y includes at least one cation selected from the group consisting of cesium cations, rubidium cations, potassium cations, methylammonium cations and formamidinium cations.

[0137] (Note 9) The photoelectric conversion component according to any one of Supplementary Notes 1 to 8, wherein the photoelectric conversion component is a solar cell.

[0138] Industrial Applicability As described above, according to the present invention, a photoelectric conversion component having a bypass diode function and not losing flexibility can be provided. The photoelectric conversion component of the present invention is useful, for example, as a solar cell. The purpose and method of use of the photoelectric conversion component of the present invention are not particularly limited, for example, it can be applied to a wide range of fields with the same purpose and method of use as a conventional photoelectric conversion component (e.g., a conventional solar cell).

[0139] This application claims the benefit of priority based on Japanese patent application No. 2022-194516, filed on December 5, 2022, the disclosure of which is incorporated herein in its entirety.

[0140] Description of Reference Numerals 10, 20 Photoelectric conversion components 11, 21 Support 12, 22 first electrode 13.23 Electron transport layer 14.24 Photoelectric conversion layer 15.25 Hole transport layer 16, 26 Second electrode 17 Mask S Shading component (shadow).

Claims

1. A photoelectric conversion component, characterized in that: The photoelectric conversion component comprises a power generation part and a bypass part. The power generation unit and the bypass unit respectively include a first electrode, a photoelectric conversion layer, and a second electrode, wherein the first electrode, the photoelectric conversion layer, and the second electrode are sequentially stacked. The power generation unit and the bypass unit each have a diode function. In a plane parallel to the light receiving surface, the diodes of the power generation section and the diodes of the bypass section are oriented in opposite directions to each other.

2. The photoelectric conversion component according to claim 1, wherein: In the power generation section and the bypass section, at least one of the first electrode, the photoelectric conversion layer, and the second electrode is formed of the same material as each other.

3. The photoelectric conversion component according to claim 1 or 2, wherein: The power generation section and the bypass section each further include a support body.

4. The photoelectric conversion component according to claim 3, wherein: In the power generation section and the bypass section, at least one of the support, the first electrode, the photoelectric conversion layer, and the second electrode is formed of the same material as each other.

5. The photoelectric conversion component according to claim 1 or 2, wherein: An area ratio S of an area Sp of the entire surface of the power generation section parallel to the light receiving surface and an area Sb of the entire surface of the bypass section parallel to the light receiving surface (Sb / Sp) is 0.2 or less.

6. The photoelectric conversion component according to claim 1 or 2, wherein: At least a portion of the bypass portion is shielded from light.

7. The photoelectric conversion component according to claim 1 or 2, wherein: The photoelectric conversion layer includes a compound having a perovskite structure represented by the following chemical formula (I), X α Y β Z γ (I) In the chemical formula (I), X is a halogen ion, Y is a monovalent cation, and Z is a divalent cation. α : β : γ The ratio is 3:(0.95~1.05):(0.95~1.05).

8. The photoelectric conversion component according to claim 7, wherein: In the chemical formula (I), the monovalent cation represented by Y includes at least one cation selected from the group consisting of a cesium cation, a rubidium cation, a potassium cation, a methylammonium cation, and a formamidinium cation.

9. The photoelectric conversion component according to claim 1 or 2, wherein: The photoelectric conversion component is a solar cell.

Images