JP2022144059A - Photoelectric conversion element, electronic device, and power supply module - Google Patents

Abstract

To provide a photoelectric conversion element capable of suppressing a decrease in output with low-illuminance light when exposed to a high-temperature light irradiation environment.SOLUTION: A photoelectric conversion element includes a first electrode, an electron transport layer, a photosensitizing compound, a hole transporting layer, and a second electrode, and the photosensitizing compound includes a compound represented by the following general formula (1).SELECTED DRAWING: None

Description

The present invention relates to photoelectric conversion elements, electronic devices, and power supply modules.

In recent years, solar cells, which can generate power efficiently even in low-illuminance light, have been attracting a lot of attention, and are expected to be used not only for applications that can be installed anywhere, but also for a wide range of applications as an independent power supply that does not require battery replacement or power wiring. ing.

For example, amorphous silicon and organic solar cells are known as photoelectric conversion elements for indoor use. Among organic solar cells, a dye-sensitized solar cell is advantageous in that it can be easily produced because it is composed of layers in which a charge generation function and a charge transport function are separated. In general, dye-sensitized solar cells enclose an electrolyte, which causes problems such as volatilization and leakage of the electrolyte. However, in recent years, solid-state dye-sensitized solar cells using P-type semiconductor materials have also been developed. and is attracting attention.

Therefore, for example, a photoelectric conversion element that can suppress a voltage drop and obtain high output even in a high-temperature environment or a weak indoor light environment has been described (see, for example, Patent Document 1).

An object of the present invention is to provide a photoelectric conversion element capable of suppressing a decrease in output under low-illuminance light when exposed to a high-temperature light irradiation environment.

ただし、前記一般式（１）中、Ａｒ_１及びＡｒ_２は、置換基を有していてもよいアリール基を表す。Ｒ_１及びＲ_２は、炭素数４～１０の直鎖又は分岐状のアルキル基を表す。Ｘは、下記構造式で表されるいずれかの置換基を表す。

ただし、前記一般式（２）中、Ｒ_３は、アリール基、下記構造式で表されるいずれかの置換基のいずれかを表す。ｎは０～１の整数を表す。

A photoelectric conversion element of the present invention as a means for solving the above problems is a photoelectric conversion element having a first electrode, an electron transport layer, a photosensitizing compound, a hole transport layer, and a second electrode. The photosensitizing compound includes a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

However, in the general formula (1), Ar ₁ and Ar ₂ represent an aryl group which may have a substituent. R ₁ and R ₂ each represent a linear or branched alkyl group having 4 to 10 carbon atoms. X represents any substituent represented by the following structural formula.

However, in the general formula (2), R ₃ represents either an aryl group or a substituent represented by the following structural formula. n represents an integer of 0 to 1;

INDUSTRIAL APPLICABILITY The present invention can provide a photoelectric conversion element capable of suppressing a decrease in output with low-illuminance light when exposed to a high-temperature light irradiation environment.

FIG. 1 is a schematic diagram showing an example of the photoelectric conversion element of the first embodiment. FIG. 2 is a schematic diagram showing an example of the photoelectric conversion element of the second embodiment. FIG. 3 is a schematic diagram showing an example of the photoelectric conversion element of the third embodiment. FIG. 4 is a schematic diagram showing an example of the photoelectric conversion element of the fourth embodiment. FIG. 5 is a block diagram of a personal computer mouse as an example of the electronic device of the present invention. 6 is a schematic external view showing an example of the mouse shown in FIG. 5. FIG. FIG. 7 is a block diagram of a personal computer keyboard as an example of the electronic device of the present invention. 8 is a schematic external view showing an example of the keyboard shown in FIG. 7. FIG. 9 is a schematic external view showing another example of the keyboard shown in FIG. 7. FIG. FIG. 10 is a block diagram of a sensor as an example of the electronic device of the invention. FIG. 11 is a block diagram of a turntable as an example of the electronic device of the invention. FIG. 12 is a block diagram showing an example of the electronic device of the invention. 13 is a block diagram showing an example in which a power supply IC is further incorporated into the electronic device shown in FIG. 12. FIG. FIG. 14 is a block diagram showing an example in which the electronic device shown in FIG. 13 further incorporates a power storage device. FIG. 15 is a block diagram showing an example of the power supply module of the present invention. 16 is a block diagram showing an example in which a power storage device is further incorporated into the power supply module shown in FIG. 15. FIG.

(Photoelectric conversion element)
The photoelectric conversion device of the present invention has a first electrode, an electron transport layer, a photosensitizing compound, a hole transport layer, a second electrode, and optionally other layers.
A photoelectric conversion element refers to an element that can convert light energy into electric energy, and is applied to solar cells, photodiodes, and the like.

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, found that in solid-state dye-sensitized solar cells, the state of association between dyes under a high-temperature light irradiation environment has a great effect on the photoelectric conversion properties. did. In particular, in solid-state dye-sensitized solar cells, the association state of dyes is important even when holes are efficiently injected from dyes into organic P-type semiconductors with large molecular sizes.
The high-temperature light irradiation environment is, for example, an environment in which light of 50° C. and 2,000 lx is irradiated, such as an environment near a window where sunlight is irradiated.

Therefore, the photoelectric conversion device of the present invention has a first electrode, an electron transport layer, a hole transport layer, a photosensitizing compound, and a second electrode, and the photosensitizing compound has the following general formula By including the compound represented by (1) and the compound represented by the following general formula (2), it is possible to prevent a decrease in output even after being exposed to a high-illuminance light environment.

ただし、前記一般式（１）中、Ａｒ_１及びＡｒ_２は、置換基を有していてもよいアリール基を表す。Ｒ_１及びＲ_２は、炭素数４～１０の直鎖又は分岐状のアルキル基を表す。Ｘは、下記構造式で表されるいずれかの置換基を表す。

However, in the general formula (1), Ar ₁ and Ar ₂ represent an aryl group which may have a substituent. R ₁ and R ₂ each represent a linear or branched alkyl group having 4 to 10 carbon atoms. X represents any substituent represented by the following structural formula.

ただし、前記一般式（２）中、Ｒ_３は、アリール基、下記構造式で表されるいずれかの置換基のいずれかを表す。ｎは０～１の整数を表す。

However, in the general formula (2), R ₃ represents either an aryl group or a substituent represented by the following structural formula. n represents an integer of 0 to 1;

Each constituent member of the photoelectric conversion device of the present invention will be described in detail below.

<First substrate>
The shape, structure, and size of the first substrate are not particularly limited, and can be appropriately selected according to the purpose.
The material of the first substrate is not particularly limited as long as it has translucency and insulation, and can be appropriately selected according to the purpose. Examples include substrates such as glass, plastic film, and ceramics. be done. Among these, a substrate having heat resistance to the firing temperature is preferable when the step of firing is included when forming the electron transport layer. Moreover, as the first substrate, one having flexibility is preferable.

<First electrode>
The shape and size of the first electrode are not particularly limited, and can be appropriately selected according to the purpose.
The structure of the first electrode is not particularly limited and can be appropriately selected according to the purpose.

The material of the first electrode is not particularly limited as long as it has transparency to visible light and conductivity, and can be appropriately selected according to the purpose. Examples include transparent conductive metal oxides, carbon, A metal etc. are mentioned.
Examples of transparent conductive metal oxides include indium tin oxide (hereinafter referred to as "ITO"), fluorine-doped tin oxide (hereinafter referred to as "FTO"), and 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, niobium-titanium oxide, and the like.
Examples of carbon include carbon black, carbon nanotubes, graphene, and fullerene.
Examples of metals include gold, silver, aluminum, nickel, indium, tantalum, and titanium.
These may be used individually by 1 type, and may use 2 or more types together. Among these, transparent conductive metal oxides with high transparency are preferred, and ITO, FTO, ATO, and NTO are more preferred.

The average thickness of the first electrode is not particularly limited, and can be appropriately selected according to the purpose. Note that when the material of the first electrode is carbon or metal, the average thickness of the first electrode is preferably an average thickness that can provide translucency.

The first electrode can be formed by known methods such as sputtering, vapor deposition, and spraying.
The first electrode is preferably formed on the first substrate, and an integrated commercial product in which the first electrode is previously formed on the first substrate can be used.
Commercially integrated products include, for example, FTO-coated glass, ITO-coated glass, zinc oxide:aluminum-coated glass, FTO-coated transparent plastic film, and ITO-coated transparent plastic film. Other integrated commercial products include, for example, transparent electrodes obtained by doping tin oxide or indium oxide with cations or anions having different valences, or metals with a structure that allows light to pass through, such as in a mesh or stripe shape. Examples include a glass substrate provided with electrodes.
These may be used singly, or two or more of them may be mixed or laminated together. Also, a metal lead wire or the like may be used together for the purpose of lowering the electrical resistance value.
Examples of materials for the metal lead wire include aluminum, copper, silver, gold, platinum, and nickel.
A metal lead wire can be used together by forming it on a substrate by, for example, vapor deposition, sputtering, pressure bonding, etc., and providing a layer of ITO or FTO thereon.

<Hole blocking layer>
A hole blocking layer is formed between the first electrode and the electron transport layer. The hole-blocking layer can transport electrons generated in the photosensitizing compound and then transported to the electron-transporting layer to the first electrode and prevent contact with the hole-transporting layer. As a result, it is possible to suppress the inflow of holes into the first electrode and suppress the decrease in output due to recombination of electrons and holes. Solid-type photoelectric conversion elements with a hole-transporting layer have a faster recombination rate of holes in the hole-transporting material and electrons on the electrode surface than wet-type photoelectric conversion elements that use an electrolytic solution. effect is very large.

The material of the hole blocking layer is not particularly limited as long as it is transparent to visible light and has electron transport properties, and can be appropriately selected according to the purpose. Examples include silicon, germanium, and the like. Single semiconductors, compound semiconductors represented by metal chalcogenides, and compounds having a perovskite structure can be used.

Metal chalcogenides include, for example, oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum; cadmium, zinc, lead, silver, and antimony. , sulfide of bismuth; selenide of cadmium and lead; telluride of cadmium. Other compound semiconductors include phosphides such as zinc, gallium, indium, and cadmium; gallium arsenide, copper-indium-selenide, and copper-indium-sulfide.
Examples of compounds having a perovskite structure include strontium titanate, calcium titanate, sodium titanate, barium titanate, and potassium niobate.
Among these, oxide semiconductors are preferred, titanium oxide, niobium oxide, magnesium oxide, aluminum oxide, zinc oxide, tungsten oxide, tin oxide, and the like are more preferred, and titanium oxide is even more preferred.
These may be used individually by 1 type, and may use 2 or more types together. Moreover, it may be a single layer or a laminate. The crystal type of these semiconductors is not particularly limited and can be appropriately selected according to the purpose, and may be single crystal, polycrystal, or amorphous.

The method for producing the hole blocking layer is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a method of forming a thin film in vacuum (vacuum film forming method) and a wet film forming method. .
Vacuum film forming methods include, for example, a sputtering method, a pulse laser deposition method (PLD method), an ion beam sputtering method, an ion assist method, an ion plating method, a vacuum vapor deposition method, an atomic layer deposition method (ALD method), Chemical vapor deposition method (CVD method) etc. are mentioned.
The wet film-forming method includes, for example, a sol-gel method. The sol-gel method is a method in which a gel is produced from a solution through chemical reactions such as hydrolysis and polymerization/condensation, and then densification is promoted by heat treatment. When the sol-gel method is used, the method of applying the sol solution is not particularly limited and can be appropriately selected depending on the purpose. method, blade coating method, gravure coating method, and wet printing methods include letterpress, offset, gravure, intaglio, rubber plate, screen printing and the like. The temperature for the heat treatment after applying the sol solution is preferably 80° C. or higher, more preferably 100° C. or higher.
The average thickness of the hole-blocking layer is not particularly limited and can be appropriately selected depending on the intended purpose. 30 nm or less is more preferable.

<Electron transport layer>
The electron transport layer is formed for the purpose of transporting electrons generated by the photosensitizing compound to the first electrode or hole blocking layer. For this reason, the electron transport layer is preferably positioned adjacent to the first electrode or hole blocking layer.
The structure of the electron-transporting layer is not particularly limited and can be appropriately selected depending on the intended purpose. However, it is preferable that the electron-transporting layers of at least two photoelectric conversion elements adjacent to each other do not extend to each other. . If the electron transport layers are not extended from each other, electron diffusion is suppressed and leakage current is reduced, which is advantageous in terms of improving light durability. The structure of the electron-transporting layer may be a continuous monolayer or a multi-layer structure in which a plurality of layers are laminated.

The electron-transporting layer contains an electron-transporting material and, if necessary, other materials.
The electron-transporting material is not particularly limited and can be appropriately selected depending on the purpose, but a semiconductor material is preferable.
It is preferable that the semiconductor material has a shape of fine particles and is formed into a porous film by bonding these fine particles. A photosensitizing compound is chemically or physically adsorbed on the surface of the semiconductor fine particles forming the porous electron transport layer.
The electron transport layer is preferably a porous semiconductor material supporting the compound represented by the general formula (1) and the compound represented by the general formula (2).

The semiconductor material is not particularly limited, and known materials can be used. Examples thereof include single semiconductors, compound semiconductors, compounds having a perovskite structure, and the like.
Examples of single semiconductors include silicon and germanium.
Examples of compound semiconductors include metal chalcogenides, specifically oxides such as titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, and tantalum; sulfides such as cadmium, zinc, lead, silver, antimony and bismuth; selenides such as cadmium and lead; tellurides such as cadmium; Other compound semiconductors include phosphides such as zinc, gallium, indium and cadmium, gallium arsenide, copper-indium-selenide and copper-indium-sulfide.
Examples of compounds having a perovskite structure include strontium titanate, calcium titanate, sodium titanate, barium titanate, and potassium niobate.
Among these, oxide semiconductors are preferred, and titanium oxide, zinc oxide, tin oxide and niobium oxide are more preferred. When the electron-transporting material of the electron-transporting layer is titanium oxide, a high conduction band and a high open-circuit voltage can be obtained. In addition, the refractive index is high, and a high short-circuit current can be obtained due to the light confinement effect. In addition, a high fill factor is obtained due to the high dielectric constant and high mobility.
These may be used individually by 1 type, and may use 2 or more types together. The crystal type of the semiconductor material is not particularly limited and can be appropriately selected depending on the purpose, and may be single crystal, polycrystal, or amorphous.

The number average particle diameter of the primary particles of the semiconductor material is not particularly limited and can be appropriately selected according to the purpose. Also, a semiconductor material having a particle size larger than the number average particle size may be mixed or stacked, and the conversion efficiency may be improved by the effect of scattering incident light. In this case, the number average particle diameter is preferably 50 nm or more and 500 nm or less.
The average thickness of the electron transport layer is not particularly limited and can be appropriately selected depending on the intended purpose. When the average thickness of the electron transport layer is 50 nm or more and 100 μm or less, the amount of the photosensitizing compound per unit projected area can be sufficiently secured, the light capture rate can be maintained high, and the diffusion distance of the injected electrons. is less likely to increase, and loss due to charge recombination can be reduced.

The method for producing the electron transport layer is not particularly limited and can be appropriately selected according to the intended purpose. Among these, a wet film forming method is preferable from the viewpoint of manufacturing cost, and a paste in which powder or sol of a semiconductor material is dispersed is prepared, and is formed on the first electrode as an electron collecting electrode substrate or on the hole blocking layer. A top coating method is more preferred.
The wet film-forming method is not particularly limited and can be appropriately selected depending on the intended purpose. etc.
Examples of wet printing methods include letterpress, offset, gravure, intaglio, rubber plate, and screen printing.

Examples of a method for producing a dispersion liquid of a semiconductor material include a method of mechanical pulverization using a known milling device or the like. By this method, a semiconductor material dispersion can be prepared by dispersing a particulate semiconductor material alone or a mixture of a semiconductor material and a resin in water or a solvent.
Examples of resins include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, acrylic acid esters, and methacrylic acid esters, silicone resins, phenoxy resins, polysulfone resins, polyvinyl butyral resins, polyvinyl formal resins, polyester resins, Examples include cellulose ester resins, cellulose ether resins, urethane resins, phenol resins, epoxy resins, polycarbonate resins, polyarylate resins, polyamide resins, and polyimide resins. These may be used individually by 1 type, and may use 2 or more types together.

Examples of solvents include water, alcohol solvents, ketone solvents, ester solvents, ether solvents, amide solvents, halogenated hydrocarbon solvents, and hydrocarbon solvents.
Examples of alcohol solvents include methanol, ethanol, isopropyl alcohol, α-terpineol and the like.
Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
Ester solvents include, for example, ethyl formate, ethyl acetate, n-butyl acetate and the like.
Ether solvents include, for example, diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, dioxane and the like.
Amide solvents include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.
Halogenated hydrocarbon solvents include, for example, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, 1-chloronaphthalene and the like. .
Examples of hydrocarbon solvents include n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, Examples include ethylbenzene and cumene.
The solvent may be used singly or in combination of two or more.

An acid, a surfactant, a chelating agent, or the like may be added to a dispersion containing a semiconductor material or a paste containing a semiconductor material obtained by a sol-gel method or the like in order to prevent reaggregation of particles.
Acids include, for example, hydrochloric acid, nitric acid, and acetic acid.
Examples of surfactants include polyoxyethylene octylphenyl ether.
Chelating agents include, for example, acetylacetone, 2-aminoethanol, ethylenediamine and the like.

A thickener may also be added for the purpose of improving the film formability.
Examples of thickeners include polyethylene glycol, polyvinyl alcohol and ethyl cellulose.
After the semiconductor material is applied, the particles of the semiconductor material are brought into electronic contact, and in order to improve the film strength and adhesion to the substrate, it is baked, irradiated with microwaves or electron beams, or irradiated with laser light. Can be irradiated. These treatments may be performed singly or in combination of two or more.
When firing an electron transport layer formed of a semiconductor material, the firing temperature is not particularly limited and can be appropriately selected according to the purpose. , and melting, the temperature is preferably 30° C. or higher and 700° C. or lower, more preferably 100° C. or higher and 600° C. or lower. The firing time is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 minutes or more and 10 hours or less.

When an electron transport layer made of a semiconductor material is irradiated with microwaves, the irradiation time is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 hour or less. In this case, irradiation may be performed from the side on which the electron transport layer is formed, or from the side on which the electron transport layer is not formed.
After baking the electron transport layer made of a semiconductor material, for the purpose of increasing the surface area of the electron transport layer and increasing the efficiency of electron injection from the photosensitizing compound described later to the semiconductor material, for example, an aqueous solution of titanium tetrachloride or an organic solvent. Chemical plating using a mixed solution of titanium trichloride or electrochemical plating using an aqueous solution of titanium trichloride may be performed.
A film obtained by sintering a semiconductor material with a diameter of several tens of nanometers can form a porous film. Such nanoporous structures have a very high surface area, which can be expressed using a roughness factor. The roughness factor is a numerical value that represents the actual area of the porous interior with respect to the area of the semiconductor particles applied to the first substrate. Therefore, although the roughness factor is preferably as large as possible, it is preferably 20 or more in terms of the average thickness of the electron transport layer.

Also, the particles of the electron-transporting material may be doped with a lithium compound. Specifically, it is a method in which a solution of a lithium bis(trifluoromethanesulfonimide) compound is deposited on particles of an electron-transporting material by using spin coating or the like, and then calcined.
The lithium compound is not particularly limited and can be appropriately selected depending on the intended purpose. methanesulfonyl)imide, lithium perchlorate, lithium iodide and the like.

<Photosensitizing compound>
The photosensitizing compound is a compound that is photoexcited by light irradiated to the photoelectric conversion element. compounds are adsorbed.
The photosensitizing compound includes a compound represented by the following general formula (1) and a compound represented by the following general formula (2). The electron-transporting layer contains, as the photosensitizing compound, a compound represented by the following general formula (1) and a compound represented by the following general formula (2), so that in the general formula (1) The compound represented by the following general formula (2) and the compound represented by the following general formula (2) are in a mixed adsorption state, and a high output can be obtained in a high-temperature environment in a solid-type dye-sensitized solar cell.

ただし、前記一般式（１）中、Ａｒ_１及びＡｒ_２は、置換基を有していてもよいアリール基を表す。Ｒ_１及びＲ_２は、炭素数４～１０の直鎖又は分岐状のアルキル基を表す。Ｘは、下記構造式で表されるいずれかの置換基を表す。

However, in the general formula (1), Ar ₁ and Ar ₂ represent an aryl group which may have a substituent. R ₁ and R ₂ each represent a linear or branched alkyl group having 4 to 10 carbon atoms. X represents any substituent represented by the following structural formula.

Ａｒ_１及びＡｒ_２のアリール基としては、例えば、フェニル基、ナフチル基、ビフェニル基などが挙げられる。
置換基としては、例えば、アルキル基、アルコキシ基などが挙げられる。

Aryl groups for Ar ₁ and Ar ₂ include, for example, a phenyl group, a naphthyl group, a biphenyl group and the like.
Examples of substituents include alkyl groups and alkoxy groups.

ただし、前記一般式（２）中、Ｒ_３は、アリール基、下記構造式で表されるいずれかの置換基のいずれかを表す。ｎは０～１の整数を表す。

However, in the general formula (2), R ₃ represents either an aryl group or a substituent represented by the following structural formula. n represents an integer of 0 to 1;

The compound represented by the general formula (1) is a compound represented by the following general formula (3), because high output can be obtained from a low-illuminance light environment to a high-illuminance light environment. preferred from
The low illuminance light includes, for example, light of 500 lx. High illuminance light includes, for example, light at 50° C. and 2,000 lx.

ただし、前記一般式（３）中、Ａｒ_４及びＡｒ_５は、置換基を有してもよいフェニル基、又は置換基を有してもよいナフチル基を表す。Ａｒ_６は、フェニル基、又はチオフェン基を表す。
置換基としては、例えば、アルキル基、アルコキシ基などが挙げられる。

However, in the general formula (3), Ar ₄ and Ar ₅ represent an optionally substituted phenyl group or an optionally substituted naphthyl group. Ar ₆ represents a phenyl group or a thiophene group.
Examples of substituents include alkyl groups and alkoxy groups.

Specific exemplary compounds of the basic compounds represented by the general formulas (1) and (3) are shown below, but the present invention is not limited thereto.

Specific exemplary compounds of the photosensitizing compound represented by the general formula (2) are shown below, but the present invention is not limited thereto.

(B2-1)

(B2-2)

(B2-3)

(B2-4)

(B2-5)

(B2-6)

(B2-1)

(B2-2)

(B2-3)

(B2-4)

(B2-5)

(B2-6)

As a method for adsorbing the photosensitizing compound on the surface of the semiconductor material of the electron transporting layer, the electron transporting layer containing the semiconductor material is immersed in a photosensitizing compound solution or a photosensitizing compound dispersion. method, a solution of a photosensitizing compound, or a method of applying a dispersion of a photosensitizing compound to the electron-transporting layer for adsorption. In the case of the method of immersing the electron transport layer formed with the semiconductor material in the solution of the photosensitizing compound or the dispersion of the photosensitizing compound, an immersion method, a dipping method, a roller method, an air knife method, or the like can be used. can be done. In the case of the method of applying a solution of a photosensitizing compound or a dispersion of a photosensitizing compound to the electron transport layer and adsorbing it, the wire bar method, the slide hopper method, the extrusion method, the curtain method, the spin method, and the spray method. method, etc. can be used. Adsorption in a supercritical fluid using carbon dioxide or the like is also possible.

A condensing agent may be used in combination when the photosensitizing compound is adsorbed on the semiconductor material.
The condensing agent may be one that has a catalytic action such as physically or chemically binding the photosensitizing compound to the surface of the semiconductor material, or one that has a stoichiometric action and favorably shifts the chemical equilibrium. Either can be used. Furthermore, a thiol or hydroxy compound may be added as a condensation aid.

Solvents for dissolving or dispersing the photosensitizing compound include, for example, water, alcohol solvents, ketone solvents, ester solvents, ether solvents, amide solvents, halogenated hydrocarbon solvents, and hydrocarbon solvents.
Examples of alcohol solvents include methanol, ethanol, isopropyl alcohol and the like.
Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
Ester solvents include, for example, ethyl formate, ethyl acetate, n-butyl acetate and the like.
Ether solvents include, for example, diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, dioxane and the like.
Amide solvents include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.
Halogenated hydrocarbon solvents include, for example, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, 1-chloronaphthalene and the like. .
Examples of hydrocarbon solvents include n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, Examples include ethylbenzene and cumene.
These may be used individually by 1 type, and may use 2 or more types together.

Since some photosensitizing compounds work more effectively by suppressing aggregation between compounds depending on the type, an aggregation dissociation agent may be used in combination. Aggregating dissociation agents include steroid compounds such as cholic acid and chenodeoxycholic acid, long-chain alkylcarboxylic acids and long-chain alkylphosphonic acids, and 4-benzyloxybenzoic acid is particularly preferred.

The content of the aggregation dissociation agent is preferably 0.5 mol parts or more and 100 mol parts or less, more preferably 10 mol parts or more and 50 mol parts or less, relative to 1 mol part of the photosensitizing compound.

The temperature at which the photosensitizing compound or the photosensitizing compound and the cohesive dissociation agent is adsorbed onto the surface of the semiconductor material constituting the electron transport layer is preferably -50°C or higher and 200°C or lower. The adsorption time is preferably from 5 seconds to 1,000 hours, more preferably from 10 seconds to 500 hours, and even more preferably from 1 minute to 150 hours. The adsorption step is preferably performed in a dark place. Moreover, the step of adsorbing may be carried out while standing still, or may be carried out while stirring.
The stirring method is not particularly limited and can be appropriately selected depending on the intended purpose. be done.

<Hole transport layer>
The hole transport layer is not particularly limited as long as it has a function of transporting holes, and known materials can be used. gel electrolytes in which a polymer matrix is impregnated with a liquid dissolved in , molten salts containing redox couples, solid electrolytes, inorganic hole transport materials, organic hole transport materials, and the like. Among these, electrolytic solutions and gel electrolytes can be used, but solid electrolytes are preferred, and organic hole transport materials are more preferred.

The hole transport layer preferably further contains an alkali metal salt. When the hole transport layer contains an alkali metal salt, the output can be improved, and the light irradiation resistance and high-temperature storage resistance can be improved.
Specific examples of the alkali metal salt include those shown in (C-1) to (C-86) below, but are not limited thereto.

Among these, lithium bis (trifluoromethanesulfonylimide) (Li-TFSI), lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide (Li-FTFSI) is preferable, lithium (fluorosulfonyl) (trifluoromethanesulfonyl) imide (Li -FTFSI) is particularly preferred.

The content of the alkali metal salt is preferably 5 mol % or more and 50 mol % or less, more preferably 20 mol % or more and 35 mol % or less, relative to the total amount of the hole transport material.

ただし、前記一般式（５）中、Ａｒ_７及びＡｒ_８は、置換基を有していてもよいアリール基を表す。
Ａｒ_７及びＡｒ_８のアリール基としては、例えば、フェニル基、ナフチル基、ビフェニル基などが挙げられる。置換基としては、例えば、アルキル基、アルコキシ基などが挙げられる。 The hole transport layer preferably contains a basic compound represented by the following general formula (5).

However, in the general formula (5), Ar ₇ and Ar ₈ represent an aryl group which may have a substituent.
Aryl groups for Ar ₇ and Ar ₈ include, for example, a phenyl group, a naphthyl group, a biphenyl group and the like. Examples of substituents include alkyl groups and alkoxy groups.

The hole transport layer preferably contains a basic compound represented by the general formula (5). When the hole-transporting layer contains the basic compound represented by the general formula (5), it is advantageous in terms of enhancing the output stability of the photoelectric conversion device. In particular, it is advantageous in that it is possible to reduce variations in output characteristics for low-illuminance light and stably generate power.

Specific exemplary compounds of the basic compound represented by the general formula (5) are shown below, but the present invention is not limited thereto.

In addition to the basic compound represented by the general formula (5), 4-dimethylaminopyridine (DMAP), 4-pyrrolidinopyridine (PYP), 4-piperidinopyridine (PPP), tert-butylpyridine (TBP) ) are also preferred.

The content of the basic compound represented by the general formula (5) in the hole transport layer is preferably 20 mol % or more and 65 mol % or less, more preferably 35 mol % or more and 50 mol %, relative to the hole transport material. % or less. When the content of the basic compound is within the preferred range, a high open-circuit voltage can be maintained, a high output can be obtained, and high stability and durability can be obtained even after long-term use in various environments.

The hole transport layer contains a hole transport material or a P-type semiconductor material in order to obtain the function of transporting holes. A known organic hole-transporting compound is used as the hole-transporting material or the P-type semiconductor material. Specific examples thereof include oxadiazole compounds, triphenylmethane compounds, pyrazoline compounds, hydrazone compounds, oxadiazole compounds, tetraarylbenzidine compounds, stilbene compounds, and spiro-type compounds. Among these, spiro-type compounds are more preferable.

ただし、前記一般式（７）中、Ｒ_４からＲ_７は、それぞれ独立して、ジメチルアミノ基、ジフェニルアミノ基、ナフチル－４－トリルアミノ基などの置換アミノ基を表す。 As the spiro-type compound, a compound containing the following general formula (7) is preferable.

However, in the general formula (7), R ₄ to R ₇ each independently represent a substituted amino group such as a dimethylamino group, a diphenylamino group and a naphthyl-4-tolylamino group.

The spiro-type compound is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include exemplary compounds (D-1) to (D-20) shown below, but are limited to not something. These may be used individually by 1 type, and may use 2 or more types together.

In addition to having high hole mobility, these spiro-type compounds form a nearly spherical electron cloud due to the twisted bonding of two benzidine skeleton molecules, and intermolecular hopping conductivity. A good photoelectric conversion characteristic is exhibited. In addition, since it is highly soluble, it dissolves in various organic solvents, and since it is an amorphous substance (amorphous substance having no crystal structure), it tends to be densely packed in the porous electron transport layer. Furthermore, since it does not have a light absorption characteristic of 450 nm or more, the photosensitizing compound can efficiently absorb light, which is particularly preferable for solid dye-sensitized solar cells.

It is preferable to add an oxidizing agent to the hole transport layer in addition to the hole transport material and the basic compound. By containing an oxidizing agent, the electrical conductivity is improved, and the durability and stability of the output characteristics can be enhanced.
Examples of the oxidizing agent include tris(4-bromophenyl)aminium hexachloroantimonate, silver hexafluoroantimonate, nitrosonium tetrafluoroborate, silver nitrate, metal complexes, hypervalent iodine compounds, and the like. Among them, metal complexes are more preferable. More preferred are hypervalent iodine compounds. When the oxidizing agent is a metal complex or a hypervalent iodine compound, it is advantageous in that it can be added in large amounts due to its high solubility in organic solvents.
Metal complexes consist of metal cations, ligands and anions.
Examples of metal cations include cations such as chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, tungsten, rhenium, osmium, iridium, gold, and platinum. Among them, cations of cobalt, iron, nickel, and copper are preferred, and cobalt complexes are more preferred. The ligand is preferably one containing at least one nitrogen-containing 5- and/or 6-membered heterocyclic ring, and may have a substituent. Specific examples include, but are not limited to, the following.

Examples of anions include hydride ion (H ⁻ ), fluoride ion (F ⁻ ), chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodide ion (I ⁻ ), hydroxide ion ( OH ⁻ ), cyanide ion (CN ⁻ ), nitrate ion (NO ₃ ⁻ ), nitrite ion (NO ₂ ⁻ ), hypochlorite ion (ClO ⁻ ), chlorite ion (ClO ₂ ⁻ ), chlorine acid ion (ClO ₃ ⁻ ), perchlorate ion (ClO ₄ ⁻ ), permanganate ion (MnO ₄ ⁻ ), acetate ion (CH ₃ COO ⁻ ), hydrogen carbonate ion (HCO ₃ ⁻ ), dihydrogen phosphate ion (H ₂ PO ₄ ⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), hydrogen sulfide ion (HS ⁻ ), thiocyanate ion (SCN ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), tetracyanoborate ion (B(CN) ₄ ⁻ ), dicyanoamine ion (N(CN) ₂ ⁻ ), p-toluenesulfonate ion (TsO ⁻ ), trifluoromethylsulfonate ion (CF ₃ SO ²⁻ ), bis(trifluoromethylsulfonyl)amine ion (N(SO ₂ CF ₃ ) ²⁻ ), tetrahydroxoaluminate ion ([Al(OH) ₄ ] ⁻ , or [Al(OH) ₄ (H ₂ O) ₂ ] ⁻ ), dicyanoargentate ([Ag(CN) ₂ ] ⁻ ), tetrahydroxochromate (III) ion ([Cr(OH) ₄ ] ⁻ ), tetrachloro Au(III) acid ion ([AuCl ₄ ] ⁻ ), oxide ion (O ₂ ⁻ ), sulfide ion (S ₂ ⁻ ), peroxide ion (O ₂ ²⁻ ), sulfate ion (SO ₄ ²⁻ ) ), sulfite ion (SO ₃ ^2- ), thiosulfate ion (S ₂ O ₃ ^2- ), carbonate ion (CO ₃ ^2- ), chromate ion (CrO ₄ ^2- ), dichromate ion (Cr ₂ O ₇ ^2- ), monohydrogen phosphate ion (HPO ₄ ^2- ), tetrahydroxozinc(II) ion ([Zn(OH) ₄ ] ^2- ), tetracyanozinc(II) ion ([Zn(CN) ₄ ] ^2- ), tetrachlorocuprate ion ([CuCl ₄ ] ^2- ), phosphate ion (PO ₄ ^3- ), hexa cyanoferrate (III) ([Fe(CN) ₆ ] ^3- ), bis(thiosulfato)argentate (I) ([Ag(S ₂ O ₃ ) ₂ ] ^3- ), hexacyanoferrate (II) ions ([Fe(CN) ₆ ] ^4- ) and the like. These may be used individually by 1 type, and may use 2 or more types together.
Among these, tetrafluoroboronate ion, hexafluorophosphate ion, tetracyanoborate ion, bis(trifluoromethylsulfonyl)amine ion, and perchlorate ion are preferred.

Among these metal complexes, trivalent cobalt complexes represented by the following structural formulas (8) and (9) are preferred. If the metal complex is a trivalent cobalt complex, it is advantageous in terms of oxidizing the hole transport material.

ただし、前記一般式（４）中、Ｒ_３～Ｒ_５は、水素原子、メチル基、エチル基、ターシャルブチル基、又はトリフルオロメチル基を示す。Ｙは、下記構造式（２）から（５）で表されるいずれかを示す。

More preferably, it is a trivalent cobalt complex represented by the following general formula (4).

However, in the general formula (4), R ₃ to R ₅ represent a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, or a trifluoromethyl group. Y represents any one of the following structural formulas (2) to (5).

Examples of the trivalent cobalt complex represented by the general formula (4) include (F-1) to (F-16) shown below. However, it is not limited to these.

The hole transport layer may have a single layer structure made of a single material, or may have a laminated structure containing a plurality of compounds. When the hole transport layer has a laminated structure, it is preferable to use a polymer material for the hole transport layer near the second electrode. The use of a polymeric material having excellent film-forming properties is advantageous in that the surface of the porous electron transport layer can be made smoother and the photoelectric conversion characteristics can be improved. In addition, since the polymer material hardly permeates into the porous electron transport layer, the coverage of the surface of the porous electron transport layer is excellent, and it is effective in preventing short circuits when electrodes are provided. There is

Polymer materials used for the hole transport layer include known hole transport polymer materials.
Examples of hole-transporting polymer materials include polythiophene compounds, polyphenylene vinylene compounds, polyfluorene compounds, polyphenylene compounds, polyarylamine compounds, polythiadiazole compounds, and the like.

Examples of polythiophene compounds include poly(3-n-hexylthiophene), poly(3-n-octyloxythiophene), poly(9,9'-dioctyl-fluorene-co-bithiophene), poly(3,3' ''-didodecyl-quaterthiophene), poly(3,6-dioctylthieno[3,2-b]thiophene), poly(2,5-bis(3-decylthiophen-2-yl)thieno[3,2- b]thiophene), poly(3,4-didecylthiophene-co-thieno[3,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thieno[3 ,2-b]thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-thiophene), poly(3,6-dioctylthieno[3,2-b]thiophene-co-bithiophene) ) and the like.

Examples of polyphenylene vinylene compounds include poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1 ,4-phenylenevinylene], poly[(2-methoxy-5-(2-ethylphexyloxy)-1,4-phenylenevinylene)-co-(4,4′-biphenylene-vinylene)], and the like. .

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

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

Examples of polyarylamine compounds 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-dioctyl oxy-1,4-phenylenevinylene-1,4-phenylene], poly[p-tolylimino-1,4-phenylenevinylene-2,5-di(2-ethylhexyloxy)-1,4-phenylenevinylene-1, 4-phenylene], poly[4-(2-ethylhexyloxy)phenylimino-1,4-biphenylene] and the like.

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

Among the hole-transporting polymer materials, polythiophene compounds and polyarylamine compounds are preferable from the viewpoint of carrier mobility and ionization potential.

The average thickness of the hole-transporting layer is not particularly limited and can be appropriately selected according to the purpose. is preferably 0.01 μm or more and 20 μm or less, more preferably 0.1 μm or more and 10 μm or less, and still more preferably 0.2 μm or more and 2 μm or less.

The hole-transporting layer can be formed directly on the electron-transporting layer with the photosensitizing compound adsorbed thereon. The method for producing the hole transport layer is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include a method of forming a thin film in a vacuum such as vacuum deposition, a wet film forming method, and the like. Among these, the wet film-forming method is particularly preferable from the viewpoint of manufacturing cost, and the method of coating on the electron-transporting layer is preferable.
When a wet film-forming method is used, the coating method is not particularly limited and can be carried out according to known methods such as dipping, spraying, wire bar method, spin coating, roller coating, blade coating, etc. Various methods such as letterpress, offset, gravure, intaglio, rubber plate, and screen printing can be used as coating methods, gravure coating methods, and wet printing methods.

Alternatively, the film may be formed in a supercritical fluid or a subcritical fluid at a temperature and pressure lower than the critical point. A supercritical fluid exists as a non-aggregating high-density fluid in a temperature and pressure range that exceeds the limit (critical point) at which gas and liquid can coexist. There is no particular limitation as long as the fluid is in the state of, and it can be appropriately selected according to the purpose, but a fluid with a low critical temperature is preferable.

Examples of supercritical fluids include carbon monoxide, carbon dioxide, ammonia, nitrogen, water, alcohol solvents, hydrocarbon solvents, halogen solvents, and ether solvents.

Examples of alcohol solvents include methanol, ethanol, n-butanol and the like.

Examples of hydrocarbon solvents include ethane, propane, 2,3-dimethylbutane, benzene, and toluene. Halogen solvents include, for example, methylene chloride and chlorotrifluoromethane.

Ether solvents include, for example, dimethyl ether.

These may be used individually by 1 type, and may use 2 or more types together.
Among these, carbon dioxide is preferable because it has a critical pressure of 7.3 MPa and a critical temperature of 31° C., so that a supercritical state can be easily created, and it is nonflammable and easy to handle.

The subcritical fluid is not particularly limited as long as it exists as a high-pressure liquid in the temperature and pressure regions near the critical point, and can be appropriately selected according to the purpose. Compounds listed as supercritical fluids can also be suitably used as subcritical fluids.

The critical temperature and critical pressure of the supercritical fluid are not particularly limited and can be appropriately selected according to the purpose. more preferred.

Furthermore, in addition to supercritical fluids and subcritical fluids, organic solvents and entrainers can also be used in combination. Addition of an organic solvent and an entrainer makes it easier to adjust the solubility in the supercritical fluid.
The organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ketone solvents, ester solvents, ether solvents, amide solvents, halogenated hydrocarbon solvents, and hydrocarbon solvents.

Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.

Ester solvents include, for example, ethyl formate, ethyl acetate, n-butyl acetate and the like.

Ether solvents include, for example, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, dioxane and the like.

Amide solvents include, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

Halogenated hydrocarbon solvents include, for example, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, 1-chloronaphthalene and the like. .

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

The said organic solvent may be used individually by 1 type, and may use 2 or more types together.

Moreover, after laminating a hole-transporting material on the electron-transporting layer on which the photosensitizing compound is adsorbed, a pressing process may be performed. By applying the press treatment, the hole-transporting material is brought into close contact with the electron-transporting layer, which is a porous electrode, so that the efficiency can be improved in some cases.
The method of press treatment is not particularly limited and can be appropriately selected according to the purpose. Examples include a press molding method using a flat plate as typified by an IR tablet molding machine, a roll press method using rollers, and the like. can be mentioned.
The pressure is preferably 10 kgf/cm ² or higher, more preferably 30 kgf/cm ² or higher.
The time for the press treatment is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 hour or less. Also, heat may be applied during the press treatment. During the press treatment, a release agent may be interposed between the press and the electrode.

Release agents include, for example, polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene hexafluoropropylene copolymer, perfluoroalkoxy fluororesin, polyvinylidene fluoride, and ethylene tetrafluoroethylene copolymer. , ethylene chlorotrifluoride ethylene copolymer, and fluororesin such as polyvinyl fluoride. These may be used individually by 1 type, and may use 2 or more types together.
After performing the pressing step and before providing the second electrode, a metal oxide may be provided between the hole transport material and the second electrode.
Examples of metal oxides include molybdenum oxide, tungsten oxide, vanadium oxide, and nickel oxide. These may be used individually by 1 type, and may use 2 or more types together. Among these, molybdenum oxide is preferred.
The method for providing the metal oxide on the hole transport layer is not particularly limited and can be appropriately selected according to the purpose. Examples include a method of forming a thin film in vacuum such as sputtering and vacuum deposition, a wet film forming method, and the like. is mentioned.
As a wet film-forming method, a method of preparing a paste in which metal oxide powder or sol is dispersed and applying the paste onto the hole transport layer is preferable. The coating method in the case of using a wet film-forming method is not particularly limited, and can be carried out according to known methods such as dipping, spraying, wire bar method, spin coating, roller coating, blade coating, etc. Various methods such as letterpress, offset, gravure, intaglio, rubber plate, and screen printing can be used as coating methods, gravure coating methods, and wet printing methods.
The average thickness of the applied metal oxide is preferably 0.1 nm or more and 50 nm or less, more preferably 1 nm or more and 10 nm or less.

<Second electrode>
A second electrode can be formed on the hole transport layer or on the metal oxide in the hole transport layer. Also, the second electrode can be the same as the first electrode, and the support is not necessarily required if the strength is sufficiently maintained.
Examples of materials for the second electrode include metals, carbon compounds, conductive metal oxides, and conductive polymers.
Examples of metals include platinum, gold, silver, copper, and aluminum.
Carbon compounds include, for example, graphite, fullerene, carbon nanotubes, and graphene.
Examples of conductive metal oxides include ITO, FTO, and ATO.
Examples of conductive polymers include polythiophene and polyaniline.
These may be used individually by 1 type, and may use 2 or more types together.
The second electrode can be formed on the hole transport layer by coating, lamination, vapor deposition, CVD, bonding, or the like depending on the type of material used and the type of the hole transport layer.
In the photoelectric conversion element, at least one of the first electrode and the second electrode is preferably substantially transparent. A method in which the first electrode side is transparent and the incident light is incident from the first electrode side is preferable. In this case, it is preferable to use a material that reflects light on the second electrode side, such as metal, glass deposited with a conductive oxide, plastic, or a metal thin film. It is also effective to provide an antireflection layer on the incident light side.

<Second substrate>
The second substrate is not particularly limited, and known substrates can be used. Examples thereof include substrates such as glass, plastic film, and ceramics. An uneven portion may be formed in the joint portion between the second substrate and the sealing member in order to improve adhesion.
The method for forming the uneven portion is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include sandblasting, waterblasting, abrasive paper, chemical etching, and laser processing.
As means for increasing the adhesion between the second substrate and the sealing member, for example, organic matter on the surface may be removed, or hydrophilicity may be improved. The means for removing the organic substances on the surface of the second substrate is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include UV ozone cleaning and oxygen plasma treatment.

<Sealing member>
Examples of sealing resins include acrylic resins, epoxy resins, and low-melting glass resins.
As the cured acrylic resin, any known material can be used as long as it is a cured monomer or oligomer having an acrylic group in the molecule.
As the cured epoxy resin, any known material can be used as long as it is a cured monomer or oligomer having an epoxy group in the molecule.
Epoxy resins include, for example, water dispersion type, solventless type, solid type, heat curing type, curing agent mixed type, ultraviolet curing type, and the like. Among these, the thermosetting type and the ultraviolet curable type are preferred, and the ultraviolet curable type is more preferred. It should be noted that even if it is an ultraviolet curing type, it is possible to heat, and it is preferable to heat even after ultraviolet curing.
Examples of epoxy resins include bisphenol A type, bisphenol F type, novolac type, cyclic aliphatic type, long chain aliphatic type, glycidylamine type, glycidyl ether type, glycidyl ester type, and the like. These may be used individually by 1 type, and may use 2 or more types together.
The epoxy resin is preferably mixed with a curing agent and various additives as necessary.

Curing agents are classified into amine-based, acid anhydride-based, polyamide-based and other curing agents, and are appropriately selected according to the purpose.
Examples of amine curing agents include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, and aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone.
Acid anhydride-based curing agents include, for example, phthalic anhydride, tetra- and hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, hetic anhydride, and dodecenylsuccinic anhydride. .
Other curing agents include, for example, imidazoles and polymercaptans. These may be used individually by 1 type, and may use 2 or more types together.

Additives include, for example, fillers, gap agents, polymerization initiators, desiccants (hygroscopic agents), curing accelerators, coupling agents, flexible agents, coloring agents, flame retardant aids, and antioxidants. agents, organic solvents, and the like. Among these, fillers, gap agents, curing accelerators, polymerization initiators, and desiccants (hygroscopic agents) are preferred, and fillers and polymerization initiators are more preferred.
In addition to being effective in suppressing the infiltration of moisture and oxygen, fillers reduce volume shrinkage during curing, reduce outgassing during curing or heating, improve mechanical strength, thermal conductivity and fluidity. It is very effective in maintaining stable output even in various environments. In particular, the output characteristics and durability of a photoelectric conversion element cannot be ignored not only due to the effects of intruding moisture and oxygen, but also due to the effects of outgassing generated during curing or heating of the sealing member. In particular, the influence of outgassing generated during heating has a great influence on the output characteristics in high-temperature environment storage.
In this case, by including a filler, a gap agent, and a desiccant in the sealing member, these themselves can suppress the infiltration of moisture and oxygen. can be obtained. This is effective not only during curing, but also when the photoelectric conversion element is stored in a high-temperature environment.

The filler is not particularly limited, and known fillers can be used. For example, inorganic fillers such as crystalline or amorphous silica, talc, alumina, aluminum nitride, silicon nitride, calcium silicate, and calcium carbonate System fillers are preferably used. These may be used individually by 1 type, and may use 2 or more types together. The average primary particle size of the filler is preferably 0.1 μm or more and 10 μm, more preferably 1 μm or more and 5 μm or less. When the amount added is within the preferable range, the effect of suppressing the intrusion of moisture and oxygen can be sufficiently obtained, the viscosity becomes appropriate, the adhesion to the substrate and the defoaming property are improved, or the width of the sealing portion is improved. It is also effective for the control and workability of
The content 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 with respect to 100 parts by mass of the entire sealing member. When the content of the filler is within the above range, the effect of suppressing penetration of moisture and oxygen is sufficiently obtained, the viscosity becomes appropriate, and the adhesion and workability become good.

A gap agent is also called a gap control agent or a spacer agent, and makes it possible to control the gap of the sealing portion. For example, when a sealing member is provided on the first substrate or the first electrode, and the second substrate is placed thereon for sealing, the gap agent is mixed with the epoxy resin. Since the gap of the sealing portion is uniform in size of the gap agent, the gap of the sealing portion can be easily controlled.
As the gap agent, known materials can be used as long as they are granular, have a uniform particle size, and have high solvent resistance and heat resistance. Those having a high affinity with the epoxy resin and having a spherical particle shape are preferable. Specific examples include glass beads, silica fine particles, organic resin fine particles, and the like. These may be used individually by 1 type, and may use 2 or more types together.
The particle diameter of the gap agent can be selected according to the gap of the sealing portion to be set, but is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less.

A polymerization initiator is a material added for the purpose of initiating polymerization using heat or light.
Thermal polymerization initiators are compounds that generate active species such as radicals and cations by heating. Specifically, azo compounds such as 2,2'-azobisbutyronitrile (AIBN) and benzoyl peroxide (BPO ) and other peroxides are used. A benzenesulfonic acid ester, an alkylsulfonium salt, or the like is used as the thermal cationic polymerization initiator. On the other hand, as the photopolymerization initiator, a photocationic polymerization initiator is preferably used in the case of an epoxy resin. When a cationic photopolymerization initiator is mixed with an epoxy resin and irradiated with light, the cationic photopolymerization initiator decomposes to generate a strong acid, which causes polymerization of the epoxy resin and progresses the curing reaction. A photocationic polymerization initiator has effects such as little volume shrinkage during curing, no oxygen inhibition, and high storage stability.

Examples of photocationic polymerization initiators include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, metacelone compounds, and silanol/aluminum complexes.
A photoacid generator having a function of generating an acid upon irradiation with light can also be used. The photoacid generator acts as an acid that initiates cationic polymerization, and includes, for example, ionic sulfonium salt-based and iodonium salt-based onium salts composed of a cation portion and an anion portion. These may be used individually by 1 type, and may use 2 or more types together.
The amount of the polymerization initiator added may vary depending on the material used, but is preferably 0.5 parts by mass or more and 10 parts by mass or less, and 1 part by mass or more and 5 parts by mass with respect to 100 parts by mass of the entire sealing member. The following are more preferred. When the addition amount is within the above range, curing proceeds appropriately, the residual uncured material can be reduced, and excessive outgassing can be prevented, which is effective.

A desiccant, also called a hygroscopic agent, is a material that has the function of physically or chemically adsorbing and absorbing moisture. It is effective because there are cases where it can be done.
The desiccant is preferably particulate, and examples thereof 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 these, zeolites with high moisture absorption are preferred. These may be used individually by 1 type, and may use 2 or more types together.

Curing accelerators, also called curing catalysts, are used for the purpose of increasing the curing speed, and are mainly used for thermosetting epoxy resins.
Examples of curing accelerators include DBU (1,8-diazabicyclo(5,4,0)-undecene-7) and DBN (1,5-diazabicyclo(4,3,0)-nonene-5). Primary amines or tertiary amine salts, imidazoles such as 1-cyanoethyl-2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole, phosphines and phosphoniums such as triphenylphosphine and tetraphenylphosphonium/tetraphenylborate Examples include salt. These may be used individually by 1 type, and may use 2 or more types together.

The coupling agent has the effect of increasing the molecular bonding force, and includes silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 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- Examples include silane coupling agents such as aminopropyltrimethoxysilane hydrochloride and 3-methacryloxypropyltrimethoxysilane. These may be used individually by 1 type, and may use 2 or more types together.

The low-melting-point glass resin is adhered to the glass substrate while being melted by an infrared laser or the like after the resin component is decomposed by a baking process at about 550° C. after the resin is applied. At this time, the low-melting-point glass component diffuses into the metal oxide layer and is physically bonded, thereby obtaining high sealing performance. In addition, since the resin component disappears, outgassing such as acrylic resin and epoxy resin is not generated, so that the photoelectric conversion element is not deteriorated.
Further, as the sealing member, an epoxy resin composition commercially available as a sealing material, sealing material or adhesive is known and can be effectively used in the present invention. Among others, there are epoxy resin compositions developed and marketed for use in solar cells and organic EL devices, which can be used particularly effectively in the present invention. For example, TB3118, TB3114, TB3124, TB3125F (manufactured by ThreeBond), WorldRock5910, WorldRock5920, WorldRock8723 (manufactured by Kyoritsu Chemical Co., Ltd.), WB90US(P) (manufactured by Moresco), and the like.

A sheet-like sealing material can be used in the present invention.
The sheet sealing material is a sheet on which an epoxy resin layer is formed in advance, and the sheet is made of glass, a film having a high gas barrier property, or the like, and corresponds to the second substrate in the present invention. The sealing member and the second substrate can be formed at once by attaching the sheet-like sealing material to the second substrate and then curing it. It is also effective to provide a structure having a hollow portion depending on the formation pattern of the epoxy resin layer formed on the sheet.
The method for forming the sealing member is not particularly limited, and can be carried out according to known methods such as dispensing, wire bar, spin coating, roller coating, blade coating, gravure coating, letterpress. , offset, intaglio, rubber plate, screen printing, etc. can be used.
Furthermore, a passivation layer may be provided between the sealing member and the second electrode. The passivation layer is not particularly limited as long as it is arranged so that the sealing member is not in contact with the second electrode, and can be appropriately selected depending on the purpose. It is preferably used.

Next, the photoelectric conversion element of the present invention will be described with reference to the drawings. However, the present invention is not limited to these, and for example, the number, position, shape, etc. of the following constituent members, which are not described in the present embodiment, are also included in the scope of the present invention.

<First embodiment>
FIG. 1 is a schematic diagram showing an example of the photoelectric conversion element of the first embodiment. The photoelectric conversion element 101 of the first embodiment shown in FIG. 1 has a first electrode 2 formed on a first substrate 1 . An electron-transporting layer 4 is formed on the first electrode 2 , and a photosensitizing compound 5 is adsorbed on the surface of the electron-transporting material forming the electron-transporting layer 4 . A hole transport layer 6 is formed on and inside the electron transport layer 4 , and a second electrode 7 is formed on the hole transport layer 6 . A second substrate 9 is arranged above the second electrode 7 , and the second substrate 9 is fixed between the first electrode 2 and the sealing member 8 .
A photoelectric conversion element 101 of the first embodiment shown in FIG. 1 has a hollow portion 10 between a second electrode 7 and a second substrate 9 . By having the hollow portion 10, it is possible to control the moisture content and oxygen concentration in the hollow portion, and there is an advantage that the power generation performance and durability thereof can be improved. Furthermore, since the second electrode 7 and the second substrate 9 are not in contact with each other, peeling and breakage of the second electrode 7 can be prevented. The oxygen concentration in the hollow portion is not particularly limited and can be freely selected, but is preferably 0% or more and 21% or less, more preferably 5% or more and 15% or less.
Although illustration is omitted, each of the first electrode 2 and the second electrode 7 has a path leading to an electrode extraction terminal.

<Second embodiment>
FIG. 2 is a schematic diagram showing an example of the photoelectric conversion element of the second embodiment. A photoelectric conversion element 101 of the second embodiment shown in FIG. 2 has a hole blocking layer 3 formed between a first substrate 1 and an electron transport layer 4 . By forming the hole blocking layer 3, recombination of electrons and holes can be prevented, which is effective in improving power generation performance. The photoelectric conversion element shown in FIG. 2 has a hollow portion 10 between the second electrode 7 and the second substrate 9 as in FIG.

<Third Embodiment>
FIG. 3 is a schematic diagram showing an example of the photoelectric conversion element of the third embodiment. The photoelectric conversion element 101 of the third embodiment shown in FIG. 3 is obtained by covering the hollow portion 10 shown in FIG. For example, it can be formed by applying the sealing member 8 to the entire surface of the second electrode 7 and providing the second substrate 9 thereon, or by using the aforementioned sheet-like sealing material. In this case, the hollow part inside the sealing may be completely eliminated, or a part of the hollow part may be left. By covering almost the entire surface with the sealing member in this way, the second substrate 9 can be prevented from being peeled off or destroyed, and the mechanical strength of the photoelectric conversion element can be increased.

<Fourth Embodiment>
FIG. 4 is a schematic diagram showing an example of the photoelectric conversion element of the fourth embodiment. In the photoelectric conversion element 101 of the fourth embodiment shown in FIG. 4, the sealing member 8 is adhered to the first substrate 1 and the second substrate 9 . By adopting such a structure, the adhesiveness of the sealing member 8 to the substrate is increased, and the effect of increasing the mechanical strength of the photoelectric conversion element is obtained. In addition, by increasing the adhesion, it is possible to obtain the effect of further enhancing the sealing effect to prevent the infiltration of moisture and oxygen.

(Photoelectric conversion element module)
In the photoelectric conversion element module of the present invention, the photoelectric conversion elements of the present invention are electrically connected in series or in parallel.
The photoelectric conversion element module of the present invention has, for example, a photoelectric conversion element arrangement region in which a plurality of photoelectric conversion elements are arranged adjacently and connected in series or in parallel, and the plurality of photoelectric conversion elements are arranged in a first and a second electrode, a photoelectric conversion layer including an electron-transporting layer and a hole-transporting layer is formed.
The photoelectric conversion element module of the present invention can be configured to have a plurality of the photoelectric conversion elements. Moreover, the plurality of photoelectric conversion elements may be connected in series and/or in parallel, or may include independent photoelectric conversion elements that are not connected.
The structure of each layer of the photoelectric conversion element module can be the same as that of the photoelectric conversion element.
The structure of the photoelectric conversion element module is not particularly limited and can be appropriately selected according to the purpose. , it is preferable to be divided, thereby reducing the risk of short circuit. On the other hand, the hole transport layer may be divided in at least two photoelectric conversion elements adjacent to each other, or may be in the form of a continuous layer in which the hole transport layers are extended from each other.
Further, in the photoelectric conversion element module, in at least two photoelectric conversion elements adjacent to each other, the first electrode of one photoelectric conversion element and the second electrode of the other photoelectric conversion element are at least The hole transport layer and the hole blocking layer may be electrically connected to each other by a conductive portion penetrating therethrough.
A photoelectric conversion element module has a pair of substrates, a photoelectric conversion element arrangement region connected in series or in parallel between the pair of substrates, and the sealing member is sandwiched between the pair of substrates. can be configured.

The photoelectric conversion module of the present invention can be applied to a power supply device by combining it with a circuit board or the like that controls the generated current. Devices that use power supply devices include, for example, electronic desk calculators and wristwatches. Moreover, the power supply device having the photoelectric conversion module of the present invention can also be applied to mobile phones, electronic notebooks, electronic paper, and the like. A power supply device having the photoelectric conversion module of the present invention can also be used as an auxiliary power source for extending the continuous use time of electric appliances of a rechargeable type or a dry battery type, or as a power source that can be used even at night by combining with a secondary battery or the like. can be used. Furthermore, it can also be used for IoT devices, artificial satellites, etc. as a self-sustaining power source that does not require battery replacement or power supply wiring.

(Electronics)
An electronic device of the present invention includes the photoelectric conversion module of the present invention, a device that operates on electric power generated by photoelectric conversion by the photoelectric conversion module, and further includes other devices as necessary.

(power supply module)
The power supply module of the present invention includes the photoelectric conversion module of the present invention, a power supply IC (Integrated Circuit), and, if necessary, other devices.

Next, a specific embodiment of an electronic device having a photoelectric conversion module of the present invention and a device that operates on the power obtained by generating power from the module will be described.

FIG. 5 is a block diagram of a personal computer mouse as an example of the electronic device of the present invention.
As shown in FIG. 5, a photoelectric conversion module, a power supply IC, and a power storage device are combined, and the supplied power is connected to the power supply of the control circuit of the mouse. As a result, the electric storage device can be charged when the mouse is not in use, and the electric power can be used to operate the mouse, and a mouse that does not require wiring or battery replacement can be obtained. In addition, it is possible to reduce the weight by eliminating the need for a battery, which is effective.

6 is a schematic external view showing an example of the mouse shown in FIG. 5. FIG.
As shown in FIG. 6, the photoelectric conversion module, the power supply IC, and the electric storage device are mounted inside the mouse. It is It is also possible to mold the entire housing of the mouse with transparent resin. The arrangement of the photoelectric conversion element is not limited to this. For example, it is possible and preferable to arrange the photoelectric conversion element in a position where it is irradiated with light even when the mouse is covered with a hand.

Next, another embodiment of an electronic device having a photoelectric conversion module of the present invention and a device that operates on the electric power obtained by the photoelectric conversion module will be described.

FIG. 7 is a block diagram of a personal computer keyboard as an example of the electronic device of the present invention.
As shown in FIG. 7, the photoelectric conversion element of the photoelectric conversion module, the power supply IC, and the electric storage device are combined, and the supplied electric power is connected to the power supply of the control circuit of the keyboard. As a result, the power storage device can be charged when the keyboard is not in use, and the keyboard can be operated with the electric power, and a keyboard that does not require wiring or battery replacement can be obtained. In addition, it is possible to reduce the weight by eliminating the need for a battery, which is effective.

8 is a schematic external view showing an example of the keyboard shown in FIG. 7. FIG.
As shown in FIG. 8, the photoelectric conversion element of the photoelectric conversion module, the power supply IC, and the electric storage device are mounted inside the keyboard. It is It is also possible to mold the entire keyboard housing with transparent resin. The arrangement of the photoelectric conversion elements is not limited to this. In the case of a small keyboard having a small space for incorporating a photoelectric conversion element, it is possible and effective to embed a small photoelectric conversion element in a part of the key as shown in FIG.

Next, another embodiment of an electronic device having a photoelectric conversion module of the present invention and a device that operates on the electric power obtained by the photoelectric conversion module will be described.

FIG. 10 is a block diagram of a sensor as an example of the electronic device of the invention.
As shown in FIG. 10, the photoelectric conversion element of the photoelectric conversion module, the power supply IC, and the electric storage device are combined, and the supplied electric power is connected to the power supply of the sensor circuit. This makes it possible to configure the sensor module without connecting to an external power source and without the need to replace the battery. As a sensing object, it can be applied to various sensors such as temperature and humidity, illuminance, human sensation, _CO2 , acceleration, UV, noise, geomagnetism, atmospheric pressure, etc., and is effective. As shown in FIG. 11, the sensor module periodically senses the object to be measured and transmits the read data to a PC, smartphone, or the like by wireless communication.
With the advent of the IoT (Internet of Things) society, the number of sensors is expected to increase rapidly. Replacing the batteries of these countless sensors one by one takes a lot of time and effort, and is not practical. In addition, the sensor is located in a location where it is difficult to replace the battery, such as the ceiling or wall, which also reduces workability. The fact that electric power can be supplied by a photoelectric conversion element is also a great advantage. Further, the photoelectric conversion module of the present invention can obtain a high output even at low illuminance, and has a small dependence of the output on the light incident angle, so that it can be installed with a high degree of freedom.

Next, another embodiment of an electronic device having a photoelectric conversion module of the present invention and a device that operates on the electric power obtained by the photoelectric conversion module will be described.

FIG. 11 is a block diagram of a turntable as an example of the electronic device of the invention.
As shown in FIG. 11, a photoelectric conversion element, a power supply IC, and an electricity storage device are combined, and the supplied power is connected to the power supply of the turntable circuit. As a result, the turntable can be configured without connecting to an external power source and without the need to replace the battery.
Turntables are used, for example, as showcases for displaying products, but the wiring for the power supply is unattractive, and the displayed items must be removed when replacing the batteries, which is a great deal of time and effort. By using the photoelectric conversion module of the present invention, such problems can be effectively eliminated.

So far, the photoelectric conversion module of the present invention, an electronic device having a device that operates on the power generated by the photoelectric conversion module, and the power supply module have been described. The modules are not limited to these uses.

<Application>
The photoelectric conversion element and the photoelectric conversion module of the present invention can function as an independent power supply, and the power generated by photoelectric conversion can be used to operate the device. Since the photoelectric conversion module of the present invention can generate power when irradiated with light, it is not necessary to connect the electronic device to a power source or replace the battery. Therefore, it is possible to operate the electronic device even in a place where there is no power supply facility, carry it around by wearing it, or operate the electronic device without replacing the battery even in a place where it is difficult to replace the battery. In the case of using a dry battery, the weight of the electronic device is increased and the size of the electronic device is increased. Since the module is lightweight and thin, it has a high degree of freedom in installation, and is highly advantageous in terms of being worn or carried around.

Thus, the photoelectric conversion element and photoelectric conversion module of the present invention can be used as an independent power source and can be combined with various electronic devices. For example, electronic desk calculators, wristwatches, mobile phones, electronic notebooks, display devices such as electronic paper, personal computer accessories such as mice and keyboards, various sensor devices such as temperature/humidity sensors and human sensors, and transmission of beacons, GPS, etc. It can be used in combination with a large number of electronic devices such as machines, auxiliary lights, and remote controls.

INDUSTRIAL APPLICABILITY The photoelectric conversion element and photoelectric conversion module of the present invention can generate power even with light of low illuminance, so that they can generate power indoors or even in dimly lit areas, and thus have a wide range of applications. In addition, unlike dry batteries, there is no liquid leakage, and unlike button batteries, there is no accidental ingestion, so safety is high. Furthermore, it can be used as an auxiliary power source for extending the continuous use time of rechargeable or dry battery electric appliances. In this way, by combining the photoelectric conversion module of the present invention with a device that operates on the power generated by the photoelectric conversion, it is lightweight and easy to use, has a high degree of freedom in installation, does not require replacement, and is safe. It can be reborn as an electronic device that is highly durable and effective in reducing environmental impact.

FIG. 12 shows a basic configuration diagram of an electronic device in which the photoelectric conversion module of the present invention and a device that operates on the power generated by the photoelectric conversion are combined. This can generate power when the photoelectric conversion element is irradiated with light, and power can be taken out. The circuitry of the device is allowed to operate from that power.

However, since the output of the photoelectric conversion element of the photoelectric conversion module changes depending on the ambient illuminance, the electronic device shown in FIG. 12 may not operate stably. In this case, as shown in FIG. 13, in order to supply a stable voltage to the circuit side, it is possible and effective to incorporate a power source IC for the photoelectric conversion element between the photoelectric conversion element and the circuit of the device. .
However, the photoelectric conversion element of the photoelectric conversion module can generate electricity if it is irradiated with light of sufficient illuminance, but if the illuminance for generating power is insufficient, the desired electric power cannot be obtained. be. In this case, as shown in FIG. 14, by mounting an electricity storage device such as a capacitor between the power supply IC and the equipment circuit, it becomes possible to charge the electricity storage device with the surplus power from the photoelectric conversion element. is too low or the photoelectric conversion element is not exposed to light, the electric power stored in the electricity storage device can be supplied to the equipment circuit, and stable operation is possible.

In this way, by combining a power supply IC and a power storage device in an electronic device that combines the photoelectric conversion module of the present invention and a device circuit, it is possible to operate even in an environment without a power supply, and battery replacement is not required and stable. can be driven, and the advantages of the photoelectric conversion element can be maximized.

On the other hand, the photoelectric conversion module of the present invention can also be used as a power supply module and is useful. For example, as shown in FIG. 15, when the photoelectric conversion module of the present invention is connected to a power supply IC for photoelectric conversion elements, the power generated by the photoelectric conversion of the photoelectric conversion elements of the photoelectric conversion module is kept constant by the power supply IC. A DC power supply module capable of supplying a voltage level of
Furthermore, as shown in FIG. 16, by adding a power storage device to the power supply IC, it becomes possible to charge the power storage device with the power generated by the photoelectric conversion element of the photoelectric conversion module. Thus, it is possible to configure a power supply module capable of supplying electric power even when the photoelectric conversion element is not exposed to light.
The power supply module of the present invention shown in FIGS. 15 and 16 can be used as a power supply module without replacing batteries unlike conventional primary batteries.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1)
<Production of photoelectric conversion element>
Indium-doped tin oxide (ITO) and niobium-doped tin oxide (NTO) as a first electrode were sequentially formed by sputtering on a glass substrate as a first substrate.
Next, a dense layer (average thickness: 20 nm) made of titanium oxide was formed as a hole blocking layer by reactive sputtering with oxygen gas.

Next, a titanium oxide (18NR-T, manufactured by Greatcell Solar Materials) paste was applied onto the hole blocking layer so as to have an average thickness of about 1.2 μm, dried at 120° C., and then dried in air at 500° C. It was baked for 30 minutes to form a porous electron transport layer.
The glass substrate on which the electron transport layer was formed was coated with the photosensitizing compound (0.2 mM) represented by the above “B1-10” and the photosensitizing compound (0.2 mM) represented by the above “B2-1”. A mixed solution of acetonitrile/t-butanol (volume ratio 1:1) was added to the electron transport layer, and the sample was immersed in the stirred solution and allowed to stand in a dark place for 1 hour to adsorb the photosensitizing compound on the surface of the electron transport layer.

In advance, 1 mL of a chlorobenzene solution was added with 150 mM of the organic hole transport material (SHT-263, manufactured by Merck Co., Ltd.) represented by the above "D-7", and a lithium salt of lithium bis(trifluoromethanesulfonyl)imide) (manufactured by Kishida Chemical Co., Ltd.). ) 70 mM, 135 mM of the basic compound represented by “H-1” above, and 15 mM of the cobalt complex (FK209, Greatcell solar materials) represented by “F-11” above were added and dissolved to form a hole transport layer coating solution. was prepared.

Next, a hole-transporting layer coating liquid was used to form a hole-transporting layer having an average thickness of 500 nm on the electron-transporting layer on which the photosensitizing compound was adsorbed by a die coating method. After that, the end portion of the glass substrate on which the sealing member was to be provided was etched by laser processing, and a through hole for connecting to the ITO layer serving as the terminal extraction portion was formed by laser processing. Furthermore, silver was vacuum-deposited thereon to form a second electrode of about 70 nm.

Next, an ultraviolet curable resin (TB3118, manufactured by ThreeBond Holdings Co., Ltd.) was applied to the edge of the glass substrate using a dispenser (2300N, manufactured by Sanei Tech Co., Ltd.) so as to surround the power generation area. After that, it was transferred to a glove box controlled to have a dew point of minus 40 ° C. and an oxygen concentration of 10%, a cover glass as a second substrate was placed on the ultraviolet curing resin, cured by ultraviolet irradiation, and then at 80 ° C. Heated for 60 minutes. The power generation region was sealed, and the photoelectric conversion element of Example 1 as shown in FIG. 1 was produced.

(Examples 2 to 15)
In Example 1, in the same manner as in Example 1, except that "B1-10" and "B2-1" as photosensitizer compounds were changed to the materials shown in Table 1, as shown in FIG. Photoelectric conversion elements of Examples 2 to 15 were produced.

(Example 16)
In Example 2, the basic compound represented by "H-1" was changed to 4-dimethylaminopyridine (DMAP) (manufactured by Tokyo Kasei Co., Ltd.) in the same manner as in Example 2, FIG. A photoelectric conversion device as shown in was produced.

(Example 17)
In Example 2, in the same manner as in Example 2, except that the basic compound represented by "H-1" was changed to 4-pyrrolidinopyridine (PYP) (manufactured by Tokyo Kasei Co., Ltd.), FIG. A photoelectric conversion device as shown in was produced.

(Example 18)
In Example 2, the basic compound represented by "H-1" was changed to 4-piperidinopyridine (PPP) (manufactured by Aldrich) in the same manner as in Example 2, as shown in FIG. A photoelectric conversion device as shown was produced.

(Example 19)
In Example 2, the basic compound represented by "H-1" was changed to the basic compound represented by "H-3" in the same manner as in Example 9, as shown in FIG. A photoelectric conversion device was produced.

(Comparative example 1)
Photoelectric conversion as shown in FIG. A device was produced.

(Comparative example 2)
Photoelectric conversion as shown in FIG. A device was produced.

(Comparative Example 3)
Photoelectric conversion as shown in FIG. A device was produced.

(Comparative Example 4)
In Example 2, photoelectric conversion as shown in FIG. A device was produced.

(Comparative Example 5)
In Example 1, in the same manner as in Example 1, except that "B2-1" as a photosensitizer compound was changed to 4-heptyloxybenzoic acid (HeBA) (manufactured by Tokyo Chemical Industry Co., Ltd.), A photoelectric conversion device as shown in FIG. 1 was produced.

(Comparative Example 6)
A photoelectric conversion device as shown in FIG. 1 was produced in the same manner as in Example 1, except that "B2-1" as a dye was not added.

(Comparative Example 7)
A photoelectric conversion device as shown in FIG. 1 was produced in the same manner as in Example 2, except that "B1-10" was not added as a dye.

Next, various characteristics of each obtained photoelectric conversion element were evaluated as follows. The results are shown in Tables 1-3.

<Evaluation of photoelectric conversion element>
For each photoelectric conversion element obtained, IV characteristics were evaluated using a solar cell evaluation system (As-510-PV03, manufactured by NF Circuit Design Block Co., Ltd.) under illumination of a 5000K white LED adjusted to 500 lux. , the initial open-circuit voltage Voc1 (V) and the maximum output power Pmax1 (μW/cm ² ) were obtained.
A white LED of 5,000 K was irradiated at 2,000 lux, 50 ° C., 1,000 hours, and the IV characteristics of the light source under the same conditions were evaluated again, and the open circuit voltage Voc2 and the maximum output power Pmax2 ( μW/cm ² ) was measured, and the Voc retention rate (Voc2/Voc1) (%) and Pmax retention rate (Pmax2/Pmax1) (%) were determined.

From the results in Tables 1 and 2, it was found that Examples 1 to 19 can suppress the deterioration of characteristics with low illuminance light after being exposed to high temperature light irradiation as compared with Comparative Examples 1 to 7. In solid-state dye-sensitized solar cells, it has been found that the association state and interaction between dyes are very important for efficient photoelectric conversion under high-temperature light irradiation environments.

ただし、前記一般式（１）中、Ａｒ_１及びＡｒ_２は、置換基を有していてもよいアリール基を表す。Ｒ_１及びＲ_２は、炭素数４～１０の直鎖又は分岐状のアルキル基を表す。Ｘは、下記構造式で表されるいずれかの置換基を表す。

ただし、前記一般式（２）中、Ｒ_３は、アリール基、下記構造式で表されるいずれかの置換基のいずれかを表す。ｎは０～１の整数を表す。

＜２＞ 前記電子輸送層は、前記光増感化合物が担持された酸化チタン粒子からなる多孔質状である、前記＜１＞に記載の光電変換素子である。
＜３＞前記一般式（１）で表される化合物が下記一般式（３）で表される化合物である、前記＜１＞から＜２＞のいずれかに記載の光電変換素子である。

ただし、前記一般式（３）中、Ａｒ_４及びＡｒ_５は、置換基を有してもよいフェニル基、又は置換基を有してもよいナフチル基を表す。Ａｒ_６は、フェニル基、又はチオフェン基を表す。
＜４＞前記ホール輸送層が下記一般式（４）で表される３価のコバルト錯体化合物を含有する、前記＜１＞から＜３＞のいずれかに記載の光電変換素子である。

ただし、前記一般式（４）中、Ｒ_３～Ｒ_５は、水素原子、メチル基、エチル基、ターシャルブチル基、又はトリフルオロメチル基を示す。Ｙは、下記構造式（２）から（５）で表されるいずれかを示す。

＜５＞ 前記ホール輸送層が下記一般式（５）で表される塩基性化合物を含有する、前記＜１＞から＜４＞のいずれかに記載の光電変換素子である。

ただし、前記一般式（５）中、Ａｒ_７及びＡｒ_８は、置換基を有していてもよいアリール基を表す。
＜６＞ 前記ホール輸送層がスピロ型化合物を含有する、前記＜１＞から＜５＞のいずれかに記載の光電変換素子である。
＜７＞ 前記スピロ型化合物が、下記一般式（６）を含む化合物である、前記＜６＞に記載の光電変換素子である。

ただし、前記一般式（６）中、Ｒ_４からＲ_７は、それぞれ独立して、ジメチルアミノ基、ジフェニルアミノ基、ナフチル－４－トリルアミノ基などの置換アミノ基を表す
＜８＞ 前記＜１＞から＜７＞のいずれかに記載の光電変換素子が光電変換することによって発生した電力によって動作する装置を有することを特徴とする電子機器である。
＜９＞ 前記＜１＞から＜７＞のいずれかに記載の光電変換素子と、
電源ＩＣと、
を有することを特徴とする電源モジュールである。 Embodiments of the present invention are, for example, as follows.
<1> A photoelectric conversion element having a first electrode, an electron transport layer, a photosensitizing compound, a hole transport layer, and a second electrode,
The photoelectric conversion device is characterized in that the photosensitizing compound includes a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

However, in the general formula (1), Ar ₁ and Ar ₂ represent an aryl group which may have a substituent. R ₁ and R ₂ each represent a linear or branched alkyl group having 4 to 10 carbon atoms. X represents any substituent represented by the following structural formula.

However, in the general formula (2), R ₃ represents either an aryl group or a substituent represented by the following structural formula. n represents an integer of 0 to 1;

<2> The photoelectric conversion element according to <1>, wherein the electron transport layer is porous and made of titanium oxide particles supporting the photosensitizing compound.
<3> The photoelectric conversion device according to any one of <1> to <2>, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

However, in the general formula (3), Ar ₄ and Ar ₅ represent an optionally substituted phenyl group or an optionally substituted naphthyl group. Ar ₆ represents a phenyl group or a thiophene group.
<4> The photoelectric conversion device according to any one of <1> to <3>, wherein the hole transport layer contains a trivalent cobalt complex compound represented by the following general formula (4).

However, in the general formula (4), R ₃ to R ₅ represent a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, or a trifluoromethyl group. Y represents any one of the following structural formulas (2) to (5).

<5> The photoelectric conversion device according to any one of <1> to <4>, wherein the hole transport layer contains a basic compound represented by the following general formula (5).

However, in the general formula (5), Ar ₇ and Ar ₈ represent an aryl group which may have a substituent.
<6> The photoelectric conversion element according to any one of <1> to <5>, wherein the hole transport layer contains a spiro-type compound.
<7> The photoelectric conversion device according to <6>, wherein the spiro-type compound is a compound containing the following general formula (6).

However, in general formula (6), R ₄ to R ₇ each independently represent a substituted amino group such as a dimethylamino group, a diphenylamino group, or a naphthyl-4-tolylamino group <8> above <1> An electronic device comprising a device operated by electric power generated by photoelectric conversion of the photoelectric conversion element according to any one of <7> to <7>.
<9> the photoelectric conversion element according to any one of <1> to <7>;
a power supply IC;
A power supply module characterized by comprising:

The photoelectric conversion element according to any one of <1> to <7>, the electronic device according to <8>, and the power supply module according to <9> solve the conventional problems, and The object of the present invention can be achieved.

REFERENCE SIGNS LIST 1 first substrate 2 first electrode 3 hole blocking layer 4 electron transport layer 5 photosensitizing compound 6 hole transport layer 7 second electrode 8 sealing member 9 second substrate 10 hollow portion 101 photoelectric conversion element

JP 2018-113305 A

Claims (9)

A photoelectric conversion element having a first electrode, an electron transport layer, a photosensitizing compound, a hole transport layer, and a second electrode,
A photoelectric conversion device, wherein the photosensitizing compound includes a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

However, in the general formula (1), Ar ₁ and Ar ₂ represent an aryl group which may have a substituent. R ₁ and R ₂ each represent a linear or branched alkyl group having 4 to 10 carbon atoms. X represents any substituent represented by the following structural formula.

However, in the general formula (2), R ₃ represents either an aryl group or a substituent represented by the following structural formula. n represents an integer of 0 to 1;

2. The photoelectric conversion device according to claim 1, wherein the electron transport layer is porous and made of titanium oxide particles supporting the photosensitizing compound. 3. The photoelectric conversion device according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

However, in the general formula (3), Ar ₄ and Ar ₅ represent an optionally substituted phenyl group or an optionally substituted naphthyl group. Ar ₆ represents a phenyl group or a thiophene group. The photoelectric conversion device according to any one of claims 1 to 3, wherein the hole transport layer contains a trivalent cobalt complex compound represented by the following general formula (4).

However, in the general formula (4), R ₃ to R ₅ represent a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, or a trifluoromethyl group. Y represents any one of the following structural formulas (2) to (5).

The photoelectric conversion device according to any one of claims 1 to 4, wherein the hole transport layer contains a basic compound represented by the following general formula (5).

However, in the general formula (5), Ar ₇ and Ar ₈ represent an aryl group which may have a substituent. The photoelectric conversion device according to any one of claims 1 to 5, wherein the hole transport layer contains a spiro-type compound. 7. The photoelectric conversion device according to claim 6, wherein the spiro-type compound is a compound containing the following general formula (6).

However, in the general formula (6), R ₄ to R ₇ each independently represent a substituted amino group such as a dimethylamino group, a diphenylamino group and a naphthyl-4-tolylamino group. 8. An electronic apparatus comprising a device that operates by electric power generated by photoelectric conversion of the photoelectric conversion element according to any one of claims 1 to 7. a photoelectric conversion element according to any one of claims 1 to 7;
a power supply IC;
A power supply module comprising:

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