Photoelectric conversion module and method for manufacturing a photoelectric conversion module

Abstract

The present invention provides a photoelectric conversion module in which the degradation of performance is suppressed by inhibiting the reaction between the photoelectric conversion layer and the second electrode. [Solution] A photoelectric conversion module 10 comprising a first electrode 12, a photoelectric conversion layer 14, a second electrode 16, and an isolation layer 15, wherein the photoelectric conversion layer 14 is disposed between the first electrode 12 and the second electrode 16, and the isolation layer 15 is disposed between the photoelectric conversion layer 14 and the second electrode 16, and the isolation layer 15 separates the photoelectric conversion layer 14 and the second electrode 16 so as not to come into direct contact with each other, and a conductive portion 20 is provided in a part between the first electrode 12 and the second electrode 16 where the photoelectric conversion layer 14 and the isolation layer 15 are absent, and the first electrode 12 and the second electrode 16 are electrically conductive in the conductive portion 20 by coming into direct contact with each other or via an electrical conductor.

Description

[Technical Field]

[0001] This disclosure relates to a photoelectric conversion module and a method for manufacturing a photoelectric conversion module. [Background technology]

[0002] In recent years, solar power generation has attracted attention as a clean energy source. As a result, the development of solar cells, a type of photoelectric conversion module, is progressing. One such next-generation solar cell that can be manufactured at low cost is rapidly gaining attention, and solar cells that use perovskite material as a light-absorbing layer are attracting attention. For example, Patent Document 1 discloses a solar cell module that uses perovskite material as a light-absorbing layer. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2024-130358 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] For example, in order to improve power generation efficiency, a structure is being considered for solar cell modules in which multiple strip-shaped cells are divided into several sections and connected in series. In this module structure, adjacent strip-shaped cells are connected in series by electrically connecting a first electrode and a second electrode formed on each surface of the photoelectric conversion layer in a predetermined region where the photoelectric conversion layer is not formed.

[0005] This predetermined region is formed by cutting the photoelectric conversion layer using a laser or other method. This process exposes the processed surface of the photoelectric conversion layer, and a second electrode is formed on this processed surface.

[0006] However, if the photoelectric conversion layer and the second electrode are in direct contact and current flows between the first and second electrodes, there is a risk of material degradation at this contact point. This degradation is thought to be due to migration occurring at the interface between the photoelectric conversion layer and the second electrode, leading to chemical reactions with the materials of the photoelectric conversion layer and the second electrode. This could potentially degrade the performance of the photoelectric conversion module.

[0007] Therefore, the present disclosure aims to provide a photoelectric conversion module in which the deterioration of characteristics is suppressed by suppressing the reaction between the photoelectric conversion layer and the second electrode, and a method for manufacturing the photoelectric conversion module. [Means for solving the problem]

[0008] To achieve the aforementioned objective, the photoelectric conversion module of this disclosure is provided. It includes a first electrode, a photoelectric conversion layer, a second electrode, and an isolation layer. The photoelectric conversion layer is disposed between the first electrode and the second electrode, The isolation layer is placed between the photoelectric conversion layer and the second electrode, and the isolation layer separates the photoelectric conversion layer and the second electrode so that they do not come into direct contact. A conductive portion is provided between the first electrode and the second electrode, where the photoelectric conversion layer and the isolation layer are absent. In the conductive portion, the first electrode and the second electrode are in contact either directly or via an electrical conductor, thereby enabling electrical conductivity between them.

[0009] The method for manufacturing the photoelectric conversion module disclosed herein is: A method for manufacturing a photoelectric conversion module, The photoelectric conversion module includes a first electrode, a photoelectric conversion layer, a second electrode, and an isolation layer. The method for manufacturing the photoelectric conversion module includes a photoelectric conversion layer formation step, a photoelectric conversion layer partial removal step, an isolation layer formation step, an isolation layer partial removal step, and a second electrode formation step. The photoelectric conversion layer formation step is a step of forming the photoelectric conversion layer on the first electrode, The photoelectric conversion layer partial removal step is a step of removing a part of the photoelectric conversion layer to expose a part of the first electrode, The isolation layer formation step is a step of forming the isolation layer on the photoelectric conversion layer and on the exposed portion of the first electrode after the partial removal step of the photoelectric conversion layer. The aforementioned isolation layer partial removal step is a step of removing the isolation layer from a part of the first electrode to expose a part of the first electrode again. The second electrode formation step is a step in which, after the partial removal of the isolation layer, the second electrode is formed in contact with the isolation layer and the first electrode, but not in contact with the photoelectric conversion layer. It is characterized by the following: [Effects of the Invention]

[0010] According to this disclosure, it is possible to provide a photoelectric conversion module in which the deterioration of characteristics is suppressed by suppressing the reaction between the photoelectric conversion layer and the second electrode, and a method for manufacturing the photoelectric conversion module. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 is a cross-sectional view showing an example of a photoelectric conversion module according to the present disclosure. [Figure 2] Figures 2(a) to 2(i) are cross-sectional views showing an example of a method for manufacturing the photoelectric conversion module of the present disclosure. [Figure 3] Figure 3 shows an example of a state in which the first electrode is formed on a support. Figure 3(a) is a plan view. Figure 3(b) is a cross-sectional view. [Figure 4] Figure 4 shows an example of a photoelectric conversion module according to the present disclosure. Figure 4(a) is a plan view. Figure 4(b) is a cross-sectional view. [Figure 5] Figures 5(a) to 5(d) are plan views showing examples of photoelectric conversion modules according to the embodiment. [Figure 6]FIG. 6 is a cross-sectional view showing an example of a photoelectric conversion module related to the present disclosure. [Mode for Carrying Out the Invention]

[0012] Next, the present disclosure will be described more specifically with reference to examples. However, the present disclosure is not limited by the following description.

[0013] In the present disclosure, unless otherwise specified, "mass%" and "weight%" may be read interchangeably, and "parts by mass" and "parts by weight" may be read interchangeably.

[0014] In the present disclosure, "on" or "on a surface" may refer to a state of being in direct contact with the upper side or the surface, or a state of being interposed via other constituent elements or the like.

[0015] [1. Photoelectric Conversion Module] As described above, the photoelectric conversion module of the present disclosure includes a first electrode, a photoelectric conversion layer, a second electrode, and an isolation layer, wherein the photoelectric conversion layer is disposed between the first electrode and the second electrode, the isolation layer is disposed between the photoelectric conversion layer and the second electrode, the isolation layer separates the photoelectric conversion layer and the second electrode so that they do not come into direct contact, a conduction portion where the photoelectric conversion layer and the isolation layer do not exist is provided in a part between the first electrode and the second electrode, and in the conduction portion, the first electrode and the second electrode are in contact with each other directly or via an electrical conductor, so that the first electrode and the second electrode are electrically connected.

[0016] In the present disclosure, "do not exist" in the "conduction portion where the isolation layer does not exist" means an embodiment in which the isolation layer is removed so that the conduction between the first electrode and the second electrode is not hindered by the isolation layer, and a part of the isolation layer may remain in a part of the conduction portion to an extent that does not affect the conduction.

[0017] Figure 1 shows a cross-sectional view illustrating the configuration of an example of a photoelectric conversion module according to the present disclosure. As shown in the figure, this photoelectric conversion module 10 includes a support (also called a substrate or base material) 11, a first electrode 12, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a second electrode 16. The electron transport layer 15 corresponds to the "isolation layer" in the photoelectric conversion module according to the present disclosure. As shown in the figure, 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 are stacked in this order. That is, the photoelectric conversion layer 14 is positioned between the first electrode 12 and the second electrode 16. The electron transport layer 15 is positioned between the photoelectric conversion layer 14 and the second electrode 16. A first dividing groove 12A is provided in a part of the first electrode 12, and the hole transport layer 13 is filled into the first dividing groove 12A and partially in contact with the surface of the first electrode 12. This first dividing groove 12A makes it possible to divide the first electrode 12 to correspond to multiple strip-shaped cells. Furthermore, in a part between the first electrode 12 and the second electrode 16, a region is formed on the first electrode 12 in which the hole transport layer 13 and the photoelectric conversion layer 14 are not present. This region on the first electrode 12 in which the hole transport layer 13 and the photoelectric conversion layer 14 are not present is shown as "P2.0" in the figure and may be referred to as the "P2.0 region" below. The electron transport layer 15 covers the upper surface of the photoelectric conversion layer 14, and in the P2.0 region, it covers the side cross-sections of the hole transport layer 13 and the photoelectric conversion layer 14, and also covers the first electrode 12. In other words, the electron transport layer 15 separates the photoelectric conversion layer 14 from the second electrode 16 so that they do not come into direct contact. In a portion of the P2.0 region, a conductive section 20 is provided where the electron transport layer 15 is absent. This conductive section 20 is shown as "P2.5" in the figure and will be referred to as the "P2.5 region" below. In the conductive section 20 (P2.5 region), the first electrode 12 and the second electrode 16 are in direct contact, thereby creating electrical conductivity between them. A second dividing groove 30 is provided in the region opposite to the first dividing groove P1 across the P2.0 region, extending from the upper surface of the second electrode 16 to the upper surface of the first electrode 12.The provision of this first dividing groove 30 makes it possible to divide the second electrode 16 to correspond to multiple strip-shaped cells.

[0018] The configuration shown in Figure 1 is an example, and the configuration of the photoelectric conversion module of the present disclosure is not limited thereto. For example, the photoelectric conversion module of the present disclosure may include, or may not include, other components other than the first electrode, the photoelectric conversion layer, the second electrode, and the isolation layer. In Figure 1, the support 11 and the hole transport layer 13 correspond to the "other components". Also in Figure 1, the hole transport layer 13 is arranged between the first electrode 12 and the photoelectric conversion layer 14, and the electron transport layer 15 is arranged between the second electrode 16 and the photoelectric conversion layer 14. However, the photoelectric conversion module of the present disclosure is not limited thereto, and for example, the arrangement of the hole transport layer and the electron transport layer in Figure 1 may be swapped. In other words, the photoelectric conversion module of the present disclosure may have either 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 the order described above, or an inverted structure in which the first electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer, and the second electrode are stacked in the order described above. The photoelectric conversion module 10 in Figure 1 has an inverted structure. In a photoelectric conversion module with a forward structure, for example, the support 11 may be located on the opposite side from Figure 1 (above the second electrode 16 in Figure 1), and the second electrode 16, the electron transport layer 15, the photoelectric conversion layer 14, the hole transport layer 13, and the first electrode 12 may be stacked on the support 11 in the order described above. Furthermore, each component of the photoelectric conversion module of the present disclosure may be directly stacked without other components present, or other components may be present between them. For example, the first electrode and the electron transport layer or hole transport layer may be directly laminated without any other components present, or other components may be present between them. Similarly, the electron transport layer or hole transport layer and the photoelectric conversion layer may be directly laminated without any other components present, or other components may be present between them. Similarly, the hole transport layer or electron transport layer and the second electrode may be directly laminated without any other components present, or other components may be present between them.Furthermore, in the conductive portion, the first electrode and the second electrode may be in direct contact, for example, as shown in Figure 1, or, as mentioned above, they may be electrically conductive through contact via an electrical conductor.

[0019] Figure 6 shows a cross-sectional view of an example of a photoelectric conversion module related to this disclosure. As shown in the figure, this photoelectric conversion module 10a includes a support 11, a first electrode 12, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a second electrode 16, just like the photoelectric conversion module 10 in Figure 1. In this photoelectric conversion module 10a, the portion corresponding to the P2.0 region in Figure 1 (the portion where the hole transport layer 13 and the photoelectric conversion layer 14 are not present on the first electrode 12) corresponds to the conductive P2.5 region. As shown in the figure, in the P2.5 region of the photoelectric conversion module 10a, the electron transport layer 15 is absent, and the second electrode 16 is in direct contact with the hole transport layer 13, the photoelectric conversion layer 14, and the electron transport layer 15. Except for these, the photoelectric conversion module 10a in Figure 6 is the same as the photoelectric conversion module 10 in Figure 1.

[0020] As mentioned above, when a current flows between the first electrode 12 and the second electrode 16 while the photoelectric conversion layer 14 and the second electrode 16 are in direct contact, as shown in Figure 6, there is a risk of material degradation occurring at this contact point. This degradation phenomenon is thought to be due to migration occurring at the interface between the photoelectric conversion layer 14 and the second electrode 16, leading to chemical reactions with the materials of the photoelectric conversion layer 14 and the second electrode 16. Specifically, this degradation phenomenon may include, for example, degradation of the second electrode material, which may hinder electrical connections near the conductive part (for example, electrical connections between strip cells), potentially reducing power generation characteristics. Furthermore, for example, especially when a perovskite material is used in the light absorption layer of the photoelectric conversion layer 14, the perovskite crystal structure may be damaged, potentially reducing light absorption characteristics. In this disclosure, as described above, this problem is solved by separating the photoelectric conversion layer and the second electrode so that they do not come into direct contact with each other, using an isolation layer (electron transport layer 15 in Figure 1).

[0021] In the following, each component of the photoelectric conversion module of this disclosure will be described in more detail with examples. However, the photoelectric conversion module of this disclosure is not limited to the following examples. In the following, the case in which the photoelectric conversion module of this disclosure is a solar cell will be described in particular.

[0022] [Support 11] The support 11 is not particularly limited, and may appropriately use a substrate that can be used in a photoelectric conversion module such as a general solar cell. Examples of the substrate include glass, a plastic plate including a plastic film, a plastic film, an inorganic crystal, etc. The thickness of the substrate is not particularly limited, and is, for example, a thickness that does not hinder the flexibility of the photoelectric conversion module of this disclosure. In this disclosure, "flexible" means, for example, that the photoelectric conversion module of this disclosure is flexible enough that no cracks or fractures occur after stress is applied to it, and that the performance of the photoelectric conversion module is not affected. If the substrate is glass, for example, a thickness of 0.5 to 1.1 mm is preferred. If the substrate is a plastic film, for example, a thickness of 50 to 125 μm is preferred. In addition, a substrate on which at least one of the following films is formed on part or all of the surface of the substrate is also suitably used as the support 11. The size, thickness, etc. of the support 11 are not particularly limited, and may be the same as or similar to that of a photoelectric conversion module such as a general solar cell.

[0023] [First electrode 12] The first electrode 12 is a layer that supports, for example, the hole transport layer 13 and the electron transport layer 15, and also has the function of extracting electrons or holes from the photoelectric conversion layer 14. Furthermore, the first electrode 12 is a layer that acts as an anode (negative electrode).

[0024] The first electrode 12 may be formed directly on the support 11, for example, as shown in Figure 1. The first electrode 12 may also be a transparent electrode formed from a conductor, for example. The transparent electrode is not particularly limited, but examples include a tin-doped indium oxide (ITO) film, an impurity-doped indium oxide (In2O3) film, an impurity-doped zinc oxide (ZnO) film, a fluorine-doped tin dioxide (FTO) film, a laminated film formed by laminating two or more of these, gold, silver, copper, aluminum, tungsten, titanium, chromium, nickel, and cobalt. These may be used individually or as a mixture of two or more, and may be a single layer or a laminate. Furthermore, these films may function as a diffusion barrier layer, for example. The thickness of the first electrode 12 is not particularly limited, but it is preferable to adjust it so that the sheet resistance is 5 to 15 Ω / □ (per unit area). The method for forming the first electrode 12 is not particularly limited, but it can be obtained by known film formation methods, for example, depending on the material to be formed. Furthermore, the shape of the first electrode 12 is not particularly limited, but may be, for example, a film or a lattice-like mesh. The method for forming the first electrode 12 on the support 11 is not particularly limited, but may be a known method, for example, vacuum deposition or sputtering is preferred. The first electrode 12 may also be patterned. The patterning method is not particularly limited, but examples include immersion in a laser or etching solution, or patterning using a mask during vacuum deposition, and any of these methods may be used in this disclosure. In addition, the first electrode 12 may be used in combination with metal wiring to reduce its electrical resistance. The material of the metal wiring (metal lead wire) is not particularly limited, but examples include aluminum, copper, silver, gold, platinum, and nickel. The metal lead wire can be formed on the first substrate by, for example, deposition, sputtering, or crimping, and then a layer of ITO or FTO is provided on top of it, or provided on top of ITO or FTO to be used in combination.

[0025] [Hole transport layer 13] The hole transport layer 13 is a layer that has the function of transporting electric charge. For example, a conductor, a semiconductor, or an organic hole transport material can be used for the hole transport layer 13. The organic hole transport material can function as a hole transport material that receives holes from the perovskite layer (photoelectric conversion layer) 14 and transports the holes. As the conductor and the semiconductor, inorganic hole transport materials or the organic hole transport materials can be used. Examples of inorganic hole transport materials include compound semiconductors containing monovalent copper such as CuI, CuInSe2, and CuS; and compounds containing metals other than copper such as GaP, NiO, CiO, FeO, Bi2O3, MoO3, and Cr2O. Among these, from the viewpoint of more efficiently receiving only holes and obtaining higher hole mobility, semiconductors containing monovalent copper are preferred, and CuI or CuSCN are more preferred. Examples of the organic hole transport material include polythiophene derivatives such as poly-3-hexylthiophene (P3HT) and polyethylenedioxythiophene (PEDOT); fluorene derivatives such as 2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)-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; and polyaniline derivatives. Among these, triphenylamine derivatives and fluorene derivatives are preferred from the viewpoint of more efficiently receiving only holes and obtaining higher hole mobility, and PTAA and Spiro-OMeTAD are more preferred. In addition, as the organic hole material, for example, compounds represented by chemical formula (I) described in WO2023 / 038050A1 can also be used.

[0026] Furthermore, the aforementioned organic hole transport materials are further improved in order to enhance their hole transport properties, for example, by using 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]butanesulfonylamide, potassium nonafluoro The material may also contain oxidizing agents such as oro-N-[(trifluoromethane)sulfonyl]butanesulfonylamide, nonafluoro-N-[(trifluoromethane)sulfonyl]butanesulfonylamide, lithium N,N-hexafluoro-1,3-disulfonylimide, sodium N,N-hexafluoro-1,3-disulfonylimide, trifluoromethylsulfonyloxysilver, NOSbF6, SbCl5, SbF5, and tris(2-(1H-pyrazole-1-yl)-4-tert-butylpyridine)cobalt(III)tri[bis(trifluoromethane)sulfonimide]. Furthermore, the hole transport layer 13 may also contain basic compounds such as tert-butylpyridine (TBP), 2-picoline, and 2,6-lutidine. The content of the oxidizing agent and basic compounds can be, for example, amounts commonly used conventionally. From the viewpoint of more efficiently receiving only holes and obtaining higher hole mobility, the thickness of the hole transport layer 13 is preferably 1 to 500 nm, and more preferably 2 to 300 nm. The method for forming the hole transport layer 13 is preferably carried out under a dry atmosphere. For example, it is preferable to coat (spin coat, etc.) a solution containing an organic hole transport material onto a perovskite layer (light absorption layer) under a dry atmosphere and heat it at 30 to 180°C, particularly 100 to 150°C.

[0027] Furthermore, as the hole transport layer 13 in the inverted structure, for example, a hole transport compound that forms a monolayer (hereinafter also referred to as "monolayer hole transport compound") can be used. The monolayer hole transport compound preferably has an anchor that chemically bonds with a transparent electrode such as ITO in the inverted structure. Examples of such anchors include a phosphonic acid group (-P=O(OH)2), a carboxyl group (-COOH), a sulfo group (-SO3H), a boronic acid group (-B(OH)2), a trihalogenated silyl group (-SiX3, where X is a halogen atom), or a trialkoxysilyl group (-Si(OR)3, where R is an alkyl group). Among these, the phosphonic acid group, trihalogenated silyl group, and trialkoxysilyl group are particularly preferred.

[0028] The method for forming the hole transport layer 13 using the monomolecule hole transport material is not particularly limited, but for example, the hole transport layer 13 can be formed by adsorbing the monomolecule hole transport compound onto the first electrode 12 to form a monomolecule layer. The method for adsorbing the monomolecule hole transport compound onto the first electrode 12 to form a monomolecule layer is not particularly limited, but for example, the monomolecule hole transport compound can be dissolved in a solvent and brought into contact with the first electrode 12 to bond. The bond between the monomolecule hole transport compound and the first electrode 12 is not particularly limited and may be a physical bond or a chemical bond. The type of bond is also not particularly limited and may be any of the following: hydrogen bond, ester bond, chelate bond, etc. The solvent for dissolving the monomolecule hole transport compound is also not particularly limited and may be either water and an organic solvent, or both. More specifically, examples of the aforementioned solvents include 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; esters such as ethyl acetate, isobutyl acetate, and γ-butyrolactone; heterocyclic compounds such as tetrahydrofuran and thiophene; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; sulfoxides such as dimethyl sulfoxide; sulfones such as diethyl sulfone and sulfolane; nitriles such as acetonitrile and 3-methoxypropionitrile; aromatic compounds such as benzene, toluene, and chlorobenzene; halogenated solvents such as dichloromethane and chloroform; and fluorinated solvents such as chlorofluorocarbon, hydrochlorofluorocarbon, and hydrofluorocarbon. These can be used individually or in mixtures of two or more.

[0029] The specific method for adsorbing the monomolecule hole transport compound onto the first electrode 12 to form a monolayer is not particularly limited, but known methods such as dipping, spraying, spin coating, and bar coating can be used. The temperature during adsorption is not particularly limited, but -20°C to 100°C is preferred, and 0°C to 50°C is more preferred. The adsorption time is also not particularly limited, but for example, 1 second to 48 hours is preferred, and 10 seconds to 1 hour is more preferred. Furthermore, after the adsorption treatment, washing may or may not be performed. The washing method is also not particularly limited, but for example, known methods may be used as appropriate.

[0030] After the adsorption treatment or cleaning, a heat treatment may or may not be performed. The temperature for the heat treatment is preferably 50°C to 150°C, and more preferably 70°C to 120°C. The heat treatment time is preferably 1 second to 48 hours, and more preferably 10 seconds to 1 hour. This heat treatment may be performed, for example, in the atmosphere or in a vacuum.

[0031] When adsorbing the monomolecule hole transport compound onto the first electrode 12, a co-adsorbent may or may not be used in combination. The co-adsorbent can be added, for example, when the monomolecule hole transport compound alone cannot completely coat the electrode surface, or to inhibit the interaction between the monomolecule hole transport compounds.

[0032] The co-adsorbent is not particularly limited, but examples 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, and 1H,1H,2H,2H-perfluorophosphonic acid, as well as acetic acid, propionic acid, isobutyric acid, nonanoic acid, fluoroacetic acid, α-chloropropionic acid, glyoxylic acid, and chenodeoxycholic acid. These may be used individually or in mixtures of two or more types.

[0033] The method for adsorbing the co-adsorbent onto the first electrode 12 is not particularly limited, but, similar to the monomolecule hole transport compound, it is preferable to dissolve it in a solvent before adsorption. The solvent is also not particularly limited, but may be the same as the solvents exemplified above for the monomolecule hole transport compound. Furthermore, the co-adsorbent may be adsorbed by first adsorbing the monomolecule hole transport compound onto the substrate and then immersing the first electrode 12 in a solvent in which the co-adsorbent is dissolved, or it may be used after mixing and dissolving it together with the monomolecule hole transport compound in an organic solvent.

[0034] [Electron transport layer 15] There are no particular restrictions on the material used for the electron transport layer 15, and it can be appropriately selected according to the purpose, but semiconductor materials are preferred. There are no particular restrictions on the semiconductor material, and known materials can be used, such as elemental semiconductors, compound semiconductors, and organic n-type semiconductors.

[0035] The aforementioned single semiconductor is not particularly limited, but examples include silicon and germanium.

[0036] The aforementioned compound semiconductors are not particularly limited, but examples 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. Other compound semiconductors include phosphides of zinc, gallium, indium, cadmium, etc., gallium arsenide, copper-indium selenide, copper-indium sulfide, etc.

[0037] The aforementioned organic n-type semiconductor is not particularly limited, but examples include perylenetetracarboxylic anhydride, perylenetetracarboxydiimide compounds, naphthalenediimide-bithiophene copolymer, benzobisimidazobenzophenanthroline polymer, C 60 , C 70PCBM([6,6]-phenyl-C 61 Examples include freylan compounds such as methyl butyrate, carbonyl bridge-bithiazole compounds, ALq3 (tris(8-quinolinolato)aluminum), triphenylene bipyridyl compounds, silole compounds, and oxadiazole compounds.

[0038] Among the aforementioned materials used in the electron transport layer 15, organic n-type semiconductors are particularly preferred.

[0039] The materials used to form the electron transport layer 15 may be used individually or in combination of two or more materials. Furthermore, there are no particular restrictions on the crystal type of the semiconductor material; it can be appropriately selected according to the purpose, and may be single crystal, polycrystalline, or amorphous.

[0040] There are no particular restrictions on the thickness of the electron transport layer 15, and it can be appropriately selected depending on the purpose, but 5 nm to 1000 nm is preferred, and 10 nm to 700 nm is more preferred. However, in the side cross-section portion of the photoelectric conversion layer 14 shown in Figure 1, the thickness of the electron transport layer (isolation layer) 15 is preferably 1 to 100 nm, and more preferably 5 to 50 nm.

[0041] There are no particular restrictions on the method for forming the electron transport layer 15, and it can be appropriately selected depending on the purpose. For example, methods such as forming a thin film in a vacuum (vacuum deposition method) and wet deposition methods can be used. Examples of vacuum deposition methods include sputtering, pulsed laser deposition (PLD), ion beam sputtering, ion-assisted deposition, ion plating, vacuum evaporation, atomic layer deposition (ALD), and chemical vapor deposition (CVD). Examples of wet deposition methods include methods of forming by coating a solvent containing dissolved electron transport material, and in the case of oxide semiconductors, the sol-gel method. The sol-gel method is a method in which a gel is prepared from a solution through chemical reactions such as hydrolysis, polymerization, and condensation, and then densification is promoted by heat treatment. When using the sol-gel method, there are no particular restrictions on the method of applying the sol solution, and it can be appropriately selected according to the purpose. Examples include the dip method, spray method, wire bar method, spin coating method, roller coating method, blade coating method, and gravure coating method. Wet printing methods include letterpress, offset, gravure, intaglio, rubber plate, and screen printing. Furthermore, the temperature during the heat treatment after applying the sol solution is preferably 80°C or higher, and more preferably 100°C or higher.

[0042] In the case of an inverted structure, an electron injection layer (hole blocking layer) may be formed between the electron transport layer 15 and the second electrode 16 after the electron transport layer 15 has been formed. Examples of materials used for the electron injection layer include bathocuproine (BCP), which may be doped with cesium. The electron injection layer is preferably 1 nm to 100 nm in size, and more preferably 3 nm to 20 nm.

[0043] [Photoelectric conversion layer 14] The photoelectric conversion layer 14 is not particularly limited and may be the same as a photoelectric conversion layer used in a general photoelectric conversion module such as a solar cell. The photoelectric conversion layer 14 includes, for example, a perovskite compound. The perovskite compound may be, for example, a compound represented by the following chemical formula (I). X α Y β Z γ (I)

[0044] In the chemical formula (I) above, the ratio of α:β:γ is, for example, 3:1:1, where X represents a halogen ion, Y represents a monovalent cation, and Z represents a divalent cation. The perovskite layer is preferably positioned adjacent to the electron transport layer. Note that the ratio of α:β:γ does not necessarily have to be 3:1:1, for example, 3:1.05:0.95 or 3:0.95:1.05. The ratio of α:β:γ is, for example, 3:(0.95~1.05):(0.95~1.05).

[0045] There are no particular restrictions on X in the aforementioned chemical formula (I), and it can be appropriately selected depending on the purpose. Examples include halogen ions such as chlorine, bromine, and iodine. These may be used individually or in combination of two or more.

[0046] Examples of Y in the above chemical formula (I) include alkylamine compound ions (organic compounds having an amino group) such as methylammonium cation, ethylammonium cation, n-butylammonium cation, and formamidinium cation, as well as alkali metal ions such as cesium cation, potassium cation, and rubidium cation, which are not limited to organic compounds. Alkylamine compound ions and alkali metal ions may be used individually or in combination of two or more. Furthermore, organic (alkylamine compound ions) and inorganic (alkali metal ions) may be used in combination; for example, cesium ions and formamidinium may be used in combination.

[0047] There are no particular restrictions on Z in the chemical formula (I) above, and it can be appropriately selected depending on the purpose. Examples include divalent metal ions such as lead, indium, antimony, tin, copper, bismuth, and germanium. These may be used individually or in combination of two or more. Lead is particularly preferred, and among these, the combination of lead and tin is particularly preferred.

[0048] As described above, the photoelectric conversion layer 14 may be formed from a perovskite compound. There are no particular restrictions on the method for forming such a perovskite layer, and an appropriate method can be selected depending on the purpose. For example, a method may be used in which a solution of metal halide and alkylamine halide is dissolved or dispersed is applied and then dried.

[0049] Furthermore, methods for forming the perovskite layer include, for example, dissolving a metal halide or After coating and drying the dispersed solution, immerse it in a solution containing dissolved alkylamine halogens. Examples include a two-step precipitation method for forming perovskite compounds.

[0050] Other methods for forming a perovskite layer include, for example, a method in which a solution containing dissolved or dispersed metal halides and alkylamine halides is applied while adding a poor solvent (solvent with low solubility) for the perovskite compound to precipitate crystals. Furthermore, another method for forming a perovskite layer is, for example, a method of depositing metal halides in a gas filled with methylamine.

[0051] A particularly preferred method for forming a perovskite layer is to coat a solution containing dissolved or dispersed metal halides and alkylamine halides while adding a poor solvent for the perovskite compound to precipitate crystals. There are no particular limitations on the method of coating these solutions, and they can be appropriately selected depending on the purpose. Examples include immersion, spin coating, spraying, dipping, roller coating, and air knife coating. Alternatively, the solution may be coated using a supercritical fluid such as carbon dioxide for precipitation. Examples of poor solvents used in the method of precipitating crystals by adding the poor solvents described above include 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; esters such as ethyl acetate, isobutyl acetate, and γ-butyrolactone; nitriles such as acetonitrile and 3-methoxypropionitrile; aromatic hydrocarbon compounds such as benzene, toluene, and chlorobenzene; halogenated solvents such as dichloromethane and chloroform; and fluorinated solvents such as chlorofluorocarbons, hydrochlorofluorocarbons, and hydrofluorocarbons.

[0052] As a method for forming the perovskite layer, for example, a step aimed at removing the solvent after forming the perovskite layer (solvent removal step) or a step aimed at arranging perovskite crystals may be performed. Examples of the solvent removal step and crystal arrangement step include blowing dry air, heating with a hot plate or oven, and vacuum drying. The heating temperature is preferably 50 to 200°C, and more preferably 70 to 180°C. The heating time is preferably 1 to 150 minutes, and more preferably 5 to 60 minutes. The thickness of the photoelectric conversion layer 14 is not particularly limited, but from the viewpoint of further suppressing performance degradation due to defects and peeling, for example, 50 to 1500 nm is preferred, and more preferably 200 to 1000 nm.

[0053] A method for forming a perovskite layer may include, for example, a surface treatment step (surface treatment step) using a salt formed from one or more cations and one or more anions. Examples of the cations 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-aminovaleric acid, metamine, ethylenediamine, p-xylylenediamine, m-xylylenediamine, and 1,2-adamantine. Examples of cations obtained from organic compounds having an amino group, such as tantanediamine, 1,3-adamantanediamine, N,N-dimethylethylenediamine, 1,3-diaminopropane, 1,4-diazabicyclo[2.2.2]octane, guanidine, aniline, pyrrole, imidazole, 1-ethylimidazole, 2-ethylimidazole, benzmidazole, morpholine, pyrrolidine, pyrazole, triazole, and carbazole; and heterocycles containing nitrogen atoms, such as pyridine, pyrazine, pyridazine, pyrimidine, quinoline, isoquinoline, phenanthroline, 2,2'-bipyridyl, and 4,4'-bipyridyl. Examples of the anions include halogen ions such as fluoride ions, chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; isocyanate ions, thiocyanate ions, tetrafluoroborate ions, hexafluorophosphate ions; and trifluoromethanesulfonylimide ions.

[0054] The salt comprising the cation and the anion is preferably soluble in one or more solvents. Examples of such solvents include alcohols such as isopropanol (2-propanol), ethanol (EtOH), methanol (MeOH), and butanol; nitriles such as acetonitrile and propionitrile; and aromatic solvents such as toluene, chlorobenzene, and 1,2-dichlorobenzene. One solvent may be used alone, or two or more may be used in combination.

[0055] The surface treatment step is carried out by applying a solution containing the dissolved salt onto the formed perovskite layer and drying it. There are no particular restrictions on the method of applying the solution, and it can be appropriately selected depending on the purpose. Examples include immersion, spin coating, spraying, dipping, roller coating, and air knife coating. Heat treatment may also be performed after application. If heating is performed, the heating temperature is preferably 50 to 200°C, and more preferably 70 to 180°C. The heating time is preferably 1 to 150 minutes, and more preferably 5 to 60 minutes. There are no particular restrictions on the thickness of the film to which the solution is applied.

[0056] [Second electrode 16] The second electrode 16 (which may be, for example, a back electrode) is a layer that has the function of extracting holes or electrons from the photoelectric conversion layer 14, for example, via a hole transport layer or an electron transport layer.

[0057] The second electrode 16 may be formed directly on the electron transport layer 15 in the case of an inverted structure as shown in Figure 1, or it may be formed directly on the hole transport layer 15 in the case of a forward structure in which the arrangement of the hole transport layer and the electron transport layer is reversed. Furthermore, the material of the second electrode 16 is not particularly limited, and for example, the same material as the first electrode 12 can be used. The shape, structure, and size of the second electrode 16 are not particularly limited and can be appropriately selected according to the purpose. Examples of materials for the second electrode 16 include metals, carbon compounds, conductive metal oxides, and conductive polymers. Examples of metals include platinum, gold, silver, copper, and aluminum. Examples of carbon compounds include graphite, fullerene, carbon nanotubes, and graphene. Examples of conductive metal oxides include ITO, IZO, FTO, and ATO. Examples of conductive polymers include polythiophene and polyaniline. Furthermore, the material used to form the second electrode 16 may be a single type or two or more types may be used in combination.

[0058] The second electrode 16 can be formed on the electron transport layer 15 or hole transport layer 15 by methods such as coating, laminating, vacuum deposition, CVD, sputtering, or bonding, depending on the type of material used and the type of electron transport layer 15 or hole transport layer 15.

[0059] Furthermore, in the photoelectric conversion module of this disclosure, it is preferable that at least one of the first electrode 12 and the second electrode 16 is substantially transparent. When using the photoelectric conversion module of this disclosure, it is preferable to make the electrodes transparent and allow incident light to enter from the electrode side. In this case, it is preferable to use a light-reflecting material for the back electrode (the electrode opposite to the transparent electrode, for example, the second electrode), and metals, glass with a conductive oxide deposited on it, plastics, metal thin films, etc., are preferably used. Providing an anti-reflective layer on the electrode on the incident light side is also an effective means.

[0060] Furthermore, as mentioned above, the configuration of the photoelectric conversion module in this disclosure is not limited to the configuration shown in Figure 1. Also, although the above description mainly described an example in which the first electrode 12 is a transparent electrode and the second electrode 16 is a back electrode, the photoelectric conversion module in this disclosure is not limited to this. For example, in the photoelectric conversion module in this disclosure, the opposite may be true: the first electrode may be a back electrode and the second electrode may be a transparent electrode.

[0061] The total thickness of the photoelectric conversion module disclosed herein can be appropriately changed depending on the thickness of the support material used.

[0062] [Sealed] The photoelectric conversion module (e.g., solar cell) disclosed herein is preferably sealed to protect the device from water and oxygen. The sealing structure is not particularly limited, but may be the same as that of a general photoelectric conversion module (e.g., solar cell). Specifically, for example, the sealing material may be applied only to the outer periphery of the photoelectric conversion module disclosed herein and covered with glass or film, the sealing material may be applied to the entire surface of the photoelectric conversion module disclosed herein and covered with glass or film, or the sealing material may be applied to the entire surface of the photoelectric conversion module disclosed herein without any sealing material.

[0063] There are no particular restrictions on the material of the sealing member, and it can be appropriately selected according to the purpose. For example, a film or glass sheet that has the function of suppressing the intrusion of moisture and the permeation of oxygen can be used. In addition, it is preferable to use epoxy resin or acrylic resin as the sealing member and cure it, but it is also acceptable if it is not cured or if only partially cured.

[0064] [wiring] In order to efficiently extract the current generated by light, it is preferable to connect lead wires (wirings) to the electrodes and back electrode of the photoelectric conversion module (e.g., solar cell) disclosed herein. The lead wires are connected to the first electrode and the second electrode using a conductive material such as solder, silver paste, or graphite. The conductive material may be used alone or in a mixture or laminated structure of two or more types. Furthermore, the area to which the lead wires are attached may be covered with an acrylic resin or epoxy resin for physical protection.

[0065] Lead wires are a general term for wires used to electrically connect power sources, electronic components, and other elements in electrical circuits. Examples include vinyl-coated wires and enameled wires.

[0066] [2. Method for manufacturing a photoelectric conversion module] The method for manufacturing the photoelectric conversion module of the present disclosure is not particularly limited, but for example, it can be manufactured as follows. Below, an example of the method for manufacturing the photoelectric conversion module of the present disclosure will be described using the process cross-sectional diagrams in Figures 2(a) to (i). The first electrode 12, hole transport layer 13, photoelectric conversion layer 14, electron transport layer 15, and second electrode 16 are not particularly limited, but for example, they are as described in [1. Photoelectric Conversion Module] above. Furthermore, the method for forming the first electrode 12, hole transport layer 13, photoelectric conversion layer 14, electron transport layer 15, and second electrode 16 is not particularly limited, and for example, they can be formed by the method described in [1. Photoelectric Conversion Module] above. Also, the method for removing a part of each layer in the P1 processing, P2.0 processing, P2.5 processing, and P3 processing described later is not particularly limited, but for example, laser processing may be used. The pulse energy for laser processing is not particularly limited and may be adjusted as appropriate, for example, by considering the processing range and depth of the layer being processed among the first electrode 12, hole transport layer 13, photoelectric conversion layer 14, electron transport layer 15, and second electrode 16. The pulse energy may be in the range of 1 to 100 μJ / pulse. The wavelength of the laser pulse is also not particularly limited, but may be wavelengths such as 355 nm, 532 nm, or 1064 nm. The diameter of the laser pulse is also not particularly limited, but may be the same diameter as each laser processing pattern, for example, a diameter of about 1 to 100 μm.

[0067] First, a support 11 is prepared as shown in Figure 2(a). Next, a first electrode 12, such as an ITO film, is formed on one surface of the support 11 as shown in Figure 2(b).

[0068] Furthermore, as shown in Figure 2(c), a first dividing groove 12A is formed in a part of the first electrode 12, extending from the upper surface of the first electrode 12 to the upper surface of the support 11. The process of forming this first dividing groove 12A shown in Figure 2(c) may be referred to as "P1 processing" in this disclosure. In P1 processing, the width of the first dividing groove 12A is not particularly limited, but may be, for example, 5 to 300 μm or 30 to 150 μm.

[0069] Next, as shown in Figure 2(d), a hole transport layer 13 and a photoelectric conversion layer 14 are formed in this order on the surface of the first electrode 12 opposite to the substrate 11.

[0070] Furthermore, as shown in Figure 2(e), a portion of the hole transport layer 13 and photoelectric conversion layer 14 is removed in areas other than the portion where the first dividing groove 12A is provided. This processing shown in Figure 2(e) may be referred to as "P2.0 processing" in this disclosure. In Figure 2(e), the area where the hole transport layer 13 and photoelectric conversion layer 14 have been removed by P2.0 processing corresponds to the "P2.0 region" in Figure 1. The width of the P2.0 region is not particularly limited, but may be, for example, 50 to 1500 μm or 60 to 300 μm. In addition, it is preferable that the side cross-section of the photoelectric conversion layer 14 exposed in the P2.0 region is formed in a sloping shape such that the width of the P2.0 region narrows as it approaches the first electrode 12. This sloping shape can be formed, for example, by adjusting the output of the laser processing and the patterning position to predetermined conditions.

[0071] Next, as shown in Figure 2(f), the electron transport layer 15 is formed to cover the upper surface of the photoelectric conversion layer 14, and in the P2.0 region, to cover the cross-sections of the hole transport layer 13 and the photoelectric conversion layer 14, and to cover the first electrode 12. This separates the photoelectric conversion layer 14 from the second electrode 16 that will be formed later, preventing direct contact. At this time, if the side cross-section of the photoelectric conversion layer 14 exposed in the P2.0 region has the aforementioned inclined shape, it is advantageous that the electron transport layer 15, which functions as an isolation layer, can be easily and reliably formed.

[0072] Furthermore, as shown in Figure 2(g), the electron transport layer 15 is removed in a portion of the P2.0 region, exposing the upper surface of the first electrode 12. This processing shown in Figure 2(g) may be referred to as "P2.5 processing" in this disclosure. In Figure 2(g), the region where the electron transport layer 15 has been removed by P2.5 processing corresponds to the "P2.5 region" in Figure 1. The width of the P2.5 region is not particularly limited, but may be, for example, 5 to 500 μm or 40 to 200 μm. If, for example, it is necessary to prevent significant damage to the first electrode 12 by P2 processing or P2.5 processing, a small amount of the photoelectric conversion layer 14 or the electron transport layer 15 as an isolation layer may remain in the conductive portion 20 to the extent that it does not affect conductivity.

[0073] Furthermore, as shown in Figure 2(h), a second electrode 16 is formed on the surface opposite to the support 11 in the electron transport layer 15 outside the P2.5 region and in the first electrode 12 of the P2.5 region. In the P2.5 region, as shown in the figure, the first electrode 12 and the second electrode 16 are in direct contact, forming a conductive portion 20 in which the first electrode 12 and the second electrode 16 are electrically conductive (Figure 2(i)).

[0074] Then, as shown in Figure 2(i), a second dividing groove 30 is formed in the portion other than the P2.0 region, extending from the upper surface of the second electrode 16 to the upper surface of the first electrode 12. The process of forming this second dividing groove 30 shown in Figure 2(i) is sometimes referred to as "P3 processing" in this disclosure. The diameter of the second dividing groove 30 formed by P3 processing is not particularly limited, but may be, for example, 5 to 300 μm or 40 to 150 μm.

[0075] As described above, the photoelectric conversion module of the present disclosure can be manufactured. Although the steps in Figures 2(a) to (i) have been briefly explained, they may be carried out in a manner similar to that of a general photoelectric conversion module. More specifically, each of the steps may be carried out in a manner similar to that described in [1. Photoelectric Conversion Module], or in a manner similar to that of the embodiments described later. Furthermore, as stated above, the method of manufacturing the photoelectric conversion module of the present disclosure is not limited to this, and any manufacturing method may be used. In addition, although the configuration of the photoelectric conversion module manufactured in Figures 2(a) to (i) is the same as the configuration shown in Figure 1, as stated above, the configuration of the photoelectric conversion module of the present disclosure is not limited to this.

[0076] [3. Applications and usage methods of photoelectric conversion modules] The applications and methods of use of the photoelectric conversion module disclosed herein are not particularly limited, and it can be widely used in the same applications as a general photoelectric conversion module (e.g., a general solar cell). The photoelectric conversion module disclosed herein (e.g., a solar cell) can be applied to a power supply device by combining it with, for example, a circuit board that controls the generated current. Examples of devices that utilize a power supply device include electronic desktop calculators and solar-powered radio-controlled watches. It is also possible to apply the photoelectric conversion module disclosed herein as a power supply device to mobile phones, electronic paper, thermometers and hygrometers, etc. Furthermore, it can be used as an auxiliary power supply to extend the continuous use time of rechargeable or battery-powered electrical appliances, or for nighttime use when combined with a secondary battery. It can also be used as a self-contained power supply that does not require battery replacement or power wiring. [Examples]

[0077] The following describes embodiments of this disclosure. However, this disclosure is not limited to the following embodiments.

[0078] [Example 1] The photoelectric conversion module described herein was manufactured as follows.

[0079] First, as shown in Figure 2(b), a laminate was prepared in which ITO (transparent electrode) was formed as the first electrode 12 on a glass substrate (support) 11. Next, as shown in Figure 1(c), a part of the first electrode 12 was removed using a laser processing device to form a through hole 12A (P1 processing). In this embodiment, the first electrode 12 was formed in multiple strip shapes by forming multiple through holes 12A in a groove-like manner in equilibrium. A schematic diagram of this state is shown in Figure 3. Figure 3(a) is a plan view, and Figure 3(b) is a cross-sectional view.

[0080] Next, an N,N-dimethylformamide (DMF) solution containing the compound shown in the following chemical formula (Chemical Formula 3-PATAT-C3) (0.1 mmol / L) was placed on the side of the first electrode 12 opposite to the glass substrate 11, coated using a spin coater (3000 rpm, 30 seconds), and then heated and dried on a hot plate at 100°C for 10 minutes to form a single-molecule hole transport layer 13 as shown in Figure 2(d).

[0081] [ka]

[0082] Next, a solution of 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) dissolved in DMF (40.0 mL) and dimethyl sulfoxide (DMSO, 12.0 mL) was applied to the single-molecule hole transport layer 13 using spin coating to form a film. The spin coating was performed at a rotation speed of 3000 rpm, and chlorobenzene (0.3 mL) was dropped onto the coating layer of the substrate 30 seconds after the start. After that, it was heated at 150°C for 10 minutes to form a perovskite layer, which is the photoelectric conversion layer 14, as shown in Figure 2(d).

[0083] Next, as shown in Figure 2(e), a portion of the hole transport layer 13 and photoelectric conversion layer 14 in the region adjacent to the first dividing groove 12A was removed by laser processing (P2.0 processing). In this embodiment, the P2.0 region from which the hole transport layer 13 and photoelectric conversion layer 14 were removed by P2.0 processing was formed parallel to the first dividing groove 12A. Furthermore, the side cross-section of the photoelectric conversion layer 14 exposed in the P2.0 region was formed in a sloping shape such that the width of the P2.0 region narrows as it approaches the first electrode 12. This sloping shape was formed by adjusting the laser processing output and patterning position to predetermined conditions.

[0084] Furthermore, as shown in Figure 2(f), the electron transport layer 15 was formed to cover the upper surface of the photoelectric conversion layer 14, and in the P2.0 region, to cover the side cross-sections of the hole transport layer 13 and the photoelectric conversion layer 14, and to cover the first electrode 12. This separated the photoelectric conversion layer 14 from the second electrode 16 that would be formed later, so that they would not come into direct contact. In this embodiment, the electron transport layer 15 was formed first C 60 This was done by depositing a 20 nm thick layer of (fullerene) followed by an 8 nm thick layer of BCP (basocuproine) using vacuum deposition.

[0085] Furthermore, as shown in Figure 2(g), the electron transport layer 15 was removed in a portion of the P2.0 region using a laser processing device, exposing the upper surface of the first electrode 12 (P2.5 processing). This P2.5 processing formed a P2.5 region from which the electron transport layer 15 had been removed.

[0086] Furthermore, as shown in Figure 2(h), a second electrode 16 was formed on the surface opposite to the support 11 by vacuum deposition, creating a uniform layer of Cu (copper) with a thickness of 70 nm. As a result, in the P2.5 region, the first electrode 12 and the second electrode 16 are in direct contact, forming a conductive portion 20 that allows the first electrode 12 and the second electrode 16 to conduct electricity (Figure 2(i)).

[0087] Then, as shown in Fig. 2(i), a second dividing trench reaching from the upper surface of the second electrode 16 in the region opposite to the first dividing trench P1 across the P2.0 region to the upper surface of the first electrode 12 was formed using a laser processing apparatus (P3 processing).

[0088] As described above, the photoelectric conversion module of the present disclosure in this example was manufactured. The outline of the overall structure of the photoelectric conversion module of this example is schematically shown in FIG. 4. FIG. 4(a) is a plan view, and FIG. 4(b) is a cross-sectional view. Note that in FIG. 4, the hole transport layer 13 and the electron transport layer 15 are omitted for simplification of illustration.

[0089] [Examples 2 to 4] A photoelectric conversion module of the present disclosure was manufactured in the same manner as in Example 1, except that the pattern of P2.5 processing in the P2.0 region was changed, and the shape of the conductive portion 20 (P2.5 region) was changed from the linear shape of Example 1 to a staggered shape (Example 2), a dot shape (Example 3), and a line+dot shape (Example 4).

[0090] The formation patterns of the conductive portions 20 of Examples 1 to 4 are summarized in Table 1 below. In Table 1 below, "Contact area (mm 2 / step)" represents the actual area of the conductive portion in one P2.0 region (mm 2 ), that is, the connection area between the first electrode and the second electrode. When there are a plurality of conductive portions in one P2.0 region (for example, in Examples 2 to 4), the contact area is the sum of the areas of the plurality of conductive portions. In addition, the plan view of FIG. 5 shows the outline of the configuration of the P2.0 region and the P2.5 region in that region in each of the photoelectric conversion modules of Examples 1 to 4. FIG. 5(a) shows Example 1, FIG. 5(b) shows Example 2, FIG. 5(c) shows Example 3, and FIG. 5(d) shows Example 4, respectively. In each figure, the reference sign "P2.0" represents the P2.0 region, and "P2.5(20)" represents the conductive portion 20, that is, the P2.5 region.

[0091] [Table 1]

[0092] [Comparative Example 1] A photoelectric conversion module 10a with the configuration shown in Figure 4 was manufactured in the same manner as in Example 1, except that P2.0 processing was not performed, and instead, after the formation of the photoelectric conversion layer 15, a portion of the hole transport layer 13, the photoelectric conversion layer 14, and the electron transport layer 15 was removed by laser processing.

[0093] [Characterization of Photoelectric Conversion Modules] The photoelectric conversion modules of the examples and comparative examples manufactured as described above were evaluated for their respective characteristics. Specifically, degradation was accelerated by continuous irradiation of high-intensity simulated sunlight (equivalent to 2 SUNs) for 7 hours in a high-temperature environment (module surface temperature: approximately 80°C), and evaluation was performed using the following two methods, (1) and (2), to evaluate the characteristics before (initial) light irradiation and the characteristics after light irradiation. (1) Measure the resistance value through the conductive part using a tester. (2) Measure the amount of power generated after light irradiation due to differences in the conductive part formation pattern.

[0094] Table 2 below shows the value of the connection resistance value after light irradiation as a ratio (initial ratio) to the value before light irradiation (initial), which represents the rate of increase in connection resistance. Table 3 below shows the value of the power generation amount after light irradiation as a ratio (initial ratio) to the value before light irradiation (initial), which represents the rate of decrease in power generation characteristics.

[0095] [Table 2]

[0096] [Table 3]

[0097] As shown in Tables 2 and 3 above, it was confirmed that the degradation of characteristics was suppressed in all of the photoelectric conversion modules of the examples by suppressing the reaction between the photoelectric conversion layer and the second electrode. On the other hand, the photoelectric conversion module of the comparative example showed a significant degradation in characteristics compared to the photoelectric conversion module of the examples. Specifically, as shown in Table 2 above, the resistance value of the comparative example's photoelectric conversion module doubled after light irradiation. This is presumed to be because migration etc. was accelerated by photothermal energy, making it difficult to obtain a stable connection at the conductive part. In contrast, as shown in Table 2 above, the increase in connection resistance value was relatively small in all of the photoelectric conversion modules of the examples. Furthermore, there was no significant difference in the power generation characteristics (power generation amount) between the examples and the comparative example at the initial value. However, as shown in Table 3 above, as a result of the photothermal acceleration test, the photoelectric conversion module of the examples showed less degradation in power generation characteristics than the photoelectric conversion module of the comparative example. This is presumed to be because the connection at the conductive part is stable in the photoelectric conversion module of the examples. In addition, the same effect as Examples 2 and 3 was obtained for Example 4. By making the P2.5 processing shape a staggered or dotted pattern, the boundary line around the periphery of the conductive portion 20 becomes a partially independent non-linear shape or is formed by multiple curves. If the boundary line around the periphery of the conductive portion 20 is linear, it is conceivable that stress applied to the second electrode 16 would cause partial shearing along the boundary line, increasing the resistance value. However, by making the P2.5 processing shape a staggered or dotted pattern, thereby forming the boundary line around the periphery of the conductive portion 20 into a partially independent non-linear shape or by multiple curves, this partial shearing is thought to be suppressed.

[0098] The present disclosure has been described above using embodiments and examples. However, the present disclosure is not limited to the embodiments and examples described above, and may be combined, modified, or selected as necessary and appropriate, without departing from the spirit of the present disclosure.

[0099] <Note> The above embodiments and some or all of the examples may also be described as follows, but are not limited to these. (Note 1) A photoelectric conversion module, It includes a first electrode, a photoelectric conversion layer, a second electrode, and an isolation layer. The photoelectric conversion layer is disposed between the first electrode and the second electrode, The isolation layer is placed between the photoelectric conversion layer and the second electrode, and the isolation layer separates the photoelectric conversion layer and the second electrode so that they do not come into direct contact. A conductive portion is provided between the first electrode and the second electrode, where the photoelectric conversion layer and the isolation layer are absent. A photoelectric conversion module characterized in that, in the conductive portion, the first electrode and the second electrode are in contact either directly or via an electrical conductor, thereby causing the first electrode and the second electrode to be electrically conductive. (Note 2) The first electrode and the second electrode are each divided into multiple parts, A plurality of strip-shaped cells are formed by the first electrode and the second electrode facing each other, and the components of the photoelectric conversion module arranged between them. The first and second electrodes of adjacent strip-shaped cells are electrically connected by the conductive portion, so that the first and second electrodes are connected in series in the direction in which the plurality of strip-shaped cells are adjacent to each other. The photoelectric conversion module described in Appendix 1. (Note 3) It includes an electron transport layer and a hole transport layer, The isolation layer disposed between the photoelectric conversion layer and the second electrode is one of the electron transport layer and the hole transport layer. The electron transport layer and the other hole transport layer are arranged between the first electrode and the photoelectric conversion layer. In the conductive portion, the photoelectric conversion layer, the electron transport layer, and the hole transport layer are absent. Photoelectric conversion module as described in Appendix 1 or 2. (Note 4) The hole transport layer is provided between the photoelectric conversion layer and the first electrode. The electron transport layer is provided between the photoelectric conversion layer and the second electrode. The photoelectric conversion module described in Appendix 3. (Note 5) The photoelectric conversion layer is a photoelectric conversion module according to any one of the appendices 1 to 4, comprising a perovskite compound. (Note 6) The photoelectric conversion module according to Appendix 5, wherein the perovskite compound is a compound having a perovskite structure represented by the following chemical formula (I). X α Y β Z γ (I) In the above chemical formula (I), X is a halogen ion, Y is a monovalent cation, and Z is a divalent cation. The ratio of α:β:γ is 3:(0.95~1.05):(0.95~1.05). (Note 7) The photoelectric conversion module according to Appendix 6, wherein the monovalent cation represented by Y in the chemical formula (I) comprises at least one cation selected from the group consisting of cesium cation, rubidium cation, potassium cation, methylammonium cation, and formamidinium cation. (Note 8) The aforementioned conductive portion is multiple, The photoelectric conversion module according to any one of the appendices 1 to 7, wherein the plurality of conductive parts are arranged at intervals from each other along a predetermined direction. (Note 9) A photoelectric conversion module, which is a solar cell, as described in any of the appendices 1 to 8. (Note 10) A method for manufacturing a photoelectric conversion module, The photoelectric conversion module includes a first electrode, a photoelectric conversion layer, a second electrode, and an isolation layer. The method for manufacturing the photoelectric conversion module includes a photoelectric conversion layer formation step, a photoelectric conversion layer partial removal step, an isolation layer formation step, an isolation layer partial removal step, and a second electrode formation step. The photoelectric conversion layer formation step is a step of forming the photoelectric conversion layer on the first electrode, The photoelectric conversion layer partial removal step is a step of removing a part of the photoelectric conversion layer to expose a part of the first electrode, The isolation layer formation step is a step of forming the isolation layer on the photoelectric conversion layer and on the exposed portion of the first electrode after the partial removal step of the photoelectric conversion layer. The aforementioned isolation layer partial removal step is a step of removing the isolation layer from a part of the first electrode to expose a part of the first electrode again. The second electrode formation step is a step in which, after the partial removal of the isolation layer, the second electrode is formed in contact with the isolation layer and the first electrode, but not in contact with the photoelectric conversion layer. A manufacturing method characterized by the following features. (Note 11) The manufacturing method according to Appendix 10, wherein the photoelectric conversion module to be manufactured is a photoelectric conversion module described in any of Appendix 1 to 9. [Industrial applicability]

[0100] As described above, this disclosure provides a photoelectric conversion module in which the degradation of characteristics is suppressed by suppressing the reaction between the photoelectric conversion layer and the second electrode, and a method for manufacturing the photoelectric conversion module. The photoelectric conversion module of this disclosure is useful, for example, as a solar cell. The applications and methods of use of the photoelectric conversion module of this disclosure are not particularly limited and can be applied to a wide range of fields in the same applications and methods as a general photoelectric conversion module (for example, a general solar cell). [Explanation of Symbols]

[0101] 10, 10a Photoelectric Conversion Module 11 Support 12 First electrode 12A through hole 13 Hole transport layer 14 Photoelectric conversion layer 15 Electron transport layer 16. Second electrode 20 Conductive section 30 Through holes P2.0 P2.0 area P2.5 P2.5 area

Claims

1. A photoelectric conversion module, It includes a first electrode, a photoelectric conversion layer, a second electrode, and an isolation layer. The photoelectric conversion layer is disposed between the first electrode and the second electrode, The isolation layer is placed between the photoelectric conversion layer and the second electrode, and the isolation layer separates the photoelectric conversion layer and the second electrode so that they do not come into direct contact. A conductive portion is provided between the first electrode and the second electrode, where the photoelectric conversion layer and the isolation layer are absent. A photoelectric conversion module characterized in that, in the conductive portion, the first electrode and the second electrode are in contact either directly or via an electrical conductor, thereby causing the first electrode and the second electrode to be electrically conductive.

2. The first electrode and the second electrode are each divided into multiple parts. A plurality of strip-shaped cells are formed by the first electrode and the second electrode facing each other, and the components of the photoelectric conversion module arranged between them. The first and second electrodes of adjacent strip-shaped cells are electrically connected by the conductive portion, so that the first and second electrodes are connected in series in the direction in which the plurality of strip-shaped cells are adjacent to each other. The photoelectric conversion module according to claim 1.

3. It includes an electron transport layer and a hole transport layer, The isolation layer disposed between the photoelectric conversion layer and the second electrode is one of the electron transport layer and the hole transport layer. The electron transport layer and the other hole transport layer are arranged between the first electrode and the photoelectric conversion layer. In the conductive portion, the photoelectric conversion layer, the electron transport layer, and the hole transport layer are absent. The photoelectric conversion module according to claim 1.

4. The hole transport layer is provided between the photoelectric conversion layer and the first electrode. The electron transport layer is provided between the photoelectric conversion layer and the second electrode. The photoelectric conversion module according to claim 3.

5. The photoelectric conversion module according to claim 1, wherein the photoelectric conversion layer comprises a perovskite compound.

6. A method for manufacturing a photoelectric conversion module, The photoelectric conversion module includes a first electrode, a photoelectric conversion layer, a second electrode, and an isolation layer. The method for manufacturing the photoelectric conversion module includes a photoelectric conversion layer formation step, a photoelectric conversion layer partial removal step, an isolation layer formation step, an isolation layer partial removal step, and a second electrode formation step. The photoelectric conversion layer formation step is a step of forming the photoelectric conversion layer on the first electrode, The photoelectric conversion layer partial removal step is a step of removing a part of the photoelectric conversion layer to expose a part of the first electrode, The isolation layer formation step is a step of forming the isolation layer on the photoelectric conversion layer and on the exposed portion of the first electrode after the partial removal step of the photoelectric conversion layer. The aforementioned isolation layer partial removal step is a step of removing the isolation layer from a part of the first electrode to expose a part of the first electrode again. The second electrode formation step is a step in which, after the partial removal of the isolation layer, the second electrode is formed in contact with the isolation layer and the first electrode, but not in contact with the photoelectric conversion layer. A manufacturing method characterized by the following features.

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