Solar cell modules, electronic devices, and power modules

Abstract

A solar cell module (100) comprises: a first substrate (1); a plurality of photoelectric conversion elements (a, b) arranged on the first substrate (1), each of the plurality of photoelectric conversion elements (a, b) comprising a first electrode (2a, 2b), an electron transport layer (3), a perovskite layer (5), a hole transport layer (6) and a second electrode (7a, 7b), wherein in at least two photoelectric conversion elements (a, b) adjacent to each other, the hole transport layer (6) is an extended continuous layer, and wherein the first electrode (2a, 2b), the electron transport layer (3) and the perovskite layer (5) in the at least two photoelectric conversion elements (2a, 2b) adjacent to each other are separated by the hole transport layer (6), and the hole transport layer (6) comprises a polymer having a weight average molecular weight of 2,000 or more or a compound having a molecular weight of 2,000 or more as a hole transport material.

Description

Technical Field

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

[0002] In recent years, solar cells using photoelectric conversion elements are expected to be widely used, not only to replace fossil fuels and combat global warming, but also as independent power sources that require no battery replacement or power wiring. Furthermore, solar cells as independent power sources are attracting attention as one of the energy harvesting technologies required for Internet of Things (IoT) devices and artificial satellites.

[0003] Examples of solar cells include organic solar cells such as dye-sensitized solar cells, organic thin-film solar cells, and perovskite solar cells, and inorganic solar cells using silicon, which have been widely and conventionally used.

[0004] Perovskite solar cells are advantageous in terms of improving safety and suppressing production costs because they can be produced with conventional existing printing units without using electrolytes containing, for example, organic solvents.

[0005] Regarding organic thin-film solar cells and perovskite solar cells, it is known that a plurality of spatially separated photoelectric conversion elements are electrically connected to form a series circuit in order to increase the output voltage (see, for example, PTL 1). [Citation List]

[0006] [Patent Document]

[0007] [PTL1]

[0008] Japanese Unexamined Patent Application Publication No. 2016-195175. Summary of the Invention

[0009] [Technical Issues]

[0010] An object of the present disclosure is to provide a solar cell module capable of maintaining power generation efficiency even after being exposed to light with high illuminance for a long period of time.

[0011] [Technical solution to the problem]

[0012] According to one aspect of the present disclosure, a solar cell module includes: a first substrate; and a plurality of photoelectric conversion elements arranged on the first substrate. Each of the plurality of photoelectric conversion elements includes a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode. In at least two photoelectric conversion elements adjacent to each other, the hole transport layer is an extended continuous layer. The first electrode, the electron transport layer, and the perovskite layer in at least two photoelectric conversion elements adjacent to each other are separated by a hole transport layer. The hole transport layer includes a polymer having a weight average molecular weight of 2,000 or greater or a compound having a molecular weight of 2,000 or greater as a hole transport material.

[0013] [Beneficial Effects of the Invention]

[0014] According to the present disclosure, it is possible to provide a solar cell module capable of maintaining power generation efficiency even after long-term exposure to light with high illuminance. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 is an explanatory view showing one example of the structure of the solar cell module of the present disclosure.

[0016] Figure 2 is an explanatory view showing another example of the structure of the solar cell module of the present disclosure.

[0017] Figure 3 is an explanatory view showing another example of the structure of the solar cell module of the present disclosure.

[0018] Figure 4 is an explanatory view showing another example of the structure of the solar cell module of the present disclosure.

[0019] Figure 5 is an explanatory view showing another example of the structure of the solar cell module of the present disclosure.

[0020] Figure 6 is a block diagram of a mouse for a personal computer as one example of the electronic device of the present disclosure.

[0021] Figure 7 It is presented Figure 6 Schematic external view of one example of a mouse presented in .

[0022] Figure 8 is a block diagram of a keyboard for a personal computer as one example of the electronic device of the present disclosure.

[0023] Figure 9 It is presented Figure 8 Schematic external view of an example of a keyboard presented in .

[0024] Figure 10 It is presented Figure 8 A schematic external view of another example of a keyboard is presented in FIG.

[0025] Figure 11 is a block diagram of a sensor as an example of the electronic device of the present disclosure.

[0026] Figure 12 is a block diagram of a turntable as an example of the electronic device of the present disclosure.

[0027] Figure 13 is a block diagram illustrating one example of an electronic device of the present disclosure.

[0028] Figure 14 is presented where the power IC is further incorporated into Figure 13 A block diagram of an example of an electronic device is presented in FIG.

[0029] Figure 15 is presented wherein the power storage device is further incorporated into Figure 14 A block diagram of an example of an electronic device is presented in FIG.

[0030] Figure 16 is a block diagram presenting one example of a power module of the present disclosure.

[0031] Figure 17 is presented wherein the power storage device is further incorporated into Figure 16 A block diagram of an example of a power module is presented in FIG. DETAILED DESCRIPTION

[0032] (Solar cell module)

[0033] The solar cell module of the present disclosure includes: a first substrate; and a plurality of photoelectric conversion elements arranged on the first substrate. Each of the plurality of photoelectric conversion elements includes a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode. In at least two photoelectric conversion elements adjacent to each other, the hole transport layer is an extended continuous layer, and the first electrode, the electron transport layer, and the perovskite layer in at least two photoelectric conversion elements adjacent to each other are separated by the hole transport layer. The hole transport layer includes a polymer having a weight average molecular weight of 2,000 or more or a compound having a molecular weight of 2,000 or more as a hole transport material.

[0034] The solar cell module disclosed herein is based on the discovery that conventional solar cell modules with perovskite layers experience a sharp decrease in power generation efficiency after prolonged exposure to high-intensity light. Specifically, in conventional solar cell modules with perovskite layers, since the porous titanium oxide layer or perovskite layer is extended, this configuration causes a large amount of electron recombination through diffusion, leading to a sharp decrease in power generation efficiency after prolonged exposure to high-intensity light, which is problematic.

[0035] As another problem, since the adhesion between the hole transport layer and the second electrode is low, the hole transport layer and the second electrode are peeled off, which is problematic in terms of long-term durability.

[0036] At the same time, for the solar cell module of the present disclosure, the hole transport layer is an extended continuous layer, and the first electrode, the electron transport layer, and the perovskite layer in at least two adjacent photoelectric conversion elements are separated by the hole transport layer. Therefore, in the solar cell module of the present disclosure, the first electrode, the porous titanium oxide layer, and the perovskite layer are separated by the hole transport layer, and the hole transport layer includes a polymer with a weight average molecular weight of 2,000 or more or a compound with a molecular weight of 2,000 or more as a hole transport material. As a result, due to less electron recombination caused by diffusion, the power generation efficiency can be maintained even under long-term exposure to high-intensity light, and the durability is greatly improved.

[0037] The solar cell module of the present disclosure includes a first substrate and a plurality of photoelectric conversion elements provided on the first substrate, preferably further includes a second substrate different from the above substrate and a sealing member, and further includes other members if necessary.

[0038] <Substrate>

[0039] The shape, structure, and size of the first substrate are not particularly limited and can be appropriately selected depending on the intended purpose.

[0040] The material of the first substrate is not particularly limited and can be appropriately selected according to the intended purpose as long as it has translucency and insulation. Examples of materials include glass, plastic film and ceramic. Among them, in the case of a baking step for forming an electron transport layer described below, it is preferred that the material has heat resistance to the baking temperature. In addition, preferred examples of the first substrate include those having flexibility.

[0041] <Photoelectric Conversion Element>

[0042] The photoelectric conversion element refers to an element capable of converting light energy into electric energy, and is applied to, for example, solar cells and photodiodes.

[0043] The photoelectric conversion element of the present disclosure includes at least a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode.

[0044] <<First Electrode>>

[0045] The shape and size of the first electrode are not particularly limited and can be appropriately selected depending on the intended purpose, as long as the first electrodes in at least two photoelectric conversion elements adjacent to each other are separated by a hole transport layer to be described below.

[0046] The structure of the first electrode is not particularly limited and can be appropriately selected depending on the intended purpose.The structure of the first electrode may be a single-layer structure or a structure in which a plurality of materials are laminated.

[0047] The material of the first electrode is not particularly limited and can be appropriately selected depending on the intended purpose, as long as the material is a material having conductivity. Examples of the material include transparent conductive metal oxides, carbon, and metals.

[0048] Examples of transparent conductive metal oxides include indium tin oxide (hereinafter referred to as "ITO"), fluorine-doped tin oxide (hereinafter referred to as "FTO"), antimony-doped tin oxide (hereinafter referred to as "ATO"), niobium-doped tin oxide (hereinafter referred to as "NTO"), aluminum-doped zinc oxide, indium zinc oxide and niobium titanium oxide.

[0049] Examples of carbon include carbon black, carbon nanotubes, graphene, and fullerene.

[0050] Examples of metals include gold, silver, aluminum, nickel, indium, tantalum, and titanium.

[0051] These can be used alone or in combination. Among them, transparent conductive metal oxides having high transparency are preferred, and ITO, FTO, ATO, and NTO are more preferred.

[0052] The average thickness of the first electrode is not particularly limited and can be appropriately selected according to the intended purpose. The average thickness of the first electrode is preferably 5 nm or more and 100 μm or less, more preferably 50 nm or more and 10 μm or less. When the material of the first electrode is carbon or metal, the average thickness of the first electrode is preferably an average thickness sufficient to obtain translucency.

[0053] The first electrode can be formed by a known method such as sputtering, vapor deposition, spraying, or the like.

[0054] In addition, the first electrode is preferably formed on the first substrate. An integrated commercial product in which the first electrode is pre-formed on the first substrate can be used.

[0055] Examples of integrated commercial products include FTO-coated glass, ITO-coated glass, zinc oxide / aluminum-coated glass, FTO-coated transparent plastic films, and ITO-coated transparent plastic films. Other examples of integrated commercial products include: glass substrates provided with transparent electrodes in which tin oxide or indium oxide is doped with cations or anions having different atomic values; and glass substrates provided with metal electrodes having a structure that allows light to pass through in a mesh or stripe form.

[0056] These can be used alone, or two or more products can be combined as a combination product or laminate. In addition, in order to reduce the resistance value, metal leads can be used in combination.

[0057] The material of the metal lead is, for example, aluminum, copper, silver, gold, platinum, or nickel.

[0058] The metal wires may be used in combination, formed on the substrate by, for example, vapor deposition, sputtering, pressing, and providing a layer of ITO or FTO on the substrate, or by forming them on ITO or FTO.

[0059] <<Electron Transport Layer>>

[0060] The electron transport layer is a layer that transports electrons generated in the perovskite layer described below to the first electrode. Therefore, the electron transport layer is preferably provided adjacent to the first electrode.

[0061] The shape and size of the electron transport layer are not particularly limited and can be appropriately selected depending on the intended purpose, as long as the electron transport layers in at least two photoelectric conversion elements adjacent to each other are separated by a hole transport layer to be described below.

[0062] When the electron transport layers in at least two adjacent photoelectric conversion elements are separated by a hole transport layer, electron diffusion is prevented to reduce current leakage. As a result, light durability can be improved.

[0063] The structure of the electron transport layer may be a single layer or a multilayer formed by laminating a plurality of layers. However, its structure is preferably a multilayer. Its structure is more preferably formed by a layer having a dense structure (dense layer) and a layer having a porous structure (porous layer). In addition, the dense layer is preferably provided closer to the first electrode than the porous layer.

[0064] -Dense layer-

[0065] The dense layer is not particularly limited and can be appropriately selected according to the intended purpose as long as it includes an electron transport material and is denser than the porous layer to be described below. Here, denser than the porous layer means that the bulk density of the dense layer is higher than the bulk density of particles forming the porous layer.

[0066] The electron transport material is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably a semiconductor material.

[0067] The semiconductor material is not particularly limited, and known materials can be used. Examples of the semiconductor material include simple semiconductors and compounds with compound semiconductors.

[0068] Examples of elemental semiconductors include silicon and germanium.

[0069] Examples of compound semiconductors include metal chalcogenides. Specific examples include oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum; sulfides of cadmium, zinc, lead, silver, antimony, and bismuth; selenides of cadmium and lead; and cadmium telluride. Other examples of compound semiconductors include phosphides of zinc, gallium, indium, and cadmium; gallium arsenide; copper indium selenide; and copper indium sulfide.

[0070] Among them, oxide semiconductors are preferable, and particularly, more preferable ones include titanium oxide, zinc oxide, tin oxide, and niobium oxide.

[0071] These can be used alone or in combination. In addition, the crystal type of the semiconductor material is not particularly limited and can be appropriately selected according to the intended purpose. Its crystal type can be single crystal, polycrystalline or amorphous.

[0072] The film thickness of the dense layer is not particularly limited and can be appropriately selected depending on the intended purpose.The film thickness of the dense layer is preferably 5 nm or more and 1 μm or less, more preferably 10 nm or more and 700 nm or less.

[0073] The method for producing the dense layer is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the method include a method of forming a thin film under vacuum (vacuum film forming method) and a wet film forming method.

[0074] Examples of the vacuum film formation method include sputtering, pulsed laser deposition (PLD), ion beam sputtering, ion-assisted deposition, ion plating, vacuum deposition, atomic layer deposition (ALD), and chemical vapor deposition (CVD).

[0075] Examples of wet film-forming methods include sol-gel methods. The sol-gel method is the following method. Specifically, a solution is subjected to a chemical reaction such as hydrolysis or polymerization condensation to prepare a gel. Then, it is heat-treated to promote densification. When the sol-gel method is used, the method for applying the sol solution is not particularly limited and can be appropriately selected according to the intended purpose. Examples include dipping, spraying, wire rod coating, spin coating, roller coating, blade coating, gravure coating, and wet printing methods such as relief printing, offset printing, gravure printing (gravure printing), intaglio printing (intaglioprinting), rubber plate printing, and screen printing. The temperature for heat treatment after applying the sol solution is preferably 80°C or higher, more preferably 100°C or higher.

[0076] -Porous layer-

[0077] The porous layer is not particularly limited and can be appropriately selected according to the intended purpose as long as it is a layer containing an electron transport material and being less dense (i.e., porous) than the dense layer. Note that “less dense than the dense layer” means that the bulk density of the porous layer is lower than that of the dense layer.

[0078] The electron transport material is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably a semiconductor material similar to that in the case of the dense layer. As the semiconductor material, the same materials as those used in the dense layer can be used.

[0079] Furthermore, the electron transport material constituting the porous layer has a particle form, and these particles are preferably combined to form a porous film.

[0080] The number average particle diameter of the primary particles of electron transport material is not particularly limited, and can be appropriately selected according to the intended purpose. Its number average particle diameter is preferably 1nm or larger and 100nm or smaller, more preferably 10nm or larger and 50nm or smaller. In addition, the semiconductor material with a granularity larger than the number average particle diameter can be mixed or laminated. Due to the effect of scattered incident light, conversion efficiency can be improved using this semiconductor material. In this case, its number average particle diameter is preferably 50nm or larger and 500nm or larger.

[0081] As the electron transport material in the porous layer, titanium oxide particles can be appropriately used. When the electron transport material in the porous layer is titanium oxide particles, the conduction band is high, which makes it possible to obtain a high open circuit voltage. When the electron transport material in the porous layer is titanium oxide particles, the refractive index is high, and due to the effect of limiting light, a high short-circuit current can be obtained. In addition, when the electron transport material in the porous layer is titanium oxide particles, this is advantageous because the dielectric constant of the porous layer becomes higher and the mobility of the electrons becomes higher to obtain a high filling factor (form factor). That is, the electron transport layer preferably includes a porous layer containing titanium oxide particles, because the open circuit voltage and the filling factor can be improved.

[0082] The average thickness of the porous layer is not particularly limited and can be appropriately selected depending on the intended purpose. The average thickness thereof is preferably 30 nm or more and 1 μm or less, more preferably 100 nm or more and 600 nm or less.

[0083] In addition, the porous layer may include a multilayer structure. A porous layer having a multilayer structure may be prepared by applying a dispersion of particles of an electron transport material having different particle sizes multiple times, or by applying a dispersion of electron transport materials, resins, and additives having different formulations multiple times. When adjusting the average thickness (film thickness) of the porous layer, applying a dispersion of particles of an electron transport material multiple times is effective.

[0084] The method for producing the porous layer is not particularly limited and can be appropriately selected according to the intended purpose. Examples of the method include immersion, spin coating, spray coating, dipping, roller coating, and air knife coating. As a method for producing the porous layer, a precipitation method using a supercritical fluid such as carbon dioxide can be used.

[0085] The method for producing particles of the electron transport material is, for example, a mechanical pulverization method using a known grinding device. By this method, a dispersion of the semiconductor material can be prepared by dispersing the electron transport material in the form of individual particles or a mixture of the semiconductor material and a resin in water or a solvent.

[0086] Examples of the resin include polymers or copolymers of vinyl compounds (e.g., styrene, vinyl acetate, acrylate, and methacrylate), silicone resins, phenoxy resins, polysulfone resins, polyvinyl butyral resins, polyvinyl formal resins, polyester resins, cellulose ester resins, cellulose ether resins, polyurethane resins, phenolic resins, epoxy resins, polycarbonate resins, polyarylate resins, polyamide resins, and polyimide resins. These may be used alone or in combination.

[0087] Examples of the solvent include water, alcohol solvents, ketone solvents, ester solvents, ether solvents, amide solvents, halogenated hydrocarbon solvents, and hydrocarbon solvents.

[0088] Examples of the alcohol solvent include methanol, ethanol, isopropanol, and α-terpineol.

[0089] Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0090] Examples of the ester solvent include ethyl formate, ethyl acetate, and n-butyl acetate.

[0091] Examples of the ether solvent include diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane and dioxane.

[0092] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0093] Examples of the halogenated hydrocarbon solvent include dichloromethane, chloroform, bromoform, iodomethane, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene and 1-chloronaphthalene.

[0094] Examples of the hydrocarbon solvent include n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene.

[0095] These may be used alone or in combination.

[0096] An acid, a surfactant, or a chelating agent may be added to a dispersion containing an electron transport material or a paste containing an electron transport material obtained by, for example, a sol-gel method to prevent reaggregation of particles.

[0097] Examples of the acid include hydrochloric acid, nitric acid, and acetic acid.

[0098] Examples of the surfactant include polyoxyethylene octylphenyl ether.

[0099] Examples of chelating agents include acetylacetone, 2-aminoethanol, and ethylenediamine.

[0100] In addition, adding thickener is also an effective means to improve film-forming ability.

[0101] Examples of thickeners include polyethylene glycol, polyvinyl alcohol, and ethylcellulose.

[0102] After the electron transport material is applied, the particles of the electron transport material can be brought into electronic contact with each other and then subjected to baking, microwave or electron beam irradiation, or laser irradiation to improve the strength of the film and adhesion to the substrate. These treatments can be performed alone or in combination.

[0103] When baking the porous layer formed of the electron transport material, the baking temperature is not particularly limited and can be appropriately selected according to the intended purpose. However, the baking temperature is preferably 30°C or higher and 700°C or lower, more preferably 100°C or higher and 600°C or lower. When the baking temperature is 30°C or higher and 700°C or lower, the porous layer can be baked while preventing the resistance value of the first substrate from increasing and preventing the first substrate from melting. The baking time is not particularly limited and can be appropriately selected according to the intended purpose, but is preferably 10 minutes or longer and 10 hours or shorter.

[0104] When the porous layer formed of the electron transport material is irradiated with microwaves, the irradiation time is not particularly limited and can be appropriately selected according to the intended purpose, but is preferably 1 hour or less. In this case, light can be emitted from the surface side on which the porous layer is formed, and light can be emitted from the surface side on which the porous layer is not formed.

[0105] After the porous layer formed of the electron transport material is baked, chemical plating using a titanium tetrachloride aqueous solution or a mixed solution of an organic solvent or electrochemical plating using a titanium trichloride aqueous solution may be performed to increase the surface area of the porous layer.

[0106] In this way, for example, a film obtained by baking an electron transport material having a diameter of several tens of nanometers has a porous structure with many voids. The porous structure has a relatively high surface area, and this surface area can be represented by a roughness factor. The roughness factor is a numerical value representing the actual area inside the porous body relative to the particle area of the electron transport material coated on the first substrate or dense layer. Therefore, a larger roughness factor is preferred, but in terms of the relationship between the roughness factor and the average thickness of the electron transport layer, the roughness factor is preferably 20 or greater.

[0107] The particles of the electron transport material may be doped with a lithium compound. A specific method thereof is a method in which a solution of a lithium bis(trifluoromethanesulfonylimide) compound is deposited on the particles of the electron transport material by, for example, spin coating, and then subjected to a baking treatment.

[0108] The lithium compound is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the lithium compound include lithium bis(trifluoromethanesulfonyl imide), lithium perchlorate, and lithium iodide.

[0109] -Perovskite layer-

[0110] The perovskite layer refers to a layer containing a perovskite compound. Therefore, the perovskite layer is preferably provided adjacent to the electron transport layer.

[0111] The shape and size of the perovskite layer are not particularly limited and can be appropriately selected depending on the intended purpose, as long as the perovskite layers in at least two photoelectric conversion elements adjacent to each other are separated by a hole transport layer to be described below.

[0112] The perovskite compound is a composite substance of an organic compound and an inorganic compound, and is represented by the following general formula (A).

[0113] XαYβMγ···General formula (A)

[0114] In the above general formula (A), the ratio of α:β:γ is 3:1:1, and β and γ represent integers greater than 1. For example, X may be a halogen ion, Y may be an ion of an alkylamine compound, and M may be a metal ion.

[0115] X in the above general formula (A) is not particularly limited and can be appropriately selected according to the intended purpose. Examples thereof include halogen ions such as chlorine, bromine and iodine. These can be used alone or in combination.

[0116] Y in the above general formula (A) is, for example, an alkylamine compound (eg, methylamine, ethylamine, n-butylamine, and formamidine), cesium, potassium, and rubidium ions, which can be used alone or in combination.

[0117] In the case of a perovskite compound of lead halide and methylammonium, the peak λmax of the light absorption spectrum is approximately 350 nm when the halogen ion is Cl, approximately 410 nm when the halogen ion is Br, and approximately 540 nm when the halogen ion is I. As described above, the peak λmax shifts toward the longer wavelength side, and thus the available spectral width (bandwidth) changes.

[0118] The M in the above general formula (A) is not particularly limited and can be appropriately selected according to the intended purpose. Examples thereof include metals such as lead, indium, antimony, tin, copper and bismuth. These can be used alone or in combination.

[0119] The perovskite layer preferably has a laminated perovskite structure in which layers formed of metal halide and layers in which organic cation molecules are arranged are alternately laminated.

[0120] The perovskite layer preferably includes at least one selected from an alkali metal and an antimony atom. Inclusion of at least one of an alkali metal and an antimony atom in the perovskite layer is advantageous because output becomes high.

[0121] The method for forming the perovskite layer is not particularly limited and can be appropriately selected according to the intended purpose. Examples of the method include a method in which a solution in which a metal halide and a haloalkylamine are dissolved or dispersed is applied and then dried.

[0122] Examples of methods for forming a perovskite layer include a two-step precipitation method as described below. Specifically, a solution containing a metal halide dissolved or dispersed therein is applied and then dried. The resulting solution is then immersed in a solution containing a haloalkylamine to form a perovskite compound.

[0123] Examples of methods for forming a perovskite layer include a method of applying a solution in which a metal halide and a haloalkylamine are dissolved or dispersed and adding a poor solvent (a solvent with low solubility) for the perovskite compound to precipitate crystals. Examples of methods for forming a perovskite layer include a method of depositing a metal halide in a gas filled with, for example, methylamine.

[0124] Among these, a method of applying a solution in which a metal halide and a haloalkylamine are dissolved or dispersed and simultaneously adding a poor solvent for the perovskite compound to precipitate crystals is preferred.

[0125] The method for applying the solution is not particularly limited and can be appropriately selected according to the intended purpose. Examples of the method include immersion, spin coating, spray coating, dipping, roller coating, and air knife coating. As a method for applying the solution, a precipitation method using, for example, carbon dioxide in a supercritical fluid can be used.

[0126] Furthermore, the perovskite layer may include a sensitizing dye.

[0127] The method for forming the perovskite layer containing the sensitizing dye is not particularly limited and can be appropriately selected according to the intended purpose. Examples of the method include: a method in which a perovskite compound and a sensitizing dye are mixed; a method in which a perovskite layer is formed and then the sensitizing dye is adsorbed.

[0128] The sensitizing dye is not particularly limited and can be appropriately selected depending on the intended purpose, as long as it is a compound that is photoexcited by excitation light to be used.

[0129] Examples of the sensitizing dye include: metal complex compounds as described in, for example, the Japanese translation of PCT International Application Publication No. JP-T-07-500630, Japanese Unexamined Patent Application Publication No. 10-233238, Japanese Unexamined Patent Application Publication No. 2000-26487, Japanese Unexamined Patent Application Publication No. 2000-323191, and Japanese Unexamined Patent Application Publication No. 2001-59062; coumarin compounds as described in, for example, Japanese Unexamined Patent Application Publication No. 10-93118, Japanese Unexamined Patent Application Publication No. 2002-164089, Japanese Unexamined Patent Application Publication No. 2004-95450, and J. Phys. Chem. C, 7224, Vol. 111 (2007); polyene compounds as described in, for example, Japanese Unexamined Patent Application Publication No. 2004-95450 and Chem. Commun. , 4887 (2007); indoline compounds as described below, for example, Japanese Unexamined Patent Application Publication No. 2003-264010, Japanese Unexamined Patent Application Publication No. 2004-63274, Japanese Unexamined Patent Application Publication No. 2004-115636, Japanese Unexamined Patent Application Publication No. 2004-200068, Japanese Unexamined Patent Application Publication No. 2004-235052, J. Am. Chem. Soc. Am. c., 12218, Vol. 126 (2004), Chem. Commun., 3036 (2003) and Angew. Chem. Int. Ed., 1923, Vol. 47 (2008); thiophene compounds as described in, for example, J. Am. Chem. Soc., 16701, Vol. 128 (2006) and J. Am. Chem. Soc., 14256, Vol.128 (2006); cyanine dyes as described below, for example, Japanese Unexamined Patent Application Publication No. 11-86916, Japanese Unexamined Patent Application Publication No. 11-214730, Japanese Unexamined Patent Application Publication No. 2000-106224, Japanese Unexamined Patent Application Publication No. 2001-76773, and Japanese Unexamined Patent Application Publication No. 2003-7359; merocyanine dyes as described below, for example, Japanese Unexamined Patent Application Publication No. 11-21 4731, Japanese Unexamined Patent Application Publication No. 11-238905, Japanese Unexamined Patent Application Publication No. 2001-52766, Japanese Unexamined Patent Application Publication No. 2001-76775, and Japanese Unexamined Patent Application Publication No. 2003-7360; 9-arylxanthene compounds described below, for example, Japanese Unexamined Patent Application Publication No. 10-92477, Japanese Unexamined Patent Application Publication No. 11-273754, Japanese Unexamined Patent Application Publication No. 1 1-273755 and Japanese Unexamined Patent Application Publication No. 2003-31273; triarylmethane compounds as described below, for example, Japanese Unexamined Patent Application Publication No. 10-93118 and Japanese Unexamined Patent Application Publication No. 2003-31273; and phthalocyanine compounds and porphyrin compounds as described below, for example, Japanese Unexamined Patent Application Publication No. 09-199744, Japanese Unexamined Patent Application Publication No. 10-233238, Japanese Unexamined Patent Application Publication No. Patent Application Publication No. 11-204821, Japanese Unexamined Patent Application Publication No. 11-265738, J. Phys. Chem., 2342, Vol. 91 (1987), J. Phys. Chem. B, 6272, Vol. 97 (1993), Electroanal. Chem., 31, Vol. 537 (2002), Japanese Unexamined Patent Application Publication No. 2006-032260, J. Porphyrins Phthalocyanines, 230, Vol. 3 (1999), Angew. Chem. Int. Ed., 373, Vol. 46 (2007), and Langmuir, 5436, Vol. 24 (2008). Among them, metal complex compounds, indoline compounds, thiophene compounds, and porphyrin compounds are preferred.

[0130] <<Hole Transport Layer>>

[0131] The hole transport layer is a layer that transports holes generated in the perovskite layer to the second electrode described below. Therefore, the hole transport layer is preferably provided adjacent to the perovskite layer.

[0132] The shape and size of the hole transport layer are not particularly limited and can be appropriately selected according to the intended purpose, as long as the hole transport layer is an extended continuous layer and the hole transport layer can separate the first electrode, the electron transport layer and the perovskite layer in at least two adjacent photoelectric conversion elements.

[0133] By separating the first electrode, the electron transport layer, and the perovskite layer using a hole transport layer that is an extended continuous layer in at least two photoelectric conversion elements adjacent to each other, the porous titanium oxide layer is separated and electron recombination by diffusion is reduced, which makes it possible to maintain power generation efficiency even after long-term exposure to light with high illuminance.

[0134] The hole transport layer includes a polymer having a weight average molecular weight of 2,000 or more or a compound having a molecular weight of 2,000 or more as a hole transport material, and further includes a compound having a weight average molecular weight of less than 2,000 or other components if necessary.

[0135] -Polymer having a weight average molecular weight of 2,000 or more-

[0136] The polymer having a weight average molecular weight of 2,000 or more is not particularly limited and can be appropriately selected according to the intended purpose as long as it is a hole transport material. Examples of polymers having a weight average molecular weight of 2,000 or more include polythiophene compounds, polyphenylene vinylene compounds, polyfluorene compounds, polyphenylene compounds, polyarylamine compounds, and polythiadiazole compounds. Among them, in view of carrier mobility and ionization potential, polythiophene compounds, polyarylamine compounds, and polymers including repeating units represented by the following general formula (1) or (2) are preferred, and polymers including repeating units represented by the following general formula (1) or (2) are particularly preferred.

[0137] Note that the weight average molecular weight is a value in terms of polystyrene measured by gel filtration chromatography (GPC).

[0138] Examples of the polythiophene compound include poly(3-n-hexylthiophene), poly(3-n-octyloxythiophene), poly(9,9′-dioctyl-fluorene-co-dithiophene), poly(3,3″′-didodecanyl-quaternary thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene), poly(2,5-bis(3-decylthiophen-2-yl)thieno[3,2-b]thiophene), poly(3,4-didecylthiophene-co-thieno[3,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thieno[3,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thieno[3,2-b]thiophene), and poly(3,6-dioctylthieno[3,2-b]thiophene-co-bithiophene).

[0139] Examples of the polyphenylene vinylene compound include poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene vinylene], and poly[(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene)-co-(4,4′-bisphenylene-vinylene)].

[0140] Examples of the polyfluorene compound include poly(9,9′-docosylfluorenyl-2,7-diyl), poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co-(9,10-anthracene)], poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co-(4,4′-biphenylene)], poly[(9,9-dioctyl-2,7-divinylenefluorene)-alt-co-(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene)], and poly[(9,9-dioctyl-2,7-diyl)-co-(1,4-(2,5-dihexyloxy)benzene)].

[0141] Examples of the polyphenylene compound include poly[2,5-dioctyloxy-1,4-phenylene] and poly[2,5-di(2-ethylhexyloxy-1,4-phenylene].

[0142] Examples of the polyarylamine compound include poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(N,N'-diphenyl)-N,N'-di(p-hexylphenyl)-1,4-diaminobenzene], poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(N,N'-bis(4-octyloxyphenyl)benzidine-N,N'-(1,4-diphenylene)], poly[(N,N'-bis(4-octyloxyphenyl)benzidine-N,N'-(1,4-diphenylene)], poly[( N,N'-bis(4-(2-ethylhexyloxy)phenyl)benzidine-N,N'-(1,4-diphenylene)], poly[phenylimino-1,4-phenylenevinylene-2,5-dioctyloxy-1,4-phenylenevinylene-1,4-phenylene], poly[p-tolylimino-1,4-phenylenevinylene-2,5-di(2-ethylhexyloxy)-1,4-phenylenevinylene-1,4-phenylene], and poly[4-(2-ethylhexyloxy)phenylimino-1,4-diphenylene].

[0143] Examples of the polythiadiazole compound include poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(1,4-benzo(2,1′,3)thiadiazole] and poly(3,4-didecylthiophene)-co-(1,4-benzo(2,1′,3)thiadiazole).

[0144] The polymer having a weight average molecular weight of 2,000 or more is suitably a polymer including a repeating unit represented by the following general formula (1) or (2).

[0145] [Chemical Formula 1]

[0146]

[0147] In the general formula (1), R1 and R2, which may be the same as or different from each other, each represent at least one selected from a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group and an aryl group.

[0148] Examples of the alkyl group include a methyl group, an ethyl group and a 2-isobutyl group.

[0149] Examples of the aralkyl group include a benzyl group and a 2-naphthylmethyl group.

[0150] Examples of the alkoxy group include a methoxy group and an ethoxy group.

[0151] Examples of the aryl group include a phenyl group and a 1-naphthyl group.

[0152] R3 represents one selected from an alkyl group, an aralkyl group, an aryl group and a heterocyclic group.

[0153] Examples of the alkyl group include a methyl group, an ethyl group and a 2-isobutyl group.

[0154] Examples of the aralkyl group include a benzyl group and a 2-naphthylmethyl group.

[0155] Examples of the aryl group include a phenyl group and a 1-naphthyl group.

[0156] Examples of the heterocyclic group include a thiophene ring group and a furan ring group.

[0157] X1 represents one selected from an alkylene group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group.

[0158] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

[0159] Examples of the alkenyl group include a vinyl group.

[0160] Examples of the alkynyl group include acetylene.

[0161] Examples of the aryl group include a phenyl group and a 1-naphthyl group.

[0162] Examples of the heterocyclic group include a thiophene ring group and a furan ring group.

[0163] n represents an integer of 2 or more and allows the polymer containing the repeating unit represented by the general formula (1) to have a weight average molecular weight of 2,000 or more.

[0164] [Chemical Formula 2]

[0165]

[0166] In the general formula (2), R4 represents one selected from the group consisting of a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group and an aryl group.

[0167] Examples of the alkyl group include a methyl group, an ethyl group and a 2-isobutyl group.

[0168] Examples of the aralkyl group include a benzyl group and a 2-naphthylmethyl group.

[0169] Examples of the alkoxy group include a methoxy group and an ethoxy group.

[0170] Examples of the alkenyl group include a vinyl group.

[0171] Examples of the aryl group include a phenyl group and a 1-naphthyl group.

[0172] X2 represents one selected from an oxygen atom, a sulfur atom and a selenium atom.

[0173] X3 represents one selected from an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group.

[0174] Examples of the alkenyl group include a vinyl group.

[0175] Examples of the alkynyl group include acetylene.

[0176] Examples of the aryl group include a phenyl group and a 1-naphthyl group.

[0177] Examples of the heterocyclic group include a thiophene ring group and a furan ring group.

[0178] m represents an integer of 2 or more and allows the polymer including the repeating unit represented by the general formula (2) to have a weight average molecular weight of 2,000 or more.

[0179] Examples of polymers comprising a repeating unit represented by general formula (1) include the following (A-1) to (A-25). In the formula, n represents an integer of 2 or greater and allows the polymer comprising a repeating unit represented by general formula (1) to have a weight average molecular weight of 2,000 or greater.

[0180] [Chemical Formula 3]

[0181]

[0182] [Chemical Formula 4]

[0183]

[0184] [Chemical Formula 5]

[0185]

[0186] [Chemical Formula 6]

[0187]

[0188] [Chemical Formula 7]

[0189]

[0190] [Chemical Formula 8]

[0191]

[0192] [Chemical Formula 9]

[0193]

[0194] [Chemical Formula 10]

[0195]

[0196] [Chemical Formula 11]

[0197]

[0198] Examples of polymers including repeating units represented by general formula (2) include the following (B-1) to (B-32): In the formula, m represents an integer of 2 or greater, and the polymer represented by general formula (2) has a weight average molecular weight of 2000 or greater.

[0199] [Chemical Formula 12]

[0200]

[0201] [Chemical Formula 13]

[0202]

[0203] [Chemical Formula 14]

[0204]

[0205] [Chemical Formula 15]

[0206]

[0207] [Chemical Formula 16]

[0208]

[0209] [Chemical Formula 17]

[0210]

[0211] [Chemical Formula 18]

[0212]

[0213] [Chemical Formula 19]

[0214]

[0215] [Chemical Formula 20]

[0216]

[0217] [Chemical Formula 21]

[0218]

[0219] [Chemical Formula 22]

[0220]

[0221] -Compounds having a molecular weight of 2,000 or more-

[0222] Examples of the compound having a molecular weight of 2,000 or more include the following compounds.

[0223] [Chemical Formula 23]

[0224]

[0225] -Compounds with a molecular weight of less than 2,000-

[0226] The compound having a molecular weight of less than 2,000 is a hole transport material, and its chemical structure is not particularly limited. Specific examples of the compound having a molecular weight of less than 2,000 include: for example, oxadiazole compounds described in Japanese Examined Patent Publication No. 34-5466; for example, triphenylmethane compounds described in Japanese Examined Patent Publication No. 45-555; for example, pyrazoline compounds described in Japanese Examined Patent Publication No. 52-4188; for example, hydrazone compounds described in Japanese Examined Patent Publication No. 55-42380; for example, oxadiazole compounds described in Japanese Unexamined Patent Application Publication No. 56-123544; tetraarylbenzidine compounds described in Japanese Unexamined Patent Application Publication No. 54-58445; and Japanese Unexamined Patent Application Publication No. 5 8-65440 and Japanese Unexamined Patent Application Publication No. 60-98437; Japanese Unexamined Patent Application Publication No. 2007-115665, Japanese Unexamined Patent Application Publication No. 2014-72327, Japanese Patent Application No. 2000-067544, WO2004 / 063283, WO2011 / 030220401919, and WO2013 / 121835; and the thiophene compounds and triarylamine compounds described in Japanese Unexamined Patent Application Publication No. 2-250881 and Japanese Unexamined Patent Application Publication No. 2013-033868.

[0227] Among them, spirobifluorene compounds, triarylamine compounds and thiophene compounds are preferred.

[0228] --Spirobifluorene compounds--

[0229] The spirobifluorene compound is not particularly limited and can be appropriately selected according to the intended purpose. In terms of power generation efficiency, examples of the spirobifluorene compound include: (2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamino)-9,9'-spirobifluorene: spiro-OMeTAD) as a hole transport layer described in "J.Am.Chem.Soc., 133 (2011) 18042"; (N2',N2',N5,N5,N7',N7',N9,N9-octa(4-methoxyphenyl)spiro[dibenzo-[c,h]anthracene-7,9'-fluorene]-2',5,7',9-tetramine: X62) as a hole transport layer; The hole transport material described in “Chem. Commun., 54, (2018) 9571”; (N2, N7-bis (4-methoxyphenyl) -N2, N7-bis (spiro [fluorene -9,9'- xanthene] -2-yl) spiro [fluorene -9,9'- xanthene] -2,7- diamine: X55) as the hole transport material described in “Chem, 2 (2017) 676”; (N2, N2, N7, N7-tetrakis (4-methoxyphenyl) spiro [fluorene -9,9'- xanthene] -2,7- diamine: X59) as the hole transport material described in “Nano Energy, 23 (2016) 138"; and (octa(4-methoxyphenyl)spiro[fluorene-9,9'-xanthene]-2,2',7,7'-tetramine): X60) as the hole transport material described in "Energy & Environmental Science, 9 (2016) 873". Among them, spiro-OMeTAD is preferred. Spiro-OMeTAD is represented by the following structural formula (1).

[0230] <Structural formula (1)>

[0231] [Chemical Formula 23]

[0232]

[0233] --Triarylamine compounds--

[0234] Examples of the triarylamine compound include compounds represented by Formula 3 below.

[0235] (Formula 3)

[0236] A n -B m

[0237] When n is 2, m is 0, and when n is 1, m is 0 or 1. A is a structure represented by the following general formula 4 and is selected from Z1 to Z 15 B is a structure represented by the following general formula 5, and is selected from Z 16 to Z 21Combined with A at the position in.

[0238] (Formula 4)

[0239] [Chemical Formula 24]

[0240]

[0241] (Formula 5)

[0242] [Chemical Formula 25]

[0243]

[0244] Z1 to Z 21 may be the same as or different from each other, and each represents a monovalent organic group.

[0245] Examples of each of the monovalent organic groups in Formula 4 and Formula 5 include a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, an amide group, a monoalkylaminocarbonyl group which may have a substituent, a dialkylaminocarbonyl group which may have a substituent, a monoarylaminocarbonyl group which may have a substituent, a diarylaminocarbonyl group which may have a substituent, a sulfonic acid group, an alkoxysulfonyl group which may have a substituent, an aryloxysulfonyl group which may have a substituent, an alkyl ... an arylsulfonyl group which may have a substituent, a sulfonamide group, a monoalkylaminosulfonyl group which may have a substituent, a dialkylaminosulfonyl group which may have a substituent, a monoarylaminosulfonyl group which may have a substituent, a diarylaminosulfonyl group which may have a substituent, an amino group, a monoalkylamino group which may have a substituent, a dialkylamino group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, and a heterocyclic group which may have a substituent.

[0246] Among them, an alkyl group, an alkoxy group, a hydrogen atom, an aryl group, an aryloxy group, a halogen atom, an alkenyl group, and an alkynyl group are particularly preferred in terms of stability.

[0247] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0248] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0249] Examples of aryl groups include phenyl and naphthyl.

[0250] Examples of the aralkyl group include benzyl, phenethyl and naphthylmethyl.

[0251] Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

[0252] Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.

[0253] Examples of the heterocyclic group include carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.

[0254] Examples of the substituent further substituted with a substituent include alkyl groups such as halogen atoms, nitro groups, cyano groups, methyl groups and ethyl groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups; aryl groups such as phenyl groups and naphthyl groups; and aralkyl groups such as benzyl groups and phenethyl groups.

[0255] Specific examples of the triarylamine compound include compounds (C-1) represented by the following structural formula.

[0256] [Chemical Formula 26]

[0257]

[0258] --Thiophene compounds--

[0259] The thiophene compound is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the thiophene compound include thiophene, benzothiophene, azadibenzothiophene, and a compound (C-2) represented by the following structural formula.

[0260] [Chemical Formula 27]

[0261]

[0262] [Chemical Formula 28]

[0263]

[0264] In the present disclosure, when a polymer having a weight average molecular weight of 2,000 or more is mixed with a compound having a molecular weight of less than 2,000, the difference between their respective ionization potentials is preferably 0.2 eV or less. The ionization potential is the energy required to extract one electron from a molecule, expressed in electron volts (eV). The method for measuring the ionization potential is not particularly limited. However, the ionization potential is preferably measured by photoelectron spectroscopy.

[0265] When the ionization potential of a polymer with a weight-average molecular weight of 2,000 or more is IPa, and the ionization potential of a compound with a molecular weight of less than 2,000 is Ipb, the following condition is preferably satisfied: IPa - Ipb = ±0.2 eV or less. When the difference is 0.2 eV or more, holes remain trapped on one side and have difficulty moving. As a result, holes cannot be smoothly transported.

[0266] The mixing ratio between the polymer having a weight average molecular weight of 2,000 or more and the compound having a molecular weight of less than 2,000 is preferably 4:6 to 9:1, more preferably 4:6 to 7:3, still more preferably 1:1 to 7:3, in terms of mass ratio.

[0267] Other materials included in the hole transport layer are not particularly limited and can be appropriately selected depending on the intended purpose. Examples of other materials include additives and oxidizing agents.

[0268] The additive is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the additive include iodine; metal iodides such as lithium iodide, sodium iodide, potassium iodide, cesium iodide, calcium iodide, copper iodide, iron iodide, and silver iodide; quaternary ammonium salts such as tetraalkylammonium iodides and pyridinium iodide; Metal bromides, such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, calcium bromide; bromide salts of quaternary ammonium compounds, such as tetraalkylammonium bromides and pyridinium bromide Metal chlorides, such as copper chloride and silver chloride; metal acetates, such as copper acetate, silver acetate and palladium acetate; metal sulfates, such as copper sulfate and zinc sulfate; metal complexes, such as ferrocyanide-ferrocyanide and ferrocenium-ferric ion; sulfur compounds, such as sodium polysulfide and alkylthiol-alkyl disulfide; viologen dyes; hydroquinone; basic compounds, such as pyridine, 4-tert-butylpyridine and benzimidazole.

[0269] An oxidizing agent may be further added. The type of oxidizing agent is not particularly limited and may be appropriately selected according to the intended purpose. Examples of oxidizing agents include tris(4-bromophenyl)ammonium hexachloroantimonate, silver hexafluoroantimonate, nitrous tetrafluoroborate, silver nitrate, and cobalt complexes. Note that it is not necessary to oxidize the entire hole transport material with the oxidizing agent, as long as the hole transport material is partially oxidized, it is effective. After the reaction, the oxidizing agent may be removed or not removed outside the system.

[0270] Inclusion of an oxidant in the hole transport layer may partially or entirely form the hole transport material into radical cations, which makes it possible to improve conductivity and increase safety and durability of output characteristics.

[0271] The average thickness of the hole transport layer is not particularly limited and can be appropriately selected depending on the intended purpose. However, on the perovskite layer, the average thickness is preferably 0.01 μm or more and 20 μm or less, more preferably 0.1 μm or more and 10 μm or less, still more preferably 0.2 μm or more and 2 μm or less.

[0272] The hole transport layer can be formed directly on the perovskite layer. The method for producing the hole transport layer is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of such methods include: a method in which a thin film is formed in a vacuum by vacuum deposition; and a wet film formation method. In particular, the wet film formation method is preferred in terms of production cost, and a method in which the hole transport layer is coated on the perovskite layer is more preferred.

[0273] The wet film forming method is not particularly limited and can be appropriately selected according to the intended purpose. Examples of wet film forming methods include dipping, spraying, wire rod coating, spin coating, roller coating, blade coating, and gravure coating. As wet printing methods, methods such as relief printing, offset printing, gravure printing (gravure printing), intaglio printing (intaglioprinting), rubber plate printing, and screen printing can be used.

[0274] Furthermore, the hole transport layer can be produced by forming a film in a supercritical fluid or a subcritical fluid having a temperature and a pressure lower than the critical point.

[0275] A supercritical fluid is a fluid that exists as an incondensable high-density fluid in a temperature and pressure region exceeding the limit (critical point) at which gas and liquid can coexist and does not condense even when compressed, and is a fluid in a state of being equal to or higher than the critical temperature and equal to or higher than the critical pressure. The supercritical fluid is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably a supercritical fluid having a low critical temperature.

[0276] The subcritical fluid is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a fluid that exists as a high-pressure liquid in a temperature and pressure region near the critical point. The fluid exemplified as the supercritical fluid can be appropriately used as the subcritical fluid.

[0277] Examples of the supercritical fluid include carbon monoxide, carbon dioxide, ammonia, nitrogen, water, alcohol solvents, hydrocarbon solvents, halogen solvents, and ether solvents.

[0278] Examples of the alcohol solvent include methanol, ethanol, and n-butanol.

[0279] Examples of hydrocarbon solvents include ethane, propane, 2,3-dimethylbutane, benzene, and toluene. Examples of halogen solvents include dichloromethane and chlorotrifluoromethane.

[0280] Examples of the ether solvent include dimethyl ether.

[0281] These may be used alone or in combination.

[0282] Among them, carbon dioxide having a critical pressure of 7.3 MPa and a critical temperature of 31° C. is preferable because carbon dioxide easily produces a supercritical state, is non-flammable, and is easy to handle.

[0283] The critical temperature and critical pressure of the supercritical fluid are not particularly limited and can be appropriately selected depending on the intended purpose.The critical temperature of the supercritical fluid is preferably -273°C or higher and 300°C or lower, more preferably 0°C or higher and 200°C or lower.

[0284] In addition to supercritical fluids and subcritical fluids, organic solvents or entrainers may be used in combination. By adding organic solvents or entrainers, the solubility in supercritical fluids can be easily adjusted.

[0285] The organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the organic solvent include ketone solvents, ester solvents, ether solvents, amide solvents, halogenated hydrocarbon solvents, and hydrocarbon solvents.

[0286] Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0287] Examples of the ester solvent include ethyl formate, ethyl acetate, and n-butyl acetate.

[0288] Examples of the ether solvent include diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, and dioxane.

[0289] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0290] Examples of the halogenated hydrocarbon solvent include dichloromethane, chloroform, bromoform, iodomethane, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene and 1-chloronaphthalene.

[0291] Examples of the hydrocarbon solvent include n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene.

[0292] These may be used alone or in combination.

[0293] After laminating the hole transport material on the perovskite layer, a press process may be performed. By performing the press process, the hole transport material adheres more tightly to the perovskite layer, which may improve power generation efficiency in some cases.

[0294] The press working method is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the method include a press forming method using a plate as typified by an infrared (IR) sheet forming apparatus; and a roll pressing method using a roll.

[0295] The pressure for the press working is preferably 10 kgf / cm 2 or higher, more preferably 30 kgf / cm 2 or higher.

[0296] The time of pressing is not particularly limited and can be appropriately selected according to the intended purpose. It is preferably 1 hour or less. In addition, heat can be applied during pressing.

[0297] During pressing, a release agent may be provided between the press and the electrodes.

[0298] The releasing agent is not particularly limited and can be appropriately selected according to the intended purpose. The example of the releasing agent includes fluororesin, such as polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, perfluoroalkoxy fluororesin, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer and polyvinyl fluoride. These can be used alone or in combination.

[0299] After performing the pressing but before providing the second electrode, a film including a metal oxide may be provided between the hole transport layer and the second electrode.

[0300] The metal oxide is not particularly limited and can be appropriately selected according to the intended purpose. Examples of metal oxides include molybdenum oxide, tungsten oxide, vanadium oxide and nickel oxide. These can be used alone or in combination. Among them, molybdenum oxide is preferred.

[0301] The method for providing a film containing a metal oxide on the hole transport layer is not particularly limited and can be appropriately selected according to the intended purpose. Examples of the method include: a method in which a thin film is formed in a vacuum, such as sputtering and vacuum vapor deposition; and a wet film formation method.

[0302] The wet film-forming method in the case of forming a film containing a metal oxide is preferably a method in which a paste-like dispersed powder or sol of the metal oxide is prepared and then coated on the hole transport layer.

[0303] The wet film forming method is not particularly limited and can be appropriately selected according to the intended purpose. Examples of wet film forming methods include dipping, spraying, wire rod coating, spin coating, roller coating, blade coating, and gravure coating. As wet printing methods, methods such as relief printing, offset printing, gravure printing, intaglio printing, rubber plate printing, screen printing, etc. can be used.

[0304] The average thickness of the film including the metal oxide is not particularly limited and can be appropriately selected depending on the intended purpose. However, the average thickness thereof is preferably 0.1 nm or more and 50 nm or less, more preferably 1 nm or more and 10 nm or less.

[0305] <<Second Electrode>>

[0306] The second electrode is preferably formed on the hole transport layer or on the metal oxide film in the hole transport layer.The same electrode as the first electrode can be used for the second electrode.

[0307] The shape, structure, and size of the second electrode are not particularly limited and can be appropriately selected depending on the intended purpose.

[0308] Examples of the material of the second electrode include metals, carbon compounds, conductive metal oxides, and conductive polymers.

[0309] Examples of metals include platinum, gold, silver, copper, and aluminum.

[0310] Examples of carbon compounds include graphite, fullerene, carbon nanotube, and graphene.

[0311] Examples of the conductive metal oxide include ITO, FTO, and ATO.

[0312] Examples of conductive polymers include polythiophene and polyaniline.

[0313] These may be used alone or in combination.

[0314] The second electrode may be appropriately formed on the hole transport layer by a method such as coating, lamination, vacuum deposition, CVD, or adhesion depending on the kind of material to be used or the kind of the hole transport layer.

[0315] In a photoelectric conversion element, at least one of the first and second electrodes is preferably substantially transparent. When using the solar cell module disclosed herein, the first electrode is preferably transparent to allow incident light to enter from the first electrode side. In this case, the second electrode is preferably made of a light-reflecting material, preferably glass, plastic, or a metal film deposited with a metal or conductive oxide. Furthermore, providing an antireflection layer on the side of the electrode where incident light enters is an effective method.

[0316] <Second Substrate>

[0317] The second substrate is disposed to face the first substrate so that the first substrate and the second substrate sandwich the photoelectric conversion element.

[0318] The shape, structure, and size of the substrate are not particularly limited and can be appropriately selected depending on the intended purpose.

[0319] The material of the second substrate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the material include glass, plastic films, and ceramics.

[0320] A convexo-concave portion may be formed at a connection portion of the second substrate and the sealing member, which will be described below, in order to increase adhesion.

[0321] The method for forming the convexo-concave portion is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the forming method include a sandblasting method, a water jet method, a chemical etching method, a laser processing method, and a method using sandpaper.

[0322] The method for increasing the adhesion between the second substrate and the sealing member may be, for example, a method for removing organic matter on the surface of the second substrate, or a method for increasing the hydrophilicity of the second substrate. The method for removing organic matter on the surface of the second substrate is not particularly limited and can be appropriately selected according to the intended purpose. Examples of such methods include UV ozone cleaning and oxygen plasma treatment.

[0323] <Sealing Member>

[0324] The sealing member is provided between the first substrate and the second substrate, and seals the photoelectric conversion element.

[0325] The material of the sealing member is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the material include cured products of acrylic resins and cured products of epoxy resins.

[0326] As the cured product of the acrylic resin, any material known in the art may be used as long as the cured product of the acrylic resin is a product obtained by curing a monomer or oligomer containing an acryl group in its molecule.

[0327] As the cured product of the epoxy resin, any material known in the art may be used as long as the cured product of the epoxy resin is a product obtained by curing a monomer or oligomer containing an epoxy group in its molecule.

[0328] Examples of epoxy resins include water-dispersible epoxy resins, non-solvent epoxy resins, solid epoxy resins, thermosetting epoxy resins, curing agent mixed epoxy resins, and ultraviolet curable epoxy resins. Among them, thermosetting epoxy resins and ultraviolet curable epoxy resins are preferred, and ultraviolet curable epoxy resins are more preferred. Note that even when using ultraviolet curable epoxy resins, heating may be performed, and preferably heating is performed even after curing by ultraviolet irradiation.

[0329] Examples of epoxy resins include bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, novolac-based epoxy resins, alicyclic epoxy resins, long-chain aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidylether-based epoxy resins, and glycidylester-based epoxy resins. These can be used alone or in combination.

[0330] If necessary, a curing agent or various additives are preferably mixed with the epoxy resin.

[0331] The curing agent is not particularly limited and can be appropriately selected depending on the intended purpose. The curing agent is classified into, for example, amine-based curing agents, acid anhydride-based curing agents, polyamide-based curing agents, and other curing agents.

[0332] Examples of the amine-based curing agent include aliphatic polyamines such as diethylenetriamine and triethylenetetramine; and aromatic polyamines such as toluenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

[0333] Examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnaphthalic anhydride, pyromellitic anhydride, HET anhydride, and dodecenylsuccinic anhydride.

[0334] Examples of other curing agents include imidazoles and polythiols, which can be used alone or in combination.

[0335] Additive is not particularly limited, and can be suitably selected according to intended purpose.The example of additive comprises filler, interstitial agent, polymerization initiator, desiccant (hygroscopic agent), curing accelerator, coupling agent, toughening agent, colorant, flame retardant auxiliary agent, antioxidant and organic solvent.Wherein, filler, interstitial agent, curing accelerator, polymerization initiator and desiccant (hygroscopic agent) are preferred, and filler and polymerization initiator are more preferred.

[0336] Including fillers as additives can prevent the ingress of moisture and oxygen, and can further achieve benefits such as reduced volume shrinkage during curing, reduced outgassing during curing or heating, improved mechanical strength, and control of thermal conductivity and fluidity. Therefore, including fillers as additives is very effective in maintaining stable output under various environments.

[0337] Furthermore, the output characteristics and durability of photoelectric conversion elements cannot be ignored, not only due to the influence of moisture and oxygen penetration, but also due to the influence of outgassing generated during curing or heating of the sealing member. In particular, outgassing generated during heating significantly affects the output characteristics of photoelectric conversion elements stored in high-temperature environments.

[0338] By adding fillers, gap fillers, or desiccants to the sealing member, moisture and oxygen can be prevented from entering, thereby reducing the amount of sealing member used and achieving the effect of reducing degassing. Including fillers, gap fillers, or desiccants in the sealing member is effective not only during curing but also when the photoelectric conversion element is stored in a high-temperature environment.

[0339] The filler is not particularly limited and can be appropriately selected according to the intended purpose. Examples of fillers include inorganic fillers such as crystalline or amorphous silica, talc, aluminum oxide, aluminum nitride, silicon nitride, calcium silicate, and calcium carbonate. These can be used alone or in combination.

[0340] The average primary particle size of the filler is preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less. When the average primary particle size of the filler is within the above preferred range, the effect of preventing the ingress of moisture or oxygen can be fully achieved, the viscosity becomes appropriate, and the adhesion to the substrate and the defoaming properties are improved. It is also effective in controlling the width of the seal portion and workability.

[0341] Relative to the total amount (100 parts by mass) of the sealing member, the amount of the filler is preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less. When the amount of the filler is within the above-mentioned preferred range, the effect of preventing moisture or oxygen from entering can be fully obtained, the viscosity becomes appropriate, and the adhesion and processability are good.

[0342] A gap agent is also known as a gap control agent or spacer. By including a gap agent as an additive, the gap in the seal can be controlled. For example, when a sealing member is provided on a first substrate or a first electrode and a second substrate is provided thereon for sealing, the gap in the seal can be matched to the size of the gap agent because the sealing member includes the gap agent. As a result, the gap in the seal can be easily controlled.

[0343] The spacer is not particularly limited and can be appropriately selected according to the intended purpose, as long as it is granular, has a uniform diameter, and has high solvent resistance and heat resistance. The spacer is preferably a material having a high affinity for the epoxy resin and in the form of spherical particles. Preferred examples of the spacer include glass beads, silica fine particles, and organic resin fine particles. These can be used alone or in combination.

[0344] The particle size of the gap agent can be selected according to the gap to be set in the sealing portion. The particle size is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less.

[0345] The polymerization initiator is not particularly limited and can be appropriately selected depending on the intended purpose, as long as polymerization is initiated by heat and light. Examples of the polymerization initiator include thermal polymerization initiators and photopolymerization initiators.

[0346] Thermal polymerization initiators are compounds that generate reactive species such as free radicals and cations when heated. Examples of thermal polymerization initiators include azo compounds such as 2,2'-azobisbutyronitrile (AIBN) and peroxides such as benzoyl peroxide (BPO). Examples of thermal cationic polymerization initiators include benzenesulfonates and alkylsulfonium salts.

[0347] Meanwhile, as a photopolymerization initiator, a photocationic polymerization initiator is preferably used in the case of epoxy resin. When the photocationic polymerization initiator is mixed with the epoxy resin and emits light, the photocationic polymerization initiator decomposes to produce acid, and the acid initiates polymerization of the epoxy resin. Then, a curing reaction is carried out. The photocationic polymerization initiator disclosed herein has the following effects: small volume shrinkage during curing, no oxygen inhibition, and high storage stability.

[0348] Examples of photocationic polymerization initiators include aromatic diazonium salts, aromatic iodine Onium salts, aromatic sulfonium salts, metallocene compounds and silanol-aluminum complexes.

[0349] In addition, a photoacid generator having a function of generating an acid by light irradiation can also be used as a polymerization initiator. The photoacid generator acts as an acid that initiates cationic polymerization. Examples of the photoacid generator include Salts, such as ionic sulfonium salts Salt and ionized iodine base Salts include cationic and ionic moieties. These can be used alone or in combination.

[0350] The amount of the polymerization initiator added can be different according to the material used.Relative to the total amount (100 mass parts) of sealing member, the amount of polymerization initiator is preferably 0.5 mass part or larger and 10 mass parts or less, more preferably 1 mass part or larger and 5 mass parts or less.When the amount of the polymerization initiator added is in the above-mentioned preferred range, it is possible to suitably solidify, it is possible to reduce residual uncured product, and it is possible to prevent excessive degassing.

[0351] A desiccant, also known as a moisture absorber, is a material that physically or chemically adsorbs or absorbs moisture. The inclusion of a desiccant in a sealing member can further improve moisture resistance and reduce the effects of outgassing.

[0352] The desiccant is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably a granular material. Examples of desiccant include inorganic water-absorbing materials such as calcium oxide, barium oxide, magnesium oxide, magnesium sulfate, sodium sulfate, calcium chloride, silica gel, molecular sieves, and zeolite. Among them, zeolite is preferred because it absorbs a large amount of water. These can be used alone or in combination.

[0353] A curing accelerator, also known as a curing catalyst, is a material that accelerates the curing process. Curing accelerators are primarily used for heat-curable epoxy resins.

[0354] The curing accelerator is not particularly limited and can be appropriately selected according to the intended purpose. Examples of the curing accelerator include: 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); imidazole compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole; and phosphine or Salts such as triphenylphosphine and tetraphenylphosphine Tetraphenyl borate. These can be used alone or in combination.

[0355] The coupling agent is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a material having an effect of increasing molecular bonding force. Examples of the coupling agent include silane coupling agents. Specific examples thereof include silane coupling agents such as 3-glycidoxypropylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, and 3-methacryloxypropyltrimethoxysilane. These can be used alone or in combination.

[0356] As sealing member, the epoxy resin composition that can be used as sealing material (sealing material), seal material (seal material) or adhesive commercially available is already known, and this commercially available product can be effectively used in the present disclosure. Among them, there is also an epoxy resin composition that has been developed and commercially available for solar cells or organic EL elements, and this commercially available product can be particularly effectively used in the present disclosure. The example of commercially available epoxy resin composition includes:TB3118, TB3114, TB3124 and TB3125F (available from ThreeBond); World Rock 5910, World Rock 5920 and World Rock 8723 (available from Kyoritsu Chemical Co., Ltd.); And WB90US (P) (available from MORESCO Corporation).

[0357] In the present disclosure, a sealing sheet may be used as the sealing material.

[0358] The sealing sheet is a material pre-formed with an epoxy resin layer. Glass or film with high gas barrier properties is used as the sheet. By bonding the sealing sheet to a second substrate and then curing it, the sealing member and the second substrate can be formed simultaneously. Depending on the pattern of the epoxy resin layer formed on the sheet, a structure with a hollow portion can be formed.

[0359] The method for forming sealing member is not particularly limited, and can be suitably selected according to intended purpose.The example of the method includes distribution method, wire rod method, spin coating method, roller coating method, blade coating method and gravure coating method.In addition, as the method for forming sealing member, it is possible to use, such as relief printing, offset printing, gravure printing (gravure printing), intaglio printing (intaglio printing), rubber plate printing, screen printing and other methods.

[0360] In addition, a passivation layer may be provided between the sealing member and the second electrode. The passivation layer is not particularly limited and may be appropriately selected according to the intended purpose, as long as the passivation layer is provided in a manner such that the sealing member does not contact the second electrode. Examples of the passivation layer include aluminum oxide, silicon nitride, and silicon oxide.

[0361] <Other components>

[0362] Other members are not particularly limited and can be appropriately selected depending on the intended purpose.

[0363] Hereinafter, one embodiment of the solar cell module of the present disclosure will be described with reference to the accompanying drawings. In each of the drawings, the same reference numerals are assigned to the same components, and redundant descriptions may be omitted.

[0364] <Structure of Solar Cell Module>

[0365] Figure 1 is an explanatory view showing one example of the structure of the solar cell module of the present disclosure.

[0366] like Figure 1 As shown, the solar cell module 100 includes: a first substrate 1; and a photoelectric conversion element provided on the first substrate 1, each of the photoelectric conversion elements including first electrodes 2a and 2b, a dense electron transport layer (dense layer) 3, a porous electron transport layer (porous layer) 4, a perovskite layer 5, a hole transport layer 6, and second electrodes 7a and 7b. Note that the first electrode 2a or 2b and the second electrode 7a or 7b each have a path configured to allow current to pass through the electrode lead terminal.

[0367] In the solar cell module 100 , the second substrate 10 is disposed facing the first substrate 1 so as to sandwich the photoelectric conversion element therebetween. A sealing member 9 is disposed between the first substrate 1 and the second substrate 10 .

[0368] In the solar cell module 100 , the first electrode 2 a and the first electrode 2 b are separated by the hole transport layer 6 , which is an extended continuous layer.

[0369] Figure 2 is an explanatory view showing another example of the structure of the solar cell module of the present disclosure.

[0370] like Figure 2 As shown, the solar cell module 101 is Figure 1 An embodiment is presented in which the porous electron transport layer (porous layer) 4 is not present in the solar cell module 100 .

[0371] Figure 3 is an explanatory view showing another example of the structure of the solar cell module of the present disclosure.

[0372] like Figure 3 As shown, the solar cell module 102 is Figure 1 The solar cell module 100 presented is an embodiment in which not only the hole transport layer 6 but also the porous electron transport layer (porous layer) 4 and the perovskite layer 5 are extended continuous layers.

[0373] In the solar cell module 102 , the first electrode 2 a and the first electrode 2 b are separated by the porous layer 4 and the perovskite layer 5 , which are extended continuous layers.

[0374] Figure 4 is an explanatory view showing another example of the structure of the solar cell module of the present disclosure.

[0375] like Figure 4 As shown, the solar cell module 103 is Figure 3 An embodiment is presented in which the porous layer 4 in the solar cell module 102 is not extended.

[0376] In the solar cell module 103 , the first electrode 2 a and the second electrode 2 b are separated by the perovskite layer 5 , which is an extended continuous layer.

[0377] Figure 5 is an explanatory view showing another example of the structure of the solar cell module of the present disclosure.

[0378] like Figure 5 As shown, the solar cell module 104 is Figure 4 An embodiment is presented in which the porous layer 4 is not present in the solar cell module 103 .

[0379] Each of the solar cell modules 100 to 106 is sealed using a first substrate 1, a sealing member 9, and a second substrate 10. Therefore, the amount of moisture and oxygen concentration in the hollow portion between the second electrode 7 and the second substrate 10 can be controlled. By controlling the amount of moisture and oxygen concentration in the hollow portion of each of the solar cell modules 100 to 106, power generation performance and durability can be improved. Specifically, when the solar cell module further includes: a second substrate positioned facing the first substrate such that the first and second substrates sandwich the photoelectric conversion element; and a sealing member positioned between the first and second substrates and sealing the photoelectric conversion element, the amount of moisture and oxygen concentration in the hollow portion can be controlled, which can improve power generation performance and durability.

[0380] The oxygen concentration in the hollow portion is not particularly limited and can be appropriately selected depending on the intended purpose. However, the concentration is preferably 0% or more and 21% or less, more preferably 0.05% or more and 10% or less, still more preferably 0.1% or more and 5% or less.

[0381] In each of the solar cell modules 100 to 106, the second electrode 7 and the second substrate 10 are not in contact with each other. Therefore, it is possible to prevent the second electrode 7 from being peeled off and damaged.

[0382] Furthermore, each of solar cell modules 100 to 106 includes a through-hole 8 configured to electrically connect photoelectric conversion element a with photoelectric conversion element b. In each of solar cell modules 100 to 106, the second electrode 7a of photoelectric conversion element a is electrically connected to the first electrode 2b of photoelectric conversion element b via the through-hole 8 that penetrates the hole transport layer 6, thereby connecting photoelectric conversion element a and photoelectric conversion element b in series. As described above, when multiple photoelectric conversion elements are connected in series, the open-circuit voltage of the solar cell module can be increased.

[0383] Note that the through-portion 8 can also penetrate through the first electrode 2 and reach the first substrate 1. Alternatively, the through-portion 8 can be prevented from reaching the first substrate 1 by stopping processing within the first electrode 2. If the through-portion 8 is in the form of a pore that penetrates through the first electrode 2 and reaches the first substrate 1, if the total opening area of the pores is too large relative to the area of the through-portion 8, the cross-sectional area of the first electrode 2 film decreases, resulting in an increase in resistance, which may lead to a decrease in power generation efficiency. Therefore, the ratio of the total opening area of the pores to the area of the through-portion 8 is preferably 5 / 100 or greater and 60 / 100 or less.

[0384] In addition, the method for forming the through-portion is not particularly limited and can be appropriately selected according to the intended purpose. Examples of the method include sandblasting, water jetting, chemical etching, laser processing, and a method using sandpaper. Among them, the laser processing method is preferred because pores can be formed without using sand, etching, and resist, and this makes it possible to process the pores in a clean and reproducible manner. In addition, the reason why the laser processing method is preferred is as follows. Specifically, when the through-portion 8 is formed, at least one of the dense layer 3, the porous layer 4, the perovskite layer 5, the hole transport layer 6, and the second electrode 7 can be removed by impact stripping using a laser processing method. Therefore, there is no need to set a mask during lamination, and the removal of the material forming the photoelectric conversion element and the formation of the through-portion can be easily performed at one time.

[0385] Here, the space between the perovskite layer in photoelectric conversion element a and the perovskite layer in photoelectric conversion element b can be extended or can be separated. When they are separated, the distance between them is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less. When the distance between the perovskite layer in photoelectric conversion element a and the perovskite layer in photoelectric conversion element b is 1 μm or more and 100 μm or less, the porous titanium oxide layer is separated from the perovskite layer and less electron recombination by diffusion occurs. Therefore, this makes it possible to maintain power generation efficiency even after long-term exposure to light with high illumination. That is, when the distance between the electron transport layer and the perovskite layer in one photoelectric conversion element of at least two adjacent photoelectric conversion elements and the electron transport layer and the perovskite layer in another photoelectric conversion element is 1 μm or more and 100 μm or less, power generation efficiency can be maintained even after long-term exposure to light with high illumination.

[0386] Here, the phrase "the distance between the electron transport layer and the perovskite layer in one photoelectric conversion element and the electron transport layer and the perovskite layer in the other photoelectric conversion element among at least two photoelectric conversion elements adjacent to each other" refers to the shortest distance between the electron transport layer in the photoelectric conversion element and the periphery (end portion) of the perovskite layer.

[0387] The solar cell module disclosed herein can be used in a power supply device by combining it with, for example, a circuit board configured to control the generated current. Examples of devices using such a power supply device include electronic calculators and watches. Furthermore, a power supply device including the solar cell module disclosed herein can be used in, for example, mobile phones, electronic notebooks, and electronic paper. A power supply device including the solar cell module disclosed herein can be used as an auxiliary power source configured to extend the continuous operating time of rechargeable or battery-powered appliances, or as a power source that can be used at night by combining it with a secondary battery.

[0388] Furthermore, the solar cell module of the present disclosure can be used in IoT devices or artificial satellites as a self-supporting power source without the need to replace batteries or power wiring.

[0389] (Electronic Devices)

[0390] The electronic device of the present disclosure includes: the solar cell module of the present disclosure; and a device configured to be driven by power generated by photoelectric conversion of the solar cell module. If necessary, the electronic device of the present disclosure further includes other devices.

[0391] (Power Module)

[0392] The power module of the present disclosure includes: the solar cell module of the present disclosure; and a power integrated circuit (IC). If necessary, the power module of the present disclosure may further include other devices.

[0393] Specific embodiments of an electronic device including the solar cell module of the present disclosure and a device configured to be driven by electric power obtained by power generation of the solar cell module will be described.

[0394] Figure 6 is a block diagram of a mouse for a personal computer as one example of the electronic device of the present disclosure.

[0395] like Figure 6 The solar cell module's photoelectric conversion element, power supply IC, and power storage device are combined to allow the supplied power to be transferred to the power supply of the mouse's control circuit. As a result, the power storage device is charged when the mouse is not in use, and the mouse is driven by electricity, resulting in a mouse that requires neither wiring nor battery replacement. This eliminates the need for batteries, significantly reducing its weight.

[0396] Figure 7 It is presented Figure 6 Schematic external view of one example of a mouse presented in .

[0397] like Figure 7 As shown, the solar cell module, power supply IC, and power storage device are installed within the mouse, but the upper portion of the photoelectric conversion element is covered with a transparent housing, allowing the photoelectric conversion element of the solar cell module to receive light. Furthermore, the entire housing of the mouse can be formed from a transparent resin. The placement of the photoelectric conversion element is not limited to the above. For example, the photoelectric conversion element can be placed in a position where light can be transmitted even when the mouse is covered by a hand, and this arrangement may be preferred.

[0398] Another embodiment of an electronic device including the solar cell module of the present disclosure and a device configured to be driven by electric power obtained by power generation of the solar cell module will be described.

[0399] Figure 8 is a block diagram of a keyboard for a personal computer as one example of the electronic device of the present disclosure.

[0400] like Figure 8 As presented, the solar cell module's photoelectric conversion elements, power supply IC, and power storage device are combined to deliver the supplied power to the keyboard's control circuitry. As a result, when the keyboard is not in use, the power storage device can be charged and used to power the keyboard. This provides a keyboard that requires neither wiring nor battery replacement. This configuration is effective because it eliminates the need for batteries and can therefore reduce weight.

[0401] Figure 9 It is presented Figure 8 Schematic external view of an example of a keyboard presented in .

[0402] like Figure 9 As shown, the photoelectric conversion element, power IC and power storage device of the solar cell module are installed inside the keyboard, but the upper part of the photoelectric conversion element is covered with a transparent shell so that the photoelectric conversion element receives light. The entire shell of the keyboard can be formed of a transparent resin. The arrangement of the photoelectric conversion element is not limited to the above. In the case of a small keyboard with little space for accommodating the photoelectric conversion element, the small photoelectric conversion element can be embedded in the keyboard. Figure 10 Among some of the keys presented, and this arrangement is effective.

[0403] Next, another embodiment of an electronic device including the solar cell module of the present disclosure and a device configured to be driven by electric power obtained by power generation of the solar cell module will be described.

[0404] Figure 11 is a block diagram of a sensor as an example of the electronic device of the present disclosure.

[0405] like Figure 11 As presented, the photoelectric conversion element, power IC and power storage device of the solar cell module are combined, and the supplied power is delivered to the power supply of the sensor circuit. As a result, the sensor module can be constructed without connecting to an external power supply and without replacing the battery. The sensing targets are, for example, temperature and humidity, illumination, human body detection, CO2, acceleration, UV, noise, geomagnetism and atmospheric pressure, and this electronic device can be applied to various sensors, which is effective. Figure 11 As presented, the sensor module is configured to sense a target for periodic measurement and transmit the read data to a personal computer (PC) or a smartphone through wireless communication.

[0406] With the advent of the Internet of Things (IoT) society, the use of sensors is expected to increase significantly. Replacing the batteries of multiple sensors one by one is time-consuming and unrealistic. In addition, the sensors are installed in locations such as ceilings and walls where it is not easy to replace the batteries, and this arrangement deteriorates operability. The fact that it can be powered by a photoelectric conversion element is also very advantageous. In addition, the solar cell module disclosed in the present invention has the following advantages: high output can be obtained even under low illumination light and since the output is less dependent on the light incident angle, a high degree of freedom in installation can be achieved.

[0407] Next, another embodiment of an electronic device including the solar cell module of the present disclosure and a device configured to be driven by electric power obtained by power generation of the solar cell module will be described.

[0408] Figure 12 is a block diagram of a turntable as an example of the electronic device of the present disclosure.

[0409] like Figure 12 As presented in [1], a photoelectric conversion element, a power supply IC, and a power storage device are combined together, and the supplied power is transferred to the power supply of the turntable control circuit. As a result, the turntable can be constructed without connecting to an external power supply and without replacing batteries.

[0410] Turntables are used, for example, in display cabinets for displaying products. Power supply wiring detracts from the appearance of the display, and battery replacement requires removing the displayed products, which is time-consuming. The use of the solar cell module disclosed herein is effective because it can resolve these issues.

[0411] As described above, electronic devices including the solar cell module of the present disclosure, devices configured to be driven by power generated by the solar cell module, and power supply modules have been described. However, the described embodiments are only a portion of applicable embodiments, and the uses of the solar cell module of the present disclosure are not limited to the above-described uses.

[0412] <Application>

[0413] The solar cell module disclosed in the present invention can be used as a self-sustaining power source, and the electric energy generated by photoelectric conversion can be used to drive the device. Since the solar cell module disclosed in the present invention can generate electric energy by light irradiation, there is no need to connect the electronic device to a power source or replace the battery. Therefore, the electronic device can be driven in places where there is no power supply facility, the electronic device can be worn or carried, and the electronic device can be driven without replacing the battery even in places where it is not easy to replace the battery. In addition, when dry cells are used, the electronic device becomes heavier due to the weight of the dry cells, or the electronic device becomes larger due to the size of the dry cells. Therefore, there may be problems when installing the electronic device on a wall or ceiling or transporting the electronic device. However, since the solar cell module disclosed in the present invention is light and thin, it can be freely installed and can be worn and carried, which is advantageous.

[0414] As described above, the solar cell module of the present disclosure can be used as a self-sustaining power source and can be used in combination with various electronic devices. For example, the solar cell module of the present disclosure can be used in combination with display devices (e.g., electronic desktop calculators, watches, mobile phones, electronic notepads, and electronic paper), personal computer accessories (such as mice and keyboards), various sensor devices (e.g., temperature and humidity sensors and human detection sensors), transmitters (e.g., beacons and global positioning systems (GPS)), and a variety of electronic devices (e.g., auxiliary lights and remote controls).

[0415] The solar cell module disclosed herein has a wide range of applications because it can generate electricity particularly with low illumination light and can generate electricity indoors and in darker shade. In addition, the solar cell module is highly safe because liquid leakage that occurs in the case of dry cells and accidental ingestion that occurs in the case of button cells do not occur. In addition, the solar cell module can be used as an auxiliary power source to extend the continuous operating time of rechargeable or dry cell-type electrical appliances. As described above, when the solar cell module disclosed herein is combined with a device configured to be driven by electricity generated by photoelectric conversion of the solar cell module, an electronic device that is lightweight and easy to use, has a high degree of freedom in installation, does not require battery replacement, is excellent in safety, and is effective in reducing environmental load can be obtained.

[0416] Figure 13 This diagram shows the basic configuration of an electronic device obtained by combining the solar cell module of the present disclosure with a device configured to be driven by electricity generated by photoelectric conversion in the solar cell module. When the photoelectric conversion element is illuminated by light, the electronic device can generate and extract electricity. The generated electricity can also drive the device's circuitry.

[0417] Since the output of the photoelectric conversion element of the solar cell module varies according to the ambient illuminance, Figure 13 The electronic device presented may not be able to be driven stably in some cases. In this case, Figure 14 As presented, it is effective to incorporate a power supply IC for the photoelectric conversion element between the photoelectric conversion element and the circuit of the device in order to supply a stable voltage to the circuit side.

[0418] The photoelectric conversion element of the solar cell module can generate electricity as long as it emits light with sufficient illumination. However, when there is not enough illumination to generate electricity, the required electricity cannot be obtained, which is a disadvantage of the photoelectric conversion element. In this case, Figure 15 As shown, when a power storage device such as a capacitor is installed between the power supply IC and the device circuit, excess power from the photoelectric conversion element can be stored in the power storage device. Furthermore, the power stored in the power storage device can be supplied to the device circuit, enabling stable operation even when the illumination is too low or even when no light is applied to the photoelectric conversion element.

[0419] As described above, the electronic device obtained by combining the solar cell module of the present disclosure with the device circuit can be operated even in an environment without a power source, eliminating the need for battery replacement. Furthermore, it can be stably operated in combination with a power supply IC or a power storage device. Therefore, the advantages of the photoelectric conversion element can be fully utilized.

[0420] At the same time, the solar cell module of the present disclosure can also be used as a power module, and such use is effective. Figure 16 As presented in, for example, when the solar cell module of the present disclosure is connected to a power supply IC for a photoelectric conversion element, a DC power supply module can be constructed that is capable of supplying power generated by photoelectric conversion of the photoelectric conversion element of the solar cell to the power supply IC at a predetermined voltage level.

[0421] In addition, if Figure 17 As shown, by adding a power storage device to the power IC, the power generated by the photoelectric conversion element of the solar cell module can be stored in the power storage device. This allows the power module to be configured to provide power even when the illumination is too low or even when no light is applied to the photoelectric conversion element.

[0422] Figure 16 and Figure 17 The power module of the present disclosure presented in can be used as a power module without replacing batteries like primary batteries known in the art.

[0423] [Example]

[0424] The present disclosure will be described in more detail by way of Examples and Comparative Examples. The present disclosure should not be construed as being limited to these Examples.

[0425] (Synthesis Example 1)

[0426] <Synthesis of a polymer having a repeating unit represented by the general formula (1)>

[0427] The polymer (A-11) represented by the following structural formula was synthesized by the following reaction.

[0428] [Chemical Formula 28]

[0429]

[0430] Here, n represents an integer of 2 or more, and allows the polymer (A-11) to have a weight average molecular weight of 2,000 or more.

[0431] First, the above-mentioned dialdehyde compound (0.66 g) (2.0 mmol) and the above-mentioned diphosphonate compound (1.02 g) (2.0 mmol) were placed in a 100 mL four-necked flask, the resultant was purged with nitrogen, and then tetrahydrofuran (75 mL) was added. To this solution, 1.0 mol / dm potassium tert-butoxide (6.75 mL) (6.75 mmol) was added dropwise. 3The tetrahydrofuran solution was stirred at room temperature for 2 hours. Diethyl benzylphosphonate and benzaldehyde were added thereto in sequence, and then stirred for 2 hours. Acetic acid (about 1 mL) was added thereto to terminate the reaction, and the solution was washed with water. After the solvent was removed under reduced pressure, tetrahydrofuran and methanol were used to purify the resulting product by reprecipitation to obtain a polymer (A-11) (0.95 g) represented by the above structural formula.

[0432] The obtained polymer (A-11) represented by the above structural formula had a weight average molecular weight in terms of polystyrene of 20,000, as measured by gel filtration chromatography (GPC). The ionization potential of the polymer (A-11) measured using optical emissivity spectroscopy (AC-2, available from RIKENKEIKI CO., LTD.) was 5.22 eV. All ionization potentials described below were measured using the AC-2.

[0433] (Example 1)

[0434] <Solar Cell Module Production>

[0435] First, a titanium diisopropoxide bis(acetylacetonate) isopropanol solution (obtained from Tokyo Chemical Industry Co., Ltd., B3395, 75% by mass) (0.36 g) was dissolved in isopropanol (10 mL) and the resulting liquid was applied by spin coating on an FTO glass substrate (obtained from Nippon Sheet Glass Co., Ltd.). The coating liquid was dried at 120° C. for 3 minutes and baked at 450° C. for 30 minutes to produce a first electrode and a dense electron transport layer (dense layer) on the first substrate. Note that the dense layer was set to have an average thickness of 10 μm to 40 μm.

[0436] Next, a dispersion obtained by diluting a titanium oxide paste (available from Greatcell Solar Limited, product name: MPT-20) with α-terpineol (available from KANTO CHEMICAL CO., INC.) was applied to the dense layer by spin coating. The resultant was then dried at 120°C for 3 minutes and baked at 550°C for 30 minutes.

[0437] Then, acetonitrile (obtained from KANTO CHEMICAL CO., INC.) (0.1 M) (note, M means mol / dm) in which lithium bis(trifluoromethanesulfonyl)imide (obtained from KANTO CHEMICAL CO., INC., product number: 38103) was dissolved was added. 3) was applied on the above film by spin coating and baked at 450° C. for 30 minutes to produce a porous electron transport layer (porous layer). Here, the average thickness of the porous layer was set to 150 nm.

[0438] Next, lead (II) iodide (obtained from Tokyo Chemical Industry Co., Ltd., L0279, 0.5306 g), lead (II) bromide (obtained from Tokyo Chemical Industry Co., Ltd., L0288, 0.0736 g), methylammonium bromide (obtained from Tokyo Chemical Industry Co., Ltd., M2589, 0.0224 g), formamidine hydroiodide (obtained from Tokyo Chemical Industry Co., Ltd., F0974, 0.1876 g) and potassium iodide (obtained from KANTO CHEMICAL CO., INC., 32351, 0.0112 g) were added to N,N-dimethylformamide (obtained from KANTO CHEMICAL CO., INC., 0.8 ml) and dimethyl sulfoxide (obtained from KANTO CHEMICAL CO., INC.). CO., INC., 0.2 ml) and the resultant was heated and stirred at 60°C to obtain a solution. This solution was applied to the porous layer by spin coating while adding chlorobenzene (0.3 ml) to form a perovskite film. The perovskite film was then dried at 150°C for 30 minutes to produce a perovskite layer.

[0439] Note that the average thickness of the perovskite layer is set to 200 nm or more and 350 nm or less.

[0440] The laminate obtained through the above steps was subjected to laser processing to form grooves so that the distance between adjacent laminates was 10 μm. Then, the polymer (A-11) represented by the above structural formula (weight average molecular weight = 20,000, ionization potential: 5.22 eV) (36.8 mg), 2,2(7,7(-tetrakis-(N,N-di-p-methoxyaniline)9,9(-spirobifluorene))) (hereinafter referred to as "spiro-OMeTAD", obtained from Merck, molecular weight = 1225.4, ionization potential = 5.09 eV) (36.8 mg), lithium bis(trifluoromethanesulfonyl)imide (4.9 mg), 4-tert-butylpyridine (obtained from Tokyo Chemical Industry Co., Ltd., B0388) (6.8 mg) and tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridinium)cobalt(III) hexafluorophosphate (obtained from Greatcell Solar, MS210205) (0.1 mg) were dissolved in chlorobenzene (obtained from KANTO CHEMICAL CO., INC.) (1.5 mL). The obtained solution was applied to the laminate obtained by the above steps by spin coating to produce a hole transport layer. The average thickness of the hole transport layer (the portion above the perovskite layer) was set to 100 nm to 200 nm. The difference in ionization potential of the two hole transport materials was 0.13 eV.

[0441] Gold (obtained from TANAKAKIKINZOKU KOGYO KK) (100 nm) was deposited on the laminate under vacuum.

[0442] The ends of the first substrate and the second substrate provided with a sealing member are etched by laser processing and then laser processed to form a through hole (conductive portion) for connecting the photoelectric conversion elements in series. Next, silver is deposited on the above-mentioned laminate under vacuum to form a second electrode with a thickness of about 100nm. By mask formation, the distance between adjacent second electrodes will be 200μm. Silver is also deposited on the inner wall of the through hole, and it is confirmed that adjacent photoelectric conversion elements are connected in series. The number of photoelectric conversion elements arranged in series is 6.

[0443] Then, a UV curable resin (obtained from ThreeBond Holdings Co., Ltd., product name: TB3118) was applied to the end of the first substrate with a dispenser (obtained from SAN-EI TECH Ltd., product name: 2300N) so that the photoelectric conversion element (power generation area) was surrounded. Then, it was transferred to a glove box that had been controlled to have low humidity (dew point: -30°C) and an oxygen concentration of 0.2%. Then, a cover glass as the second substrate was set on the UV curable resin, and the UV curable resin was cured by ultraviolet irradiation to seal the power generation area. As a result, a product such as Figure 1 Table 1 shows the distances between the layers constituting the photoelectric conversion elements adjacent to each other in the solar cell module 1 of the present disclosure.

[0444] <Evaluation of Solar Cell Modules>

[0445] In the presence of a solar simulator (AM1.5, 10 mW / cm 2 ) While irradiating the obtained solar cell module 1 with light, the characteristics (initial characteristics) of the solar cell of the obtained solar cell module 1 were evaluated using a solar cell evaluation system (available from NF Corporation, product name: As-510-PV03). Furthermore, after continuously emitting light for 100 hours using the above-mentioned solar simulator under the above-mentioned conditions, the characteristics of the solar cell (characteristics after 100 hours of continuous irradiation) were evaluated in the same manner as described above.

[0446] The evaluation characteristics of the solar cell were open-circuit voltage, short-circuit current density, form factor, and conversion efficiency (power generation efficiency). The conversion efficiency maintenance rate was determined by comparing the conversion efficiency after 100 hours of continuous irradiation to the conversion efficiency at the initial stage. The results are shown in Table 3.

[0447] (Example 2)

[0448] A photoelectric conversion element was produced in the same manner as in Example 1, except that the first electrode, the dense layer, the porous layer, and the perovskite layer in the photoelectric conversion element adjacent to each other were arranged to have a distance of 40 μm. Figure 1 The solar cell module 2 was presented. Each distance between the layers constituting the photoelectric conversion elements adjacent to each other is presented in Table 1. The solar cell module 2 was evaluated in the same manner as in Example 1. The evaluation results are presented in Table 3.

[0449] (Example 3)

[0450] A compound was produced in the same manner as in Example 1 except that spiro-OMeTAD (obtained from Merck, molecular weight = 1225.4, ionization potential = 5.09 eV) (36.8 mg) was changed to the compound represented by the following (C-1) (molecular weight: 844.1, ionization potential: 5.21 eV) (36.8 mg). Figure 1 The solar cell module 3 was presented. The difference in ionization potential between the two hole transport materials was 0.01 eV. The distances between the layers constituting the adjacent photoelectric conversion elements are shown in Table 1. Solar cell module 3 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0451] [Chemical Formula 29]

[0452]

[0453] (Example 4)

[0454] A 5-nitro-1,2-dimethyl-1-thiazolyl-1-propene was produced in the same manner as in Example 1, except that the polymer (A-11) represented by the above structural formula (weight average molecular weight = 20,000, ionization potential: 5.22 eV) (36.8 mg) was changed to a polymer (B-1) represented by the following formula (obtained from Aldrich, "P3HT", weight average molecular weight = 50,000, ionization potential = 5.0 eV) and spiro-OMeTAD (obtained from Merck, molecular weight = 1225.4, ionization potential = 5.09 eV) (36.8 mg) was changed to a compound (C-2) represented by the following formula (molecular weight: 554.9, ionization potential = 5.05 eV). Figure 1 The solar cell module 4 presented here has an ionization potential difference of 0.05 eV between the two hole transport materials. Table 1 lists the distances between the layers constituting the adjacent photoelectric conversion elements. The solar cell module 4 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0455] [Chemical formula 30]

[0456]

[0457] Here, m represents an integer of 2 or more and allows the polymer (B-1) represented by the above formula to have a weight average molecular weight of 2,000 or more.

[0458]

[0459] (Example 5)

[0460] The same method as in Example 1 was used to produce the porous layer. Figure 2The solar cell module 5 was presented. Each distance between the layers constituting the photoelectric conversion elements adjacent to each other is presented in Table 1. The solar cell module 5 was evaluated in the same manner as in Example 1. The results are presented in Table 3.

[0461] (Example 6)

[0462] Solar cell module 6 was produced in the same manner as in Example 5, except that the dense layer was changed to a dense layer formed of tin oxide formed by sputtering. Each distance between the layers constituting the adjacent photoelectric conversion elements is shown in Table 1. Solar cell module 6 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0463] (Example 7)

[0464] Solar cell module 7 was produced in the same manner as in Example 6, except that cesium iodide (0.0143 g) was further used in addition to lead (II) iodide (0.5306 g), lead (II) bromide (0.0736 g), methylamine bromide (0.0224 g), formamidine iodide (0.1876 g), and potassium iodide (0.0112 g) used to form the perovskite layer in Example 6. The distances between the layers constituting the adjacent photoelectric conversion elements are shown in Table 1. Solar cell module 7 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0465] (Example 8)

[0466] Solar cell module 8 was produced in the same manner as in Example 5, except that polymer (A-11) in the hole transport material was changed to polymer (A-11) (weight average molecular weight Mw = 122,000). Each distance between the layers constituting the adjacent photoelectric conversion elements is shown in Table 1. Solar cell module 8 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0467] (Example 9)

[0468] Solar cell module 9 was produced in the same manner as in Example 5, except that polymer (A-11) in the hole transport material was changed to polymer (A-11) (weight average molecular weight Mw = 282,000). Each distance between the layers constituting the adjacent photoelectric conversion elements is shown in Table 1. Solar cell module 9 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0469] (Example 10)

[0470] Solar cell module 10 was produced in the same manner as in Example 5, except that polymer (A-11) in the hole transport material was changed to polymer (A-11) (weight average molecular weight Mw = 282,000) and "spiro-OMeTAD" was changed to the compound represented by (C-1) (molecular weight 844.1, ionization potential 5.21 eV). The distances between the layers constituting the adjacent photoelectric conversion elements are shown in Table 1. Solar cell module 10 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0471] (Example 11)

[0472] Solar cell module 11 was produced in the same manner as in Example 5, except that polymer (A-11) in the hole transport material was changed to polymer (A-11) (weight average molecular weight Mw = 282,000) and "spiro-OMeTAD" was changed to the compound represented by compound (C-2) (molecular weight 554.9, ionization potential = 5.05 eV). Each distance between the layers constituting the adjacent photoelectric conversion elements is shown in Table 1. Solar cell module 11 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0473] (Example 12)

[0474] Solar cell module 12 was produced in the same manner as in Example 5, except that the polymer (A-11) in the hole transport material was changed to compound (C-3) (molecular weight = 2,157, ionization potential = 5.23 eV). The distances between the layers constituting the adjacent photoelectric conversion elements are shown in Table 1. Solar cell module 12 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0475] (Example 13)

[0476] Solar cell module 13 was produced in the same manner as in Example 5, except that the polymer (A-11) in the hole transport material was changed to compound (C-3) (molecular weight = 2,157, ionization potential = 5.23 eV) and "spiro-OMeTAD" was changed to the compound shown in (C-1) above (molecular weight 844.1, ionization potential 5.21 eV). The distances between the layers constituting the adjacent photoelectric conversion elements are shown in Table 1. Solar cell module 13 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0477] (Example 14)

[0478] Solar cell module 14 was produced in the same manner as in Example 5, except that the polymer (A-11) in the hole transport material was changed to compound (C-3) (molecular weight = 2,157, ionization potential = 5.23 eV) and "spiro-OMeTAD" was changed to the compound represented by compound (C-2) (molecular weight 554.9, ionization potential 5.05 eV). Each distance between the layers constituting the adjacent photoelectric conversion elements is shown in Table 1. Solar cell module 14 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0479] (Example 15)

[0480] Solar cell module 15 was produced in the same manner as in Example 7, except that potassium iodide (0.0112 g) was not included in the lead (II) iodide (0.5306 g), lead (II) bromide (0.0736 g), methylamine bromide (0.0224 g), formamidine iodide (0.1876 g), potassium iodide (0.0112 g), and cesium iodide (0.0143 g) used in forming the perovskite layer, and the weight of cesium iodide (0.0318 g) was increased. The distances between the layers constituting the adjacent photoelectric conversion elements are shown in Table 1. Solar cell module 15 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0481] (Example 16)

[0482] Solar cell module 16 was produced in the same manner as in Example 15, except that antimony iodide (0.0204 g) was used in addition to lead (II) iodide (0.5306 g), lead (II) bromide (0.0736 g), methylamine bromide (0.0224 g), formamidine iodide (0.1876 g), and cesium iodide (0.0318 g) used to form the perovskite layer. The distances between the layers constituting the adjacent photoelectric conversion elements are shown in Table 1. Solar cell module 16 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0483] (Example 17)

[0484] Solar cell module 17 was produced in the same manner as in Example 6, except that the weight of polymer (A-11) (weight average molecular weight = 20,000, ionization potential: 5.22 eV) in the hole transport material was changed to 51.5 mg and the weight of spiro-OMeTAD (obtained from Merck, molecular weight = 1225.4, ionization potential = 5.09 eV) was changed to 22.1 mg. Each distance between the layers constituting the adjacent photoelectric conversion elements is shown in Table 1. Solar cell module 17 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0485] (Example 18)

[0486] Solar cell module 18 was produced in the same manner as in Example 6, except that the weight of polymer (A-11) (weight average molecular weight = 20,000, ionization potential: 5.22 eV) in the hole transport material was changed to 44.2 mg and the weight of spiro-OMeTAD (obtained from Merck, molecular weight = 1225.4, ionization potential = 5.09 eV) was changed to 66.2 mg. Each distance between the layers constituting the adjacent photoelectric conversion elements is shown in Table 1. Solar cell module 18 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0487] (Comparative Example 1)

[0488] The porous layer and the perovskite layer were formed into an extended continuous layer in the same manner as in Example 1. Figure 3 The solar cell module 19 was presented. Each distance between the layers constituting the photoelectric conversion elements adjacent to each other is presented in Table 1. The solar cell module 19 was evaluated in the same manner as in Example 1. The results are presented in Table 3.

[0489] (Comparative Example 2)

[0490] A photoelectric conversion element was produced in the same manner as in Example 1, except that the first electrode and the dense layer in the adjacent photoelectric conversion element were set to have a distance of 40 μm and the porous layer and the perovskite layer were extended continuous layers. Figure 3 The solar cell module 20 presented in . Each distance between the layers constituting the photoelectric conversion elements adjacent to each other is presented in Table 1. The solar cell module 20 was evaluated in the same manner as in Example 1. The results are presented in Table 3.

[0491] (Comparative Example 3)

[0492] A photoelectric conversion element was produced in the same manner as in Example 1, except that the first electrode, the dense layer, and the porous layer in the adjacent photoelectric conversion element were set to have a distance of 40 μm and the perovskite layer was an extended continuous layer. Figure 4 The solar cell module 21 was presented. Each distance between the layers constituting the photoelectric conversion elements adjacent to each other is presented in Table 1. The solar cell module 21 was evaluated in the same manner as in Example 1. The results are presented in Table 3.

[0493] (Comparative Example 4)

[0494] A product was produced in the same manner as in Example 1, except that the polymer (A-11) represented by the above structural formula (weight average molecular weight = 20,000, ionization potential: 5.22 eV) (36.8 mg) and spiro-OMeTAD (obtained from Merck, molecular weight = 1225.4, ionization potential = 5.09 eV) (36.8 mg) were changed to spiro-OMeTAD (obtained from Merck, molecular weight = 1225.4, ionization potential = 5.09 eV) (73.6 mg). Figure 1 The solar cell module 22 was presented. Each distance between the layers constituting the photoelectric conversion elements adjacent to each other is presented in Table 1. The solar cell module 22 was evaluated in the same manner as in Example 1. The results are presented in Table 3.

[0495]

[0496] [Table 2]

[0497]

[0498]

[0499] As can be seen from the results in Table 3, Examples 1 to 18 were found to have good durability, as all the conversion efficiency maintenance rates were 90% or greater after 100 hours of continuous irradiation testing, and neither the gold provided as the second electrode nor the hole transport layer peeled off. Meanwhile, Comparative Examples 1 to 3 were found to have low durability, as they included the same hole transport material as Example 1 but were modules formed of a continuous porous layer and a continuous perovskite layer.

[0500] It was observed that, in the solar cell module 22 of Comparative Example 4, after continuous irradiation for 100 hours, the gold and hole transport layer provided as the second electrode peeled off.

[0501] As described above, in the solar cell module of the present disclosure, the hole transport layer is a continuous layer extending between at least two adjacent photoelectric conversion elements, and the first electrode, electron transport layer, and perovskite layer in at least two adjacent photoelectric conversion elements are separated by the hole transport layer. As a result, the solar cell module of the present disclosure can maintain power generation efficiency even after long-term exposure to light with high illuminance.

[0502] For example, aspects of the present disclosure are as follows.

[0503] <1> A solar cell module comprising:

[0504] a first substrate; and

[0505] A plurality of photoelectric conversion elements are provided on the first substrate, each of the plurality of photoelectric conversion elements including a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode,

[0506] wherein, in at least two photoelectric conversion elements adjacent to each other, the hole transport layer is an extended continuous layer, and wherein the first electrode, the electron transport layer, and the perovskite layer in at least two photoelectric conversion elements adjacent to each other are separated by the hole transport layer, and

[0507] The hole transport layer includes a polymer having a weight average molecular weight of 2,000 or more or a compound having a molecular weight of 2,000 or more as a hole transport material.

[0508] <2> according to <1> Solar cell modules,

[0509] wherein the polymer having a weight average molecular weight of 2,000 or more comprises a repeating unit represented by the following general formula (1) or (2):

[0510] [Chemical Formula 31]

[0511]

[0512] In the general formula (1), R1 and R2 may be the same or different from each other, and each represents at least one selected from a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, and an aryl group; R3 represents one selected from an alkyl group, an aralkyl group, an aryl group, and a heterocyclic group; X l represents one selected from an alkylene group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, n represents an integer of 2 or greater and allows the polymer represented by the general formula (1) to have a weight average molecular weight of 2,000 or greater, and p represents 0, 1, or 2; and

[0513] [Chemical Formula 32]

[0514]

[0515] Wherein, in the general formula (2), R4 represents one selected from a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group and an aryl group, X2 represents one selected from an oxygen atom, a sulfur atom and a selenium atom; X3 represents one selected from an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, m represents an integer of 2 or greater and allows the polymer represented by the general formula (2) to have a weight average molecular weight of 2,000 or greater, and q represents 0, 1 or 2.

[0516] <3> A solar cell module, comprising:

[0517] substrate; and

[0518] A plurality of photoelectric conversion elements are provided on the substrate, each of the plurality of photoelectric conversion elements including a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode,

[0519] wherein, in at least two photoelectric conversion elements adjacent to each other, the hole transport layer is an extended continuous layer, and wherein the first electrode, the electron transport layer, and the perovskite layer in at least two photoelectric conversion elements adjacent to each other are separated by the hole transport layer, and

[0520] The hole transport layer contains: a polymer containing a repeating unit represented by the following general formula (1) or (2) and having a weight average molecular weight of 2,000 or more; or a compound having a molecular weight of 2,000 or more, as a hole transport material:

[0521] [Chemical Formula 33]

[0522]

[0523] In the general formula (1), R1 and R2 may be the same or different from each other, and each represents at least one selected from a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, and an aryl group; R3 represents one selected from an alkyl group, an aralkyl group, an aryl group, and a heterocyclic group; X l represents one selected from an alkylene group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, n represents an integer of 2 or greater and allows the polymer represented by the general formula (1) to have a weight average molecular weight of 2,000 or greater, and p represents 0, 1, or 2; and

[0524] [Chemical Formula 34]

[0525]

[0526] Wherein, in the general formula (2), R4 represents one selected from a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group and an aryl group, X2 represents one selected from an oxygen atom, a sulfur atom and a selenium atom, X3 represents one selected from an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, m represents an integer of 2 or greater and allows the polymer represented by the general formula (2) to have a weight average molecular weight of 2,000 or greater, and q represents 0, 1 or 2.

[0527] <4> according to <3> Solar cell modules,

[0528] The compound having a molecular weight of less than 2,000 is selected from one of a spirobifluorene compound, a triarylamine compound and a thiophene compound.

[0529] <5> according to <1> to <4> The solar cell module according to any one of the above,

[0530] Among at least two photoelectric conversion elements adjacent to each other, a first electrode in one photoelectric conversion element and a second electrode in the other photoelectric conversion element are electrically connected to each other via a conductive portion that penetrates the hole transport layer.

[0531] <6> according to <1> to <5> The solar cell module according to any one of the above,

[0532] Among them, in at least two photoelectric conversion elements adjacent to each other, a distance between the perovskite layer in one photoelectric conversion element and the perovskite layer in the other photoelectric conversion element is 1 μm or more and 100 μm or less.

[0533] <7> according to <1> to <6> The solar cell module according to any one of the preceding claims, further comprising:

[0534] a second substrate disposed to face the first substrate so as to sandwich the plurality of photoelectric conversion elements; and

[0535] A sealing member is provided between the first substrate and the second substrate and is configured to seal the plurality of photoelectric conversion elements.

[0536] <8> An electronic device comprising:

[0537] according to <1> to <7> The solar cell module of any one of ; and

[0538] A device configured to be driven by electricity generated by photoelectric conversion of a solar cell module.

[0539] <9> An electronic device comprising:

[0540] according to <1> to <7> The solar cell module of any one of the items;

[0541] a storage battery configured to store electric power generated by photoelectric conversion of the solar cell module; and

[0542] A device configured to be driven by at least one of electric power generated by photoelectric conversion in a solar cell module and electric power stored in a storage battery.

[0543] <10> A power module comprising:

[0544] according to <1> to <7> The solar cell module of any one of ; and

[0545] Power integrated circuit (IC).

[0546] according to <1> to <7> The solar cell module according to any one of <8> or <9> electronic device, and <10> The power supply module can solve the problems existing in the prior art and achieve the purpose of the present disclosure.

[0547] [Reference Mark List]

[0548] 1: First substrate

[0549] 2, 2a, 2b: First electrode

[0550] 3: Dense electron transport layer (dense layer)

[0551] 4: Porous electron transport layer (porous layer)

[0552] 5: Perovskite layer

[0553] 6: Hole transport layer

[0554] 7, 7a, 7b: Second electrode

[0555] 8: Through part

[0556] 9: Sealing components

[0557] 100 to 104: Solar cell modules

[0558] a, b: Photoelectric conversion elements

Claims

1. A solar cell module, comprising: a first substrate; and a plurality of photoelectric conversion elements provided on the first substrate, each of the plurality of photoelectric conversion elements including a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode; wherein, in at least two of the photoelectric conversion elements adjacent to each other, the hole transport layer is an extended continuous layer, and wherein the first electrode, the electron transport layer, and the perovskite layer in the at least two photoelectric conversion elements adjacent to each other are separated by the hole transport layer, and The hole transport layer includes, as a hole transport material, a polymer having a weight average molecular weight of 2,000 or more or a compound having a molecular weight of 2,000 or more; and a compound having a molecular weight of less than 2,000.

2. The solar cell module according to claim 1, wherein the polymer having a weight average molecular weight of 2,000 or more comprises a repeating unit represented by the following general formula (1) or (2): [Chemical Formula 1] in, In the general formula (1), R1 and R2 may be the same as or different from each other, and each represents at least one selected from a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, and an aryl group; R3 represents one selected from an alkyl group, an aralkyl group, an aryl group, and a heterocyclic group; X l represents one selected from an alkylene group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, n represents an integer of 2 or greater and allows the polymer represented by the general formula (1) to have a weight average molecular weight of 2,000 or greater, and p represents 0, 1, or 2; and [Chemical Formula 2] Wherein, in the general formula (2), R4 represents one selected from a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group and an aryl group, X2 represents one selected from an oxygen atom, a sulfur atom and a selenium atom, X3 represents one selected from an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, m represents an integer of 2 or greater and allows the polymer represented by the general formula (2) to have a weight average molecular weight of 2,000 or greater, and q represents 0, 1 or 2.

3. The solar cell module according to claim 2, The compound with a molecular weight less than 2000 is selected from one of a spirobifluorene compound, a triarylamine compound and a thiophene compound.

4. The solar cell module according to any one of claims 1 to 3, in, In the at least two photoelectric conversion elements adjacent to each other, the first electrode in one photoelectric conversion element and the second electrode in the other photoelectric conversion element are electrically connected to each other via a conductive portion penetrating the hole transport layer.

5. The solar cell module according to any one of claims 1 to 4, in, In the at least two photoelectric conversion elements adjacent to each other, a distance between the perovskite layer in one photoelectric conversion element and the perovskite layer in the other photoelectric conversion element is 1 μm or more and 100 μm or less.

6. The solar cell module according to any one of claims 1 to 5, further comprising: a second substrate disposed to face the first substrate so as to sandwich the plurality of photoelectric conversion elements; and A sealing member is provided between the first substrate and the second substrate and is configured to seal the plurality of photoelectric conversion elements.

7. An electronic device comprising: The solar cell module according to any one of claims 1 to 6; and A device configured to be driven by electric power generated by photoelectric conversion of the solar cell module.

8. An electronic device comprising: The solar cell module according to any one of claims 1 to 6; a storage battery configured to store electricity generated by photoelectric conversion of the solar cell module; and A device configured to be driven by at least one of the electric power generated by photoelectric conversion of the solar cell module and the electric power stored in the storage battery.

9. A power module, comprising: The solar cell module according to any one of claims 1 to 6; and Power integrated circuit (IC).

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