JP2020102602A - Photoelectric conversion element and photoelectric conversion element module - Google Patents

Abstract

To provide a photoelectric conversion element that can maintain high output after high-temperature storage and after continuous irradiation of low-intensity light.SOLUTION: A photoelectric conversion element 101 has at least a first electrode 2, a hole blocking layer 3, an electron transport layer 4 having a photosensitization compound, a hole transport layer 6, and a second electrode 7. The photoelectric conversion element has a sealing member 8 containing an epoxy resin that shields at least the electron transport layer, hole transport layer, and second electrode from an outside environment of the photoelectric conversion element; the hole transport layer has at least one of tertiary amine compounds having a specific structure.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photoelectric conversion element and a photoelectric conversion element module.

In recent years, the importance of solar cells has increased as an alternative energy to fossil fuels and as a measure against global warming. Further, the solar cell and the photodiode are applications of a photoelectric conversion element capable of converting light energy into electric energy.
Recently, not only sunlight (illumination with direct light: about 100,000 lux), but also light with low illuminance (illuminance: 20 lux or more, 1,000 lux, etc.) such as an LED (light emitting diode) or a fluorescent lamp. Even in the following), indoor photoelectric conversion elements having high power generation performance have been attracting attention.

However, the photoelectric conversion element has a problem that its output is significantly reduced when it is stored in a high temperature and high humidity environment.
Therefore, in order to prevent water vapor or oxygen in the external environment from penetrating into the photoelectric conversion element and reducing the photoelectric conversion efficiency under a high temperature and high humidity environment, for example, a first electrode and a second substrate are used. A photoelectric conversion element in which a sealing member that seals the photoelectric conversion layer is provided between the photoelectric conversion elements has been proposed (for example, see Patent Document 1).

It is an object of the present invention to provide a photoelectric conversion element that can maintain high output after being stored at high temperature and continuously irradiated with low illuminance light.

A photoelectric conversion element of the present invention as a means for solving the above-mentioned problems includes a first electrode, a hole blocking layer, an electron transport layer having a photosensitizing compound, a hole transport layer, and a second electrode. A photoelectric conversion element having at least the electron transport layer, a hole transport layer and a second electrode, the sealing member containing an epoxy resin for shielding from the external environment of the photoelectric conversion element, the hole The transport layer has at least one of the tertiary amine compounds represented by the following general formula (1) and general formula (2).
However, the general formula (1), and in the general formula (2), Ar ₁ and Ar ₂ have substituents represent also aryl groups, wherein Ar ₁ and the Ar ₂ are also the same They may be different or may be bonded to each other.

According to the present invention, it is possible to provide a photoelectric conversion element capable of maintaining a high output after being stored at a high temperature and continuously irradiated with low-illuminance light.

FIG. 1 is a schematic diagram showing an example of the photoelectric conversion element of the present invention. FIG. 2 is a schematic diagram showing another example of the photoelectric conversion element of the present invention. FIG. 3 is a schematic view showing another example of the photoelectric conversion element of the present invention. FIG. 4 is a schematic diagram showing another example of the photoelectric conversion element of the present invention. FIG. 5 is a schematic view showing another example of the photoelectric conversion element of the present invention. FIG. 6 is a schematic view showing an example of the photoelectric conversion element module of the present invention. FIG. 7 is a schematic view of FIG. 6 observed from different angles. FIG. 8 is a schematic diagram showing an example in which a mouse is used as the electronic device. FIG. 9 is a schematic diagram showing an example in which a photoelectric conversion element is mounted on a mouse. FIG. 10 is a schematic view showing an example using a keyboard used in a personal computer as an electronic device. FIG. 11 is a schematic diagram showing an example in which a photoelectric conversion element is mounted on a keyboard. FIG. 12 is a schematic diagram showing an example in which a small photoelectric conversion element is mounted on a part of the keys of the keyboard. FIG. 13 is a schematic diagram showing an example in which a sensor is used as an electronic device. FIG. 14 is a schematic diagram showing an example in which a turntable is used as an electronic device. FIG. 15 illustrates an example of an electronic device in which the photoelectric conversion element and/or the photoelectric conversion element module of the present invention and the photoelectric conversion element and/or a device which operates by electric power generated by photoelectric conversion of the photoelectric conversion element module are combined. FIG. FIG. 16 is a schematic diagram showing an example in which a power supply IC for a photoelectric conversion element is incorporated between the photoelectric conversion element and the circuit of the device in FIG. FIG. 17 is a schematic diagram showing an example in which the power storage device is incorporated between the power supply IC and the circuit of the device in FIG. 16. FIG. 18 is a schematic diagram showing an example of a power supply module having a photoelectric conversion element and/or a photoelectric conversion element module of the present invention and a power supply IC. 19 is a schematic diagram showing an example of a power supply module in which a power storage device is added to the power supply IC in FIG.

As a result of intensive studies, the present inventors have found out the following.
In the case of the photoelectric conversion element of Patent Document 1, by providing the sealing member, it is possible to prevent the water vapor and oxygen in the external environment from penetrating into the photoelectric conversion element and reducing the photoelectric conversion efficiency under high temperature and high humidity environment. However, after storage at high temperature and after continuous irradiation with low-illuminance light, there is a problem that the output is significantly reduced and durability in a high temperature and high humidity environment is poor.
It is considered that when stored in a high temperature environment, gas is generated or the resin as the sealing member is heated and the hermeticity is deteriorated depending on the type of the resin as the sealing member.
Therefore, the present inventors have used an epoxy resin as a sealing member that shields at least the electron transport layer, the hole transport layer, and the second electrode from the external environment of the photoelectric conversion element, and uses a general formula ( By containing at least one of 1) and the tertiary amine compound represented by the general formula (2), a photoelectric conversion element capable of maintaining high output after storage at high temperature and after continuous irradiation with low illumination light is provided. I found that I can.

(Photoelectric conversion element)
The photoelectric conversion element of the present invention is a photoelectric conversion element having at least a first electrode, a hole blocking layer, an electron transport layer having a photosensitizing compound, a hole transport layer, and a second electrode, At least the electron transport layer, the hole transport layer, and the second electrode have a sealing member containing an epoxy resin that shields the photoelectric conversion element from the external environment, and the hole transport layer has the following general formula (1). , And at least one of the tertiary amine compounds represented by the general formula (2), and optionally other layers. Each layer may have a single-layer structure or a laminated structure.

However, the general formula (1), and in the general formula (2), Ar ₁ and Ar ₂ have substituents represent also aryl groups, wherein Ar ₁ and the Ar ₂ are also the same They may be different or may be bonded to each other.

<First electrode>
The photoelectric conversion element has a 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 depending on the purpose, and may be a single layer structure or a structure in which a plurality of materials are laminated.

The material of the first electrode is not particularly limited as long as it has transparency and conductivity with respect to visible light, and can be appropriately selected according to the purpose. For example, transparent conductive metal oxide, carbon, Examples include metals.

Examples of the transparent conductive metal oxide include indium tin oxide (hereinafter referred to as “ITO”), fluorine-doped tin oxide (hereinafter referred to as “FTO”), antimony-doped tin oxide (hereinafter referred to as “ATO”). ), niobium-doped tin oxide (hereinafter referred to as “NTO”), aluminum-doped zinc oxide, indium-zinc oxide, niobium-titanium oxide, and the like.
Examples of carbon include carbon black, carbon nanotubes, graphene, and fullerenes.
Examples of the metal include gold, silver, aluminum, nickel, indium, tantalum, titanium and the like.
These may be used alone or in combination of two or more. Among these, transparent conductive metal oxides having high transparency are preferable, and ITO, FTO, ATO, and NTO are more preferable.

The average thickness of the first electrode is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 nm or more and 100 μm or less, more preferably 50 nm or more and 10 μm or less. When the material of the first electrode is carbon or metal, the average thickness of the first electrode is preferably an average thickness that allows translucency.

The first electrode can be formed by a known method such as a sputtering method, a vapor deposition method, or a spray method.

Further, the first electrode is preferably formed on the first substrate, and an integrated commercially available product in which the first electrode is previously formed on the first substrate can be used.
Examples of integrated commercial products include 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, a transparent electrode in which tin oxide or indium oxide is doped with cations or anions having different valences, or a metal having a structure such as mesh or stripe that allows light to pass therethrough. Examples thereof include a glass substrate provided with an electrode.
These may be used alone or in combination of two or more and mixed or laminated. Further, a metal lead wire or the like may be used together for the purpose of lowering the electric resistance value.

Examples of the material of the metal lead wire include aluminum, copper, silver, gold, platinum, nickel and the like.
The metal lead wire can be used together by forming it on the substrate by vapor deposition, sputtering, pressure bonding, or the like, and providing an ITO or FTO layer thereon.

<Hole blocking layer>
The photoelectric conversion element has a hole blocking layer.
The hole blocking layer is formed between the first electrode and the electron transport layer. The hole blocking layer transports the electrons generated by the photosensitizing compound and transported to the electron transport layer to the first electrode, and prevents contact with the hole transport layer. As a result, the hole blocking layer makes it difficult for holes to flow into the first electrode, and can suppress a decrease in output due to recombination of electrons and holes. Since the solid-type photoelectric conversion device provided with the hole transport layer has a faster recombination rate of holes in the hole transport material and electrons on the electrode surface than in the wet type using an electrolyte solution, the formation of the hole blocking layer. The effect of is extremely large.

The material of the hole blocking layer is not particularly limited as long as it is transparent to visible light and has an electron transporting property, and can be appropriately selected according to the purpose, for example, silicon, germanium, etc. Examples include simple semiconductors, compound semiconductors represented by metal chalcogenides, compounds having a perovskite structure, and the like.
Examples of the metal chalcogenide include oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium and tantalum; cadmium, zinc, lead, silver and antimony. , Bismuth sulfide; cadmium, lead selenide; cadmium telluride. Examples of other compound semiconductors include phosphides such as zinc, gallium, indium, and cadmium; gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like.
Examples of the compound having a perovskite structure include strontium titanate, calcium titanate, sodium titanate, barium titanate, and potassium niobate.
Among these, oxide semiconductors are preferable, titanium oxide, niobium oxide, magnesium oxide, aluminum oxide, zinc oxide, tungsten oxide and tin oxide are more preferable, and titanium oxide is still more preferable.
These may be used alone or in combination of two or more. Moreover, you may laminate|stack as a single layer. The crystal type of these semiconductors is not particularly limited and can be appropriately selected depending on the purpose, and may be single crystal, polycrystal, or amorphous.

The method for forming the hole blocking layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sol-gel method for wet film formation, a hydrolysis method from titanium tetrachloride, and a sputtering method for dry film formation. Among these, the sputtering method is preferable. When the film forming method of the hole blocking layer is the sputtering method, the film density can be sufficiently increased and the loss current can be suppressed.

The thickness of the hole blocking layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 nm or more and 1 μm or less, more preferably 500 nm or more and 700 nm or less for wet film formation, and 5 nm or more and 30 nm for dry film formation. The following is more preferable.

<Electron transport layer>
The photoelectric conversion element has an electron transport layer containing a photosensitizing compound.
The electron transport layer is formed for the purpose of transporting electrons generated by the photosensitizing compound to the hole blocking layer. Therefore, the electron transport layer is preferably arranged adjacent to the hole blocking layer.

The structure of the electron transport layer is not particularly limited and may be appropriately selected depending on the purpose, but in at least two photoelectric conversion elements adjacent to each other, it is preferable that the electron transport layers are not extended to each other. .. The structure of the electron transport layer may be a continuous single layer or a multilayer in which a plurality of layers are laminated.

The electron-transporting layer contains an electron-transporting material, and optionally other materials.

The electron transporting material is not particularly limited and can be appropriately selected according to the purpose, but a semiconductor material is preferable.
It is preferable that the semiconductor material has a fine particle shape, and that these particles are joined together to form a porous film. The photosensitizing compound is chemically or physically adsorbed on the surface of the semiconductor fine particles forming the porous electron transport layer.

The semiconductor material is not particularly limited, and known materials can be used, and examples thereof include a single semiconductor, a compound semiconductor, and a compound having a perovskite structure.
Examples of the single semiconductor include silicon and germanium.
Examples of the compound semiconductor include metal chalcogenides, specifically, oxides of titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum, and the like; Examples thereof include sulfides such as cadmium, zinc, lead, silver, antimony, and bismuth; selenides such as cadmium and lead; tellurides such as cadmium. Examples of other compound semiconductors include phosphides such as zinc, gallium, indium, and cadmium, gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like.
Examples of the compound having a perovskite structure include strontium titanate, calcium titanate, sodium titanate, barium titanate, and potassium niobate.
Among these, oxide semiconductors are preferable, and titanium oxide, zinc oxide, tin oxide, and niobium oxide are particularly preferable. When the electron-transporting material of the electron-transporting layer is titanium oxide, the refractive index and the mobility are high, which is advantageous in that the output and durability are improved.
These may be used alone or in combination of two or more. The crystal type of the semiconductor material is not particularly limited and can be appropriately selected according to 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 may be appropriately selected depending on the intended purpose, but is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less. Further, a semiconductor material having a number average particle diameter larger than that may be mixed or laminated, and the conversion efficiency may be improved due to 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 may be appropriately selected depending on the intended purpose, but is preferably 50 nm or more and 100 μm or less, more preferably 100 nm or more and 50 μm or less, still more preferably 120 nm or more and 10 μm or less. When the average thickness of the electron transport layer is within the preferred range, the amount of the photosensitizing compound per unit projected area can be sufficiently secured, the light trapping rate can be maintained high, and the diffusion distance of the injected electrons also increases. This is advantageous in that it is difficult to do so and the loss due to recombination of charges can be reduced.

The method for producing the electron transport layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of forming a thin film in a vacuum such as sputtering and a wet film forming method. Among these, from the viewpoint of manufacturing cost, the wet film forming method is preferable, and a method of preparing a paste in which a powder or sol of a semiconductor material is dispersed and coating it on the hole blocking layer as the electron collecting electrode substrate is more preferable. ..
The wet film forming method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dipping method, spraying method, wire bar method, spin coating method, roller coating method, blade coating method and gravure coating method. And so on.
As the wet printing method, various methods such as letterpress, offset, gravure, intaglio, rubber plate, and screen printing can be used.

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

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

An acid, a surfactant, a chelating agent or the like may be added to the dispersion liquid containing a semiconductor material or the paste containing a semiconductor material obtained by the sol-gel method or the like in order to prevent reaggregation of particles.
Examples of the acid include hydrochloric acid, nitric acid, acetic acid and the like.
Examples of the surfactant include polyoxyethylene octyl phenyl ether and the like.
Examples of the chelating agent include acetylacetone, 2-aminoethanol, ethylenediamine and the like.
Further, addition of a thickener is also an effective means for the purpose of improving the film forming property.
Examples of the thickener include polyethylene glycol, polyvinyl alcohol, ethyl cellulose and the like.

After applying the semiconductor material, the particles of the semiconductor material are electronically contacted with each other, and baked to improve the film strength and the adhesion to the substrate, irradiated with microwaves or electron beams, or irradiated with laser light. Can be irradiated. These treatments may be performed alone or in combination of two or more.

When firing the electron transport layer formed of a semiconductor material, the firing temperature is not particularly limited and may be appropriately selected depending on the purpose, but if the temperature is too high, the resistance of the substrate may increase. Since it may melt, it is preferably 30° C. or higher and 700° C. or lower, and more preferably 100° C. or higher and 600° C. or lower. The firing time is appropriately selected depending on the intended purpose without any limitation, but it is preferably 10 minutes or more and 10 hours or less.
When the electron transport layer formed of a semiconductor material is irradiated with microwaves, the irradiation time is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 1 hour or less. In this case, the irradiation may be performed from the surface side on which the electron transport layer is formed, or from the surface 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 enhancing the efficiency of electron injection from the photosensitizing compound described later into the semiconductor material, for example, an aqueous solution of titanium tetrachloride or an organic solvent. Chemical plating using a mixed solution of or and electrochemical plating using an aqueous solution of titanium trichloride may be performed.
A film obtained by sintering a semiconductor material having a diameter of several tens of nm can form a porous state. Such a nanoporous structure has a very high surface area, which can be expressed using a roughness factor. The roughness factor is a numerical value representing the actual area of the inside of the porous material with respect to the area of the semiconductor particles coated on the first substrate. Therefore, the roughness factor is preferably as large as possible, but is preferably 20 or more in view of the relationship with the average thickness of the electron transport layer.

<<Photosensitizing compound>>
The photosensitizing compound is adsorbed on the surface of the semiconductor material forming the electron transport layer in order to further improve the output and the photoelectric conversion efficiency.
The photosensitizing compound is not particularly limited as long as it is a compound that is photoexcited by the light with which the photoelectric conversion element is irradiated, and can be appropriately selected depending on the purpose, and examples thereof include the following known compounds. ..
Specifically, metal complex compounds, J. Phys. Chem. C, 7224, Vol. 111 (2007) and the like, coumarin compounds, Chem. Commun. , 4887 (2007), the polyene compounds described in J. Am. Chem. Soc. , 12218, Vol. 126 (2004), Chem. Commun. 3036 (2003), Angew. Chem. Int. Ed. , 1923, Vol. 47 (2008) and the like, indoline compounds, J. Am. Chem. Soc. , 16701, Vol. 128 (2006), J. Am. Chem. Soc. 14256, Vol. 128 (2006) and the like, thiophene compounds, cyanine dyes, merocyanine dyes, 9-arylxanthene compounds, triarylmethane compounds, J. Phys. Chem. 2342, Vol. 91 (1987), J. Phys. Chem. B, 6272, Vol. 97 (1993), Electroanal. Chem. , 31, Vol. 537 (2002)J. Porphyrins Phthalocyanines, 230, Vol. 3 (1999), Angew. Chem. Int. Ed. , 373, Vol. 46 (2007), Langmuir, 5436, Vol. 24 (2008) and the like, phthalocyanine compounds, porphyrin compounds and the like. These may be used alone or in combination of two or more. Among these, metal complex compounds, coumarin compounds, polyene compounds, indoline compounds, and thiophene compounds are preferable, and are represented by the following structural formula (1), structural formula (2), and structural formula (3) manufactured by Mitsubishi Paper Mills Co., Ltd. And more preferably a compound containing the following general formula (3).

In the general formula (3), X ₁ and X ₂ represent an oxygen atom, a sulfur atom or a selenium atom. R ₁ represents a methine group which may have a substituent. Specific examples of the substituent include an aryl group such as a phenyl group and a naphthyl group, and a heterocycle such as a thienyl group and a furyl group.
R ₂ represents an alkyl group, an aryl group or a heterocyclic group which may have a substituent. Examples of the alkyl group include a methyl group, ethyl group, 2-propyl group, 2-ethylhexyl group and the like, and examples of the aryl group and the heterocyclic group include those described above.
R ₃ represents an acidic group such as carboxylic acid, sulfonic acid, phosphonic acid, boronic acid and phenols. Z1 and Z2 represent a substituent forming a cyclic structure.
Examples of Z1 include condensed hydrocarbon compounds such as benzene ring and naphthalene ring, and hetero rings such as thiophene ring and furan ring, each of which may have a substituent. Specific examples of the substituent include the aforementioned alkyl groups, methoxy groups, ethoxy groups, and alkoxy groups such as 2-isopropoxy group.
Examples of Z2 include (A-1) to (A-22) shown below. However, it is not limited to these.

Specific examples of the photosensitizing compound containing the above general formula (3) include (B-1) to (B-36) shown below.

As a method of 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 solution of the photosensitizing compound or a dispersion of the photosensitizing compound. A method, a method of applying a solution of a photosensitizing compound, or a method of applying a dispersion of a photosensitizing compound to an electron transporting layer and adsorbing it can be used. In the case of a method of immersing the electron transport layer formed with a semiconductor material in a solution of a photosensitizing compound or a dispersion of a photosensitizing compound, use a dipping method, a dipping method, a roller method, an air knife method or the like. You can In the case of a method in which a solution of a photosensitizing compound or a dispersion of a photosensitizing compound is applied to an electron transport layer to be adsorbed, a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, a spray method. The method etc. can be used. It is also possible to adsorb it in a supercritical fluid such as carbon dioxide.

When adsorbing the photosensitizing compound to the semiconductor material, a condensing agent may be used together.
As the condensing agent, a condensing agent that physically or chemically acts on the surface of the semiconductor material such as a catalytic action for binding a photosensitizing compound or a stoichiometric action that favorably shifts the chemical equilibrium is used. It may be either. Further, a thiol or a hydroxy compound may be added as a condensation aid.

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

Depending on the type of photosensitizing compound, it may be more effective to suppress the aggregation between the compounds. Therefore, an aggregation dissociating agent may be used in combination.
The aggregation/dissociation agent is not particularly limited and may be appropriately selected depending on the dye to be used, but steroid compounds such as cholic acid and chenodeoxycholic acid, long-chain alkylcarboxylic acids or long-chain alkylphosphonic acids are preferable.
The content of the aggregation dissociation agent is preferably 0.01 parts by mass or more and 500 parts by mass or less, and more preferably 0.1 parts by mass or more and 100 parts by mass or less with respect to 1 part by mass of the photosensitizing compound.

The temperature at which the photosensitizing compound, or the photosensitizing compound and the aggregation dissociating agent are adsorbed on the surface of the semiconductor material forming the electron transport layer, is preferably −50° C. or higher and 200° C. or lower. The adsorption time is preferably 5 seconds or more and 1,000 hours or less, more preferably 10 seconds or more and 500 hours or less, still more preferably 1 minute or more and 150 hours or less. The adsorbing step is preferably performed in a dark place. Further, the step of adsorbing may be carried out by standing still, or may be carried out with stirring.
The stirring method is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a method using a stirrer, a ball mill, a paint conditioner, a sand mill, an attritor, a disperser, ultrasonic dispersion and the like. To be

<Hall transport layer>
The photoelectric conversion element has a hole transport layer.
The hole transport layer has at least one of the tertiary amine compounds represented by the following general formula (1) and general formula (2).

However, the general formula (1), and in the general formula (2), Ar ₁ and Ar ₂ have substituents represent also aryl groups, wherein Ar ₁ and the Ar ₂ are also the same They may be different or may be bonded to each other.

Since the hole transport layer has at least one of the tertiary amine compounds represented by the general formula (1) and the general formula (2), even when the photoelectric conversion element is stored in a high temperature and high humidity environment, It is possible to maintain high output. Further, high output can be maintained even when light with low illuminance is continuously irradiated after being stored in a high temperature and high humidity environment.

Next, specific examples of the tertiary amine compound represented by the general formula (1) and the general formula (2) include, for example, the exemplified compounds C-1 to C-20 shown below. It is not limited. These may be used alone or in combination of two or more.

The content of the tertiary amine compound represented by the general formula (1) or the general formula (2) in the hole transport layer is preferably 1 part by mass or more and 50 parts by mass or less based on the total amount of the hole transport material. More preferably, it is from 30 parts by mass to 30 parts by mass. When the content of the tertiary amine compound is 1 part by mass or more and 50 parts by mass or less, high output can be maintained after high temperature storage and after continuous irradiation with low illuminance light.

The form of the hole transport layer is not particularly limited as long as it has a function of transporting holes, and can be appropriately selected according to the purpose, for example, an electrolytic solution in which a redox couple is dissolved in an organic solvent, A gel electrolyte in which a polymer matrix is impregnated with a liquid in which a redox couple is dissolved in an organic solvent, a molten salt containing a redox couple, a solid electrolyte, an inorganic hole transport material (inorganic p-type semiconductor material), an organic hole transport material (organic p Type semiconductor material). These may be used alone or in combination of two or more. Among these, solid electrolytes are preferable, and organic hole transport materials are more preferable.

The hole transport layer contains at least one of a hole transport material and a p-type semiconductor material in order to obtain a function of transporting holes.
At least one of the hole transport material and the p-type semiconductor material is not particularly limited and may be appropriately selected depending on the purpose. For example, a known organic hole transport compound may be used.
Known organic hole transporting compounds include, for example, oxadiazole compounds disclosed in JP-B-34-5466, triphenylmethane compounds disclosed in JP-B-45-555, and JP-B- No. 52-4188, etc., a pyrazoline compound, Japanese Patent Publication No. 55-42380, etc., hydrazone compound, Japanese Patent Application Laid-Open No. 56-123544, etc., oxadiazole compound, Tetraarylbenzidine compounds disclosed in JP-A-54-58445, stilbene compounds disclosed in JP-A-58-65440 or JP-A-60-98437, and JP-A-11-513522. And the spiro-type compounds shown in 1. These may be used alone or in combination of two or more. Among these, spiro type compounds are preferable.

Examples of the spiro-type compound include compounds containing the following general formula (4).
However, in the general formula (4), R ₄ to R ₇ represent a substituted amino group such as a dimethylamino group, a diphenylamino group, and a naphthyl-4-tolylamino group.

The spiro compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include Exemplified Compounds D-1 to D-20 shown below, but are not limited thereto. .. These may be used alone or in combination of two or more.

In addition to having high hole mobility, these spiro-type compounds form a nearly spherical electron cloud because two benzidine skeleton molecules are twisted and bonded to each other, resulting in hopping conductivity between molecules. Shows good photoelectric conversion characteristics. Further, since it has a high solubility, it is soluble in various organic solvents, and since it is an amorphous substance (an amorphous substance having no crystal structure), it is likely to be densely packed in the porous electron transport layer. Further, since it does not have a light absorption property of 450 nm or more, the photosensitizing compound can efficiently absorb light, which is particularly preferable for the solid dye-sensitized solar cell.

The hole transport layer preferably contains an oxidizing agent in addition to the tertiary amine compound represented by the general formulas (1) and (2) and the hole transport material. When the hole transport layer contains an oxidant, the hole transport property is improved, and the durability and stability of output characteristics can be enhanced.

The oxidizing agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tris(4-bromophenyl)aminium hexachloroantimonate, hexafluoroantimonate silver, nitrosonium tetrafluoroborate, and silver nitrate. Examples thereof include metal complexes. These may be used alone or in combination of two or more. Among these, metal complexes are preferable. When the oxidizing agent is a metal complex, it is advantageous in that it has a high solubility and a residue hardly remains.

Examples of the metal complex include a structure composed of a metal cation, a ligand, and an anion.
Examples of the metal cations include cations of chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, tungsten, rhenium, osmium, iridium, gold, platinum and the like. Among these, cations of iron, cobalt, nickel and copper are preferable, and a cobalt complex is more preferable.
As the cobalt complex, a trivalent cobalt complex is preferable.

The ligand preferably contains at least one nitrogen-containing 5- and/or 6-membered heterocycle, and may have a substituent. Specific examples include, but are not limited to, the following.

Examples of the anion 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 ⁻ ), tetrafluoroboronate 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 ions ^{_{(N (SO 2 CF 3)}} 2-) tetra hydroxo aluminate ions _{([Al (OH) 4]} -, or [Al _{(OH) 4} (H ₂ O) ₂ ] ^- ), dicyanosilver (I) acid ion ([Ag(CN) ₂ ] ^- ), tetrahydroxochrome (III) acid ion ([Cr(OH) ₄ ] ^- ), tetrachlorogold. (III) ion ([AuCl _4] ^-), oxide ions ^{(O 2-),} sulfide ^{(S 2-),} peroxide ions ^{_(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) acid ion ([Zn(OH) ₄ ] ²⁻ ), tetracyanozinc(II) acid ion ([Zn(CN) ₄ ] ^2- ), tetrachlorocopper (II) acid ion ([CuCl ₄ ] ^{2 -} ), phosphate ion (PO ₄ ^{3 -} ), hexacia Bruno iron (III) ion ^{_{([Fe (CN) 6]}} 3-), bis (thiosulfate) silver (I) ion _{([Ag (S 2 O 3} ) 2] 3-), hexacyanoferrate (II) Ions ([Fe(CN) ₆ ] ⁴⁻ ) and the like can be mentioned. These may be used alone or in combination of two or more.
Among these, tetrafluoroborate ion, hexafluorophosphate ion, tetracyanoborate ion, bis(trifluoromethylsulfonyl)amine ion, and perchlorate ion are preferable.

As the metal complex, a trivalent cobalt complex represented by the following general formula (5) is particularly preferable. When the metal complex is a trivalent cobalt complex, it is advantageous in that the function as an oxidizing agent is excellent.

However, in the general formula (5), R _{8 to} R ₁₀ represent a hydrogen atom, a methyl group, an ethyl group, a tertiary butyl group, or a trifluoromethyl group. X represents any one selected from the above anions.

Specific examples of the cobalt complex represented by the general formula (5) will be described below. However, it is not limited to these. These may be used alone or in combination of two or more.

Further, as the metal complex, a trivalent cobalt complex represented by the following general formula (6) is also effectively used.

However, in said general formula (6), R< ₁₁ >-R< ₁₂ > shows a hydrogen atom, a methyl group, an ethyl group, a tertiary butyl group, or a trifluoromethyl group. X represents any one selected from the above anions.

Specific examples of the cobalt complex represented by the general formula (6) will be described below. However, it is not limited to these. These may be used alone or in combination of two or more.

The content of the oxidizing agent is preferably 0.5 parts by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the hole transport material. It is not necessary for all the hole transport materials to be oxidized by the addition of the oxidizing agent, and it is effective if only a part thereof is oxidized.

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 further the light irradiation resistance and the high temperature storage resistance can be improved.
Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like.
Examples of the lithium salt include lithium chloride, lithium bromide, lithium iodide, lithium perchlorate, lithium bis(trifluoromethanesulfonyl)diimide, lithium diisopropylimide, lithium acetate, lithium tetrafluoroborate and lithium pentafluorophosphate. , Lithium tetracyanoborate, and the like.
Examples of the sodium salt include sodium chloride, sodium bromide, sodium iodide, sodium perchlorate, sodium bis(trifluoromethanesulfonyl)diimide, sodium acetate, sodium tetrafluoroborate, sodium pentafluorophosphate, and tetracyanoboron. Sodium acid etc. are mentioned.
Examples of the potassium salt include potassium chloride, potassium bromide, potassium iodide, potassium perchlorate and the like.
Among these, a lithium salt is preferable, and lithium bis(trifluoromethanesulfonyl)diimide and lithium diisopropylimide are more preferable, because the durability and stability of the output characteristics can be improved by improving the conductivity.

The content of the alkali metal salt is preferably 1 part by mass or more and 50 parts by mass or less, and more preferably 15 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the hole transport material.

The hole transport layer may have a single-layer structure made of a single material or 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 close to the second electrode. The use of a polymer 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, when the polymer material is difficult to penetrate into the porous electron transport layer, it has excellent coverage of the surface of the porous electron transport layer and can also be effective in preventing a short circuit when an electrode is provided. There is.

Examples of the polymer material used for the hole transport layer include known hole transporting polymer materials.
Examples of the hole transporting polymer material include polythiophene compounds, polyphenylene vinylene compounds, polyfluorene compounds, polyphenylene compounds, polyarylamine compounds, polythiadiazole compounds, and the like.
Examples of the polythiophene compound include poly(3-n-hexylthiophene), poly(3-n-octyloxythiophene), poly(9,9′-dioctyl-fluorene-co-bithiophene), and 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 the polyphenylene vinylene compound include poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1. , 4-phenylene vinylene], poly[(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene)-co-(4,4′-biphenylene-vinylene)] and the like. ..
Examples of the polyfluorene compound include poly(9,9′-didodecylfluorenyl-2,7-diyl) and 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 the polyphenylene compound include poly[2,5-dioctyloxy-1,4-phenylene] and poly[2,5-di(2-ethylhexyloxy-1,4-phenylene].
Examples of the polyarylamine compound include poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(N,N'-diphenyl)-N,N'-di(p- Hexylphenyl)-1,4-diaminobenzene], poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(N,N'-bis(4-octyloxyphenyl)benzidine] -N,N'-(1,4-diphenylene)], poly[(N,N'-bis(4-octyloxyphenyl)benzidine-N,N'-(1,4-diphenylene)], poly[( N,N'-bis(4-(2-ethylhexyloxy)phenyl)benzidine-N,N'-(1,4-diphenylene)], poly[phenylimino-1,4-phenylenevinylene-2,5-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 the polythiadiazole compound 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 can be mentioned.
Among these, polythiophene compounds and polyarylamine compounds are preferable from the viewpoint of carrier mobility and ionization potential.

The average thickness of the hole transport layer is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferable that the hole transport layer has a structure in which it penetrates into the pores of the porous electron transport layer. It is preferably 0.01 μm or more and 20 μm or less, more preferably 0.1 μm or more and 10 μm or less, still more preferably 0.2 μm or more and 2 μm or less.

The hole transport layer can be directly formed on the electron transport layer on which the photosensitizing compound is adsorbed. The method for producing the hole transport layer is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a method of forming a thin film in a vacuum such as vacuum deposition and a wet film forming method. Among these, the wet film-forming method is particularly preferable from the viewpoint of production cost, and the method of coating on the electron transport layer is preferable.
When the wet film forming method is used, the coating method is not particularly limited and can be performed according to a known method, for example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade. As the coating method, the gravure coating method, and the wet printing method, various methods such as letterpress, offset, gravure, intaglio, rubber plate, and screen printing can be used.

The film may be formed in a supercritical fluid or a subcritical fluid having a temperature and pressure lower than the critical point. Supercritical fluid exists as a non-aggregating high-density fluid in a temperature and pressure range that exceeds the limit (critical point) where gas and liquid can coexist, does not aggregate even when compressed, and is above the critical temperature and above the critical pressure. There is no particular limitation as long as it is a fluid in the above state, and it can be appropriately selected according to the purpose, but one having a low critical temperature is preferable.

Examples of the supercritical fluid include carbon monoxide, carbon dioxide, ammonia, nitrogen, water, alcohol solvents, hydrocarbon solvents, halogen solvents, ether solvents and the like.
Examples of the alcohol solvent include methanol, ethanol, n-butanol and the like.
Examples of the hydrocarbon solvent include ethane, propane, 2,3-dimethylbutane, benzene, toluene and the like. Examples of the halogen solvent include methylene chloride, chlorotrifluoromethane and the like.
Examples of the ether solvent include dimethyl ether and the like.
These may be used alone or in combination of two or more.
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 it can easily create a supercritical state, is nonflammable, and is 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 region near the critical point, and can be appropriately selected depending on the purpose. The compound mentioned as a supercritical fluid can be suitably used also as a subcritical fluid.

The critical temperature and the critical pressure of the supercritical fluid are not particularly limited and may be appropriately selected depending on the purpose, but the critical temperature is preferably -273°C or higher and 300°C or lower, and 0°C or higher and 200°C or lower. More preferable.

Further, in addition to the supercritical fluid and subcritical fluid, an organic solvent or an entrainer can be used together. By adding the organic solvent and the entrainer, the solubility in the supercritical fluid can be adjusted more easily.
The organic solvent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a ketone solvent, an ester solvent, an ether solvent, an amide solvent, a halogenated hydrocarbon solvent, and a hydrocarbon solvent.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
Examples of the ester solvent include ethyl formate, ethyl acetate, n-butyl acetate and the like.
Examples of the ether solvent include diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, dioxane and the like.
Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.
Examples of the halogenated hydrocarbon solvent include dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, 1-chloronaphthalene and the like. ..
Examples of the hydrocarbon solvent include n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, Examples include ethylbenzene and cumene.
These may be used alone or in combination of two or more.

In addition, after stacking the hole transport material on the electron transport layer on which the photosensitizing compound is adsorbed, a press treatment step may be performed. By performing the press treatment, the hole transport material is brought into closer contact with the electron transport layer, which is a porous electrode, so that efficiency may be improved in some cases.
The method of press treatment is not particularly limited and may be appropriately selected depending on the intended purpose. A press molding method using a flat plate typified by an IR tablet molding machine, a roll pressing method using a roller, etc. Can be mentioned.
The pressure is preferably 10 kgf/cm ² or more, more preferably 30 kgf/cm ² or more.
The pressing time is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 hour or less. Further, heat may be applied during the press treatment. During the press treatment, a release agent may be sandwiched between the press and the electrode.

Examples of the releasing agent include polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene hexafluoropropylene copolymer, perfluoroalkoxy fluororesin, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer. , Ethylene chlorotrifluoride ethylene copolymer, fluororesin such as polyvinyl fluoride, and the like. These may be used alone or in combination of two or more.

A metal oxide may be provided between the hole transport material and the second electrode after the press treatment step and before the second electrode is provided.
Examples of the metal oxide include molybdenum oxide, tungsten oxide, vanadium oxide, nickel oxide and the like. These may be used alone or in combination of two or more. Of these, molybdenum oxide is preferable.
The method for providing the metal oxide on the hole transport layer is not particularly limited and may be appropriately selected depending on the purpose, such as a method for forming a thin film in a vacuum such as sputtering or vacuum deposition, or a wet film forming method. Are listed.

As the wet film forming method, a method of preparing a paste in which a metal oxide powder or a sol is dispersed and coating the paste on the hole transport layer is preferable. The coating method when the wet film forming method is used is not particularly limited and can be performed according to a known method, for example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade. As the coating method, the gravure coating method, and the wet printing method, various methods such as letterpress, offset, gravure, intaglio, rubber plate, and screen printing can be used.
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>
The photoelectric conversion element has a second electrode.
The second electrode can be formed on the hole transport layer or on the metal oxide in the hole transport layer. The second electrode may be the same as the first electrode, and a support is not always necessary if the strength is sufficiently maintained.
Examples of the material of the second electrode include metals, carbon compounds, conductive metal oxides, conductive polymers, and the like.
Examples of the metal include platinum, gold, silver, copper, aluminum and the like.
Examples of the carbon compound include graphite, fullerene, carbon nanotube, graphene, and the like.
Examples of the conductive metal oxide include ITO, FTO, ATO and the like.
Examples of the conductive polymer include polythiophene and polyaniline.
These may be used alone or in combination of two or more.

The second electrode can be formed by a method such as coating, laminating, vapor deposition, CVD, or laminating on the hole transport layer, depending on the type of material used and the type of hole transport layer.
In the photoelectric conversion element, it is preferable that at least one of the first electrode and the second electrode is substantially transparent. A method is preferable in which the first electrode side is transparent and incident light is incident from the first electrode side. In this case, it is preferable to use a material that reflects light on the side of the second electrode, and metal, glass on which a conductive oxide is deposited, plastic, or a metal thin film is preferably used. Further, providing an antireflection layer on the incident light side is also an effective means.

<Sealing member>
The photoelectric conversion element has a sealing member containing an epoxy resin.
The sealing member shields at least the electron transport layer, the hole transport layer, and the second electrode from the external environment of the photoelectric conversion element.

An epoxy resin is used as the sealing member, and the hole transport layer further contains at least one of the tertiary amine compounds represented by the general formula (1) and the general formula (2), so that the photoelectric conversion element is provided in a high temperature and high humidity environment. Even when stored below, high output before storage can be maintained. Further, high output can be maintained even when light with low illuminance is continuously irradiated after being stored in a high temperature and high humidity environment.

The epoxy resin is not particularly limited as long as it is a resin in which a monomer or an oligomer having an epoxy group in the molecule is cured, and can be appropriately selected according to the purpose, for example, water dispersion type, solventless type. , Solid type, thermosetting type, curing agent mixed type, ultraviolet curing type and the like. Among these, the thermosetting type and the ultraviolet curing type are preferable, and the ultraviolet curing type is more preferable. It should be noted that it may be UV curable or heated.
Examples of the epoxy resin include bisphenol A type, bisphenol F type, novolac type, cycloaliphatic type, long chain aliphatic type, glycidyl amine type, glycidyl ether type, and glycidyl ester type. These may be used alone or in combination of two or more.

The epoxy resin may contain a curing agent and various additives as needed.
Examples of the curing agent include amine-based, acid anhydride-based, polyamide-based, and other curing agents.
Examples of the amine-based curing agent include aliphatic polyamines such as diethylenetriamine and triethylenetetramine, aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
Examples of the acid anhydride-based curing agent include phthalic anhydride, tetra- and hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, pyromellitic dianhydride, hettic anhydride, dodecenyl succinic anhydride and the like. ..
Examples of other curing agents include imidazoles and polymercaptans. These may be used alone or in combination of two or more.

Examples of additives include fillers (fillers), gap agents, polymerization initiators, desiccants (hygroscopic agents), curing accelerators, coupling agents, flexible agents, colorants, flame retardant aids, and antioxidants. Agents, organic solvents and the like. These may be used alone or in combination of two or more. Among these, a filler, a gap agent, a curing accelerator, a polymerization initiator and a drying agent (hygroscopic agent) are preferable, and a filler and a polymerization initiator are particularly preferable.

As a filler, it is effective in suppressing the ingress of moisture and oxygen in the external environment, and also reduces volume shrinkage during curing, reduces the amount of gas generated during curing or heating, and improves mechanical strength. It is possible to obtain effects such as control of thermal conductivity and fluidity, and it is very effective in the present invention as well to maintain stable output in various environments.
Regarding the output characteristics and durability of the photoelectric conversion element, not only the influence of moisture and oxygen invading the inside of the photoelectric conversion element from the external environment but also the influence of the gas generated during curing and heating of the sealing member can be ignored. Can not. In particular, the influence of the gas generated during heating has a great influence on the output characteristics when stored in a high temperature environment.
In this case, by containing a filler, a gap agent, and a desiccant in the sealing member, they can suppress ingress of water and oxygen by themselves, and the amount of the sealing member used can be reduced, thereby reducing gas generation. The effect can be obtained. This is effective not only when 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, crystalline or amorphous silica, talc, alumina, aluminum nitride, silicon nitride, calcium silicate, calcium carbonate, and other inorganic materials. Fillers are preferably used. These may be used alone or in combination of two or more.

The average primary particle size of the filler is preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less. When the average primary particle diameter of the filler is 0.1 μm or more and 10 μm or less, the effect of suppressing the penetration of moisture and oxygen can be sufficiently obtained, the viscosity becomes appropriate, the adhesion to the substrate and the defoaming property It is also effective for improving the workability, controlling the width of the sealing portion, and workability.

The content of the filler is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 20 parts by mass or more and 70 parts by mass or less with respect to the total amount of the sealing member. When the content of the filler is 10 parts by mass or more and 90 parts by mass or less, the effect of suppressing the penetration of water and oxygen is sufficiently obtained, the viscosity becomes appropriate, and the adhesion and workability also become good.

The gap agent is also referred to as a gap control agent or a spacer agent, and can 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, a gap agent is mixed with the epoxy resin. Thereby, the gap of the sealing portion is made uniform with the size of the gap agent, so that the gap of the sealing portion can be easily controlled.

As the gap agent, a known material can be used as long as it has a granular shape, a uniform particle diameter, and high solvent resistance and heat resistance. A resin having a high affinity with the epoxy resin and a spherical particle shape is preferable. Specific examples thereof include glass beads, silica fine particles, organic resin fine particles, and the like. These may be used alone or in combination of two or more.

The particle size 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.

The polymerization initiator is a material added for the purpose of initiating polymerization using heat or light.
The thermal polymerization initiator is a compound that generates active species such as radicals and cations by heating, and specifically, an azo compound such as 2,2′-azobisbutyronitrile (AIBN) and benzoyl peroxide (BPO). ) Etc. are used.
As the thermal cationic polymerization initiator, benzenesulfonic acid ester, alkylsulfonium salt, etc. are used.

On the other hand, as the photopolymerization initiator, in the case of an epoxy resin, a photocationic polymerization initiator is preferably used. 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, and the acid causes the epoxy resin to polymerize, and the curing reaction proceeds. The cationic photopolymerization initiator has effects such as a small volume shrinkage during curing, no oxygen inhibition, and high storage stability.

Examples of the cationic photopolymerization initiator include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, metacelone compounds, silanol-aluminum complexes and the like. Further, a photo-acid generator having a function of generating an acid when irradiated with light can also be used.
The photo-acid generator acts as an acid that initiates cationic polymerization, and examples thereof include ionic sulfonium salt-based or iodonium salt-based onium salts composed of a cation portion and an anion portion. These may be used alone or in combination of two or more.

The content of the polymerization initiator is preferably 0.5 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less, based on the total amount of the sealing member. When the content of the polymerization initiator is 0.5 parts by mass or more and 10 parts by mass or less, the curing proceeds properly, the remaining uncured product can be reduced, and the generation amount of gas is prevented from becoming excessive. You can and are effective.

The desiccant is also referred to as a hygroscopic agent, and is a material having a function of physically or chemically adsorbing and absorbing moisture, and by containing it in the sealing member, the moisture resistance is further enhanced or the influence of the outgas is exerted. Is effective because it can be reduced in some cases.
The desiccant is preferably in the form of particles, 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 sieve, and zeolite. Among these, zeolite having a large amount of moisture absorption is preferable. These may be used alone or in combination of two or more.

The curing accelerator is also called a curing catalyst, is used for the purpose of increasing the curing speed, and is mainly used for thermosetting epoxy resins.
Examples of the curing accelerator include three types of compounds such as 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, imidazole compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole, phosphines such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate. Alternatively, phosphonium salts and the like can be mentioned. These may be used alone or in combination of two or more.

The coupling agent has an effect of increasing the molecular bonding force, and examples thereof include a silane coupling agent, and examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 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 of the silane coupling agent include aminopropyltrimethoxysilane hydrochloride and 3-methacryloxypropyltrimethoxysilane. These may be used alone or in combination of two or more.

As the sealing member, an epoxy resin composition which is commercially available as a sealing material, a sealing material or an adhesive is known and can be effectively used in the present invention. Among them, there are epoxy resin compositions that have been developed and marketed for use in solar cells and organic EL devices, and can be used particularly effectively in the present invention.
Examples of the commercially available products include trade names: TB3118, TB3114, TB3124, TB3125F (above, manufactured by ThreeBond), WorldRock5910, WorldRock5920, WorldRock8723 (above, manufactured by Kyoritsu Chemical Industry Co., Ltd.), WB90US(P) (above, Moresco) and the like.
Further, the epoxy resin composition is disclosed in, for example, Japanese Patent No. 4918975, Japanese Patent No. 5812275, Japanese Patent No. 5835664, Japanese Patent No. 5930248, and Japanese Patent Laid-Open No. 2012-136614, and these are also used. can do.
Further, in the present invention, a sheet-shaped sealing material can also be effectively used.
The sheet-shaped sealing material is a sheet on which an epoxy resin layer is formed in advance, and the sheet is made of glass or a film having a high gas barrier property, and corresponds to the substrate in the present invention. The sheet-shaped sealing material is attached onto the photoelectric conversion element or the second electrode of the photoelectric conversion element module and then cured, whereby the sealing member and the substrate can be formed at one time. The structure in which the void portion is provided inside the photoelectric conversion element can be effectively obtained by the formation pattern of the epoxy resin layer formed on the sheet.

The position of the sealing member is not particularly limited as long as it is arranged at a position that shields at least the electron transport layer, the hole transport layer, and the second electrode from the external environment of the photoelectric conversion element, and is appropriately selected depending on the purpose. It may be selected, and for example, it may be provided on the entire surface so as to cover the electron transport layer, the hole transport layer, and the second electrode, or a substrate may be arranged above the second electrode to form a sealing member. May be provided on the outer edge of the substrate and bonded to at least one of the first substrate, the first electrode and the hole blocking layer.
As in the latter case, in the configuration in which the substrate is arranged and the sealing member is provided on the outer edge thereof, the void portion can be provided inside the photoelectric conversion element or the photoelectric conversion element module. The void portion can control oxygen and humidity, and is effective in improving output and durability.

In the present invention, it is preferable that the voids contain oxygen. By containing oxygen, the hole transport function of the hole transport layer can be stably maintained for a long period of time, and the durability of the photoelectric conversion element or the photoelectric conversion element module can be improved. In the present invention, the oxygen concentration of the void portion inside the photoelectric conversion element provided by sealing is effective if oxygen is contained, but is 1.0 vol% or more and 21.0 vol% or less. It is preferably 3.0% by volume or more and 15.0% by volume or less.

The oxygen concentration in the void can be controlled by sealing in a glove box in which the oxygen concentration is set. The oxygen concentration can be set by a method using a gas cylinder having a specific oxygen concentration or a method using a nitrogen gas generator. The oxygen concentration in the glove box is measured using a commercially available oxygen concentration meter or oxygen monitor.

The oxygen concentration in the void formed by sealing can be measured by, for example, an atmospheric pressure ionization mass spectrometer (API-MS). Specifically, the photoelectric conversion element or the photoelectric conversion element module is installed in a chamber filled with an inert gas, the seal is opened in the chamber, and the gas in the chamber is quantitatively analyzed by API-MS. The oxygen concentration can be obtained by quantifying all the components in the gas contained in the void and calculating the ratio of oxygen to the total amount.
As the gas other than oxygen, an inert gas is preferable, and examples thereof include nitrogen and argon.

At the time of sealing, it is preferable to control the dew point as well as the oxygen concentration in the glove box, which is effective in improving the output and durability thereof.
The dew point is defined as the temperature at which condensation starts when a gas containing water vapor is cooled. The dew point is preferably 0°C or lower, more preferably -20°C or lower. The lower limit is preferably −50° C. or higher.

Further, a passivation layer may be provided between the second electrode and the sealing member. The passivation layer is not particularly limited and may be appropriately selected depending on the purpose. For example, aluminum oxide, silicon nitride, silicon oxide, etc. are preferable.

The method for forming the sealing member is not particularly limited and may be appropriately selected depending on the purpose, for example, a dispensing method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, Examples include letterpress, offset, intaglio, rubber plate, screen printing and the like.

<Substrate>
The photoelectric conversion element and the photoelectric conversion element module of the present invention may have a substrate, and are effective in improving mechanical strength and preventing intrusion of oxygen and moisture. The substrate may be provided on either or both of the outermost portion on the first electrode side and the outermost portion on the second electrode side of the photoelectric conversion element and the photoelectric conversion element module.
Hereinafter, the outermost substrate on the first electrode side is referred to as a first substrate, and the outermost substrate on the second electrode side is referred to as a second substrate.

<<First substrate>>
The photoelectric conversion element may have a first substrate.
The shape, structure, and size of the first substrate are not particularly limited and can be appropriately selected depending on the purpose.
The material of the first substrate is not particularly limited as long as it has a light-transmitting property and an insulating property, and can be appropriately selected according to the purpose. Examples thereof include substrates such as glass, plastic film, and ceramics. To be Among these, a substrate having heat resistance to the firing temperature is preferable when it includes a step of firing when forming the electron transport layer as described later. Further, the first substrate is preferably one having flexibility.

<<Second substrate>>
The photoelectric conversion element may have a second substrate.
The second substrate is not particularly limited, and known substrates can be used, and examples thereof include substrates made of glass, plastic film, ceramics, and the like. An uneven portion may be formed at the joint between the second substrate and the sealing member in order to improve the adhesion.
The method for forming the uneven portion is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a sandblast method, a waterblast method, abrasive paper, a chemical etching method, and a laser processing method.
As a means for improving the adhesion between the second substrate and the sealing member, for example, the organic matter on the surface may be removed or the hydrophilicity may be improved. The means for removing the organic substance on the surface of the second substrate is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include UV ozone cleaning and oxygen plasma treatment.

[Embodiment]
Hereinafter, an example of 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.

FIG. 1 is a schematic diagram showing an example of the photoelectric conversion element of the present invention.
As shown in FIG. 1, in the photoelectric conversion element 101, the first electrode 2 is formed on the first substrate 1, and the hole blocking layer 3 is formed on the first electrode 2. The electron transport layer 4 is formed on the hole blocking layer 3, and the photosensitizing compound 5 is adsorbed on the surface of the electron transport material forming the electron transport 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 to the hole blocking layer 3 by a sealing member 8. By forming the hole blocking layer 3, recombination of electrons and holes can be prevented, so that power generation performance can be improved.
The photoelectric conversion element shown in FIG. 1 can have a void 10 between the second electrode 7 and the second substrate 9. By having the voids, the oxygen concentration in the voids can be controlled, so that power generation performance and durability can be improved. Moreover, since the second electrode 7 and the second substrate 9 do not come into direct contact with each other, it is possible to prevent the second electrode 7 from peeling or breaking.

The oxygen concentration in the void is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1.0 vol% or more and 21.0 vol% or less, and 3.0 vol% or more and 15.0 vol. % Or less is more preferable.
Although not shown, each of the first electrode 2 and the second electrode 7 may have a path that conducts to an electrode lead terminal.

FIG. 2 is a schematic view showing another example of the photoelectric conversion element of the present invention, showing a case where the void portion is not provided and the void portion of FIG. 2 is covered with the sealing member 8.
The method for producing a photoelectric conversion element having no voids is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the sealing member 8 is applied to the entire surface of the second electrode 7, The method of providing the 2nd board|substrate 9 on it, the method of using the sheet-shaped sealing material mentioned above, etc. are mentioned.
The void inside the seal may be completely eliminated, or a part of the void may be left as shown in FIG. By covering almost the entire surface with the sealing member, it is possible to reduce peeling or breakage of the second substrate 9 when stress is applied to the photoelectric conversion element due to twisting, dropping, or the like, and the photoelectric conversion element machine can be manufactured. Strength can be increased. As a modification of FIG. 2, the second substrate may not be provided as shown in FIG.

FIG. 5 is a schematic view showing another example of the photoelectric conversion element of the present invention, and shows a case where the sealing member 8 is bonded to the first substrate 1 and the second substrate 9. With such a structure, the adhesiveness of the sealing member 8 to the substrate is enhanced, and the mechanical strength of the photoelectric conversion element is enhanced. In addition, the increased adhesiveness has the effect of further increasing the sealing effect for preventing excessive infiltration of water and oxygen.

(Photoelectric conversion element module)
The photoelectric conversion element module of the present invention has 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 the first electrodes. A hole blocking layer, an electron transport layer having a photosensitizing compound, a hole transport layer, and a second electrode, and at least the electron transport layer, the hole transport layer, and the second electrode. It has a sealing member containing an epoxy resin that shields from the external environment of the photoelectric conversion element module, and the hole transport layer is at least a tertiary amine compound represented by the following general formula (1) and general formula (2). Either, and optionally other layers. Each layer may have a single-layer structure or a laminated structure.

However, the general formula (1), and in the general formula (2), Ar ₁ and Ar ₂ have substituents represent also aryl groups, wherein Ar ₁ and the Ar ₂ are also the same They may be different or may be bonded to each other.

Further, the photoelectric conversion element module of the present invention can be configured to have a plurality of the photoelectric conversion elements.
The structure of each layer of the photoelectric conversion element module may be the same as that of the photoelectric conversion element.

The photoelectric conversion element module may be in the form of a continuous layer in which at least the hole transport layers of at least two of the photoelectric conversion elements adjacent to each other are extended from each other.
Further, in the photoelectric conversion element module, in at least two photoelectric conversion elements adjacent to each other, at least the first electrode of the photoelectric conversion element and the second electrode of the other photoelectric conversion element are at least It may be in a form of being electrically connected by a conductive portion penetrating from the hole transport layer to the hole blocking layer.

The photoelectric conversion element module has a pair of substrates, and has 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. It can be configured.

[Embodiment]
Hereinafter, an example of the photoelectric conversion element module 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.

FIG. 6 is a schematic diagram showing an example of the photoelectric conversion element module of the present invention, which is an example showing a part of a cross section of a photoelectric conversion element module including a plurality of photoelectric conversion elements and connected in series. ..
In FIG. 6, after the hole transport layer 6 is formed, the penetrating part 11 is formed, and then the second electrode 7 is formed, so that the second electrode material is introduced into the penetrating part 11 to be adjacent to it. It can be electrically connected to the first electrode 2b of the cell. Although not shown in FIG. 6, the first electrode 2a and the second electrode 7b have a path that conducts to an electrode of an adjacent cell or an output extraction terminal.

The penetrating portion 11 may penetrate the first electrode 2 and reach the first substrate 1, or may stop processing inside the first electrode 2 and reach the first substrate 1. Good.
When the shape of the penetrating portion 11 is a fine hole that penetrates the first electrode 2 and reaches the first substrate 1, if the total opening area of the fine holes becomes too large with respect to the area of the penetrating portion 11, When the film cross-sectional area of the electrode 2 of No. 1 decreases, the resistance value increases, which may cause a decrease in photoelectric conversion efficiency. Therefore, the ratio of the total opening area of the fine holes to the area of the penetrating portion 11 is preferably 5/100 or more and 60/100 or less.

The method of forming the through portion 11 is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a sandblast method, a waterblast method, abrasive paper, a chemical etching method, and a laser processing method. Among these, the laser processing method is preferable. As a result, fine holes can be formed without using sand, etching, resist or the like, and can be processed cleanly and with good reproducibility. Further, when forming the penetrating portion 11, at least one of the hole blocking layer 3, the electron transport layer 4, the hole transport layer 6, and the second electrode 7 can be removed by impact peeling by a laser processing method. Become. Thereby, it is not necessary to provide a mask at the time of stacking, and the removal and the formation of the fine penetrating portion 11 can be easily performed at once.

FIG. 7 is a schematic diagram showing an example of the photoelectric conversion element module of the present invention, which includes a plurality of photoelectric conversion elements, which are connected in series, and the sealing member 12 is provided in a space between cells like a beam. It is an example showing a section of a part of the provided photoelectric conversion element module.
When a space is provided between the second electrode 7 and the second substrate 9 as shown in FIG. 2, peeling and destruction of the second electrode 7 can be prevented, but the mechanical strength of sealing is reduced. There is a case. On the other hand, as shown in FIG. 3, when the space between the second electrode 7 and the second substrate 9 is filled with a sealing member, the mechanical strength of sealing increases, but the second electrode 7 peels off. I have a concern. Here, in order to increase the power generation, it is effective to increase the area of the photoelectric conversion element module. However, when the photoelectric conversion element module has a void, a decrease in mechanical strength cannot be avoided.
Therefore, by providing the sealing member 12 like a beam as shown in FIG. 7, it is possible to prevent the second electrode 7 from peeling or breaking and to increase the mechanical strength of the sealing, which is effective. is there.
The sealing member 12 may be the same material as the sealing member 8 or may be a different material.

(Electronics)
An electronic device of the present invention includes a photoelectric conversion element and/or a photoelectric conversion element module of the present invention, and a device that operates by electric power generated by the photoelectric conversion element and/or the photoelectric conversion element module performing photoelectric conversion. In addition, it has other devices as required.

(Power supply module)
The power supply module of the present invention has the photoelectric conversion element and/or the photoelectric conversion element module of the present invention, and a power supply IC, and further has other devices as necessary.

Specific embodiments of a photoelectric conversion element, a photoelectric conversion element module of the present invention, and an electronic device including a device that operates by electric power obtained by power generation of the photoelectric conversion element will be described.
FIG. 8 shows an example in which a mouse is used as the electronic device.
As shown in FIG. 8, a photoelectric conversion element, a photoelectric conversion element module, a power supply IC, and a power storage device are combined, and the supplied power is connected to the power supply of the mouse control circuit. As a result, the electricity storage device can be charged when the mouse is not in use, and the mouse can be operated by the power, and a mouse that does not require wiring or battery replacement can be obtained. Further, since the battery is unnecessary, the weight can be reduced, which is effective.
FIG. 9 shows a schematic diagram in which the mouse is mounted with the photoelectric conversion element. The photoelectric conversion element, the power supply IC, and the electricity storage device are mounted inside the mouse, and the upper part of the photoelectric conversion element is covered with a transparent casing so that the photoelectric conversion element is exposed to light. It is also possible to mold the entire mouse housing with transparent resin. The arrangement of the photoelectric conversion element is not limited to this. For example, even if the mouse is covered with the hand, it may be arranged at a position where light is emitted, which is preferable in some cases.

Other embodiments of the electronic device including the photoelectric conversion element, the photoelectric conversion element module of the present invention, and a device that operates by the electric power obtained by power generation by the photoelectric conversion element module will be described.
FIG. 10 shows an example in which a keyboard used in a personal computer is used as the electronic device.
As shown in FIG. 10, a photoelectric conversion element, 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 keyboard. As a result, when the keyboard is not used, the power storage device can be charged and the keyboard can be operated by the power, and a keyboard that does not require wiring or battery replacement can be obtained. Further, since the battery is unnecessary, the weight can be reduced, which is effective.
FIG. 11 shows a schematic diagram in which the photoelectric conversion element is mounted on the keyboard. The photoelectric conversion element, the power supply IC, and the electricity storage device are mounted inside the keyboard, but the upper part of the photoelectric conversion element is covered with a transparent casing so that the photoelectric conversion element is exposed to light. It is also possible to mold the entire keyboard casing with transparent resin. The arrangement of the photoelectric conversion elements is not limited to this.
In the case of a small keyboard in which the space for incorporating the photoelectric conversion element is small, as shown in FIG. 12, it is possible and effective to embed the small photoelectric conversion element in a part of the key.

Other embodiments of the electronic device including the photoelectric conversion element, the photoelectric conversion element module of the present invention, and a device that operates by the electric power obtained by power generation by the photoelectric conversion element module will be described.
FIG. 13 shows an example in which a sensor is used as the electronic device.
As shown in FIG. 13, a photoelectric conversion element, a power supply IC, and a power storage device are combined, and the supplied power is connected to the power supply of the sensor circuit. As a result, the sensor module can be configured without the need to connect to an external power source and the need to replace the battery. The sensing target is effective because it can be applied to various sensors such as temperature and humidity, illuminance, human presence, CO ₂ , acceleration, UV, noise, geomagnetism, and atmospheric pressure. As shown by A in FIG. 13, the sensor module is configured to periodically sense a measurement target and transmit the read data to a PC, a smartphone or the like by wireless communication.
With the advent of the IoT society, the number of sensors is expected to increase rapidly. Replacing the batteries of this myriad of sensors one by one takes a lot of time and is not realistic. In addition, the sensor is located in a place where it is difficult to replace the battery, such as a ceiling or a wall, which deteriorates workability. The fact that power can be supplied by a photoelectric conversion element is also a great advantage. Further, the photoelectric conversion element of the present invention can obtain a high output even under a low illuminance and has a small dependency on the light incident angle of the output, so that it has an advantage that the installation flexibility is high.

Other embodiments of the electronic device including the photoelectric conversion element, the photoelectric conversion element module of the present invention, and a device that operates by the electric power obtained by power generation by the photoelectric conversion element module will be described.
FIG. 14 shows an example in which a turntable is used as the electronic device.
As shown in FIG. 14, a photoelectric conversion element, a power supply IC, and a power 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 the need for connecting to an external power source and the need for battery replacement.
The turntable is used, for example, in a showcase for displaying products, but the wiring of the power source looks unattractive, and the displayed article must be removed when the battery is replaced, which is a great deal of work. By using the photoelectric conversion element of the present invention, such a problem can be solved, which is effective.

<Use>
As described above, the photoelectric conversion element and the photoelectric conversion element module of the present invention, and the electronic device and the power supply module having the device that operates by the electric power obtained by generating the electric power, and the power supply module have been described, but these are only a part. The photoelectric conversion element or photoelectric conversion element module of the present invention is not limited to these applications.

The photoelectric conversion element and the photoelectric conversion element module can be applied to, for example, a power supply device by being combined with a circuit board that controls the generated current.
Examples of devices using the power supply device include an electronic desk calculator, a wristwatch, a mobile phone, an electronic notebook, and an electronic paper.
Further, a power supply device having a photoelectric conversion element can be used as an auxiliary power supply for prolonging the continuous use time of a rechargeable or dry battery type electric appliance.

The photoelectric conversion element and the photoelectric conversion element module of the present invention can function as a self-supporting power source, and the device can be operated using electric power generated by photoelectric conversion. Since the photoelectric conversion element and the photoelectric conversion element module of the present invention can generate power by being irradiated with light, there is no need to connect an electronic device to a power source or replace a battery. Therefore, it is possible to operate the electronic device even in a place where there is no power supply facility, carry it around while wearing it, or operate the electronic device in a place where battery replacement is difficult without replacing the battery. Further, when a dry battery is used, the electronic device becomes heavier or larger in size to that extent, which may hinder installation on a wall or ceiling or carry, but the photoelectric conversion element of the present invention Since the photoelectric conversion element module is light and thin, it has a high degree of freedom in installation, and has great merit in wearing and carrying.
As described above, the photoelectric conversion element and the photoelectric conversion element module of the present invention can be used as a self-standing power source and can be combined with various electronic devices. For example, display devices such as electronic desk calculators, wrist watches, mobile phones, electronic organizers, electronic paper, computer accessories such as mice and keyboards, various sensor devices such as temperature/humidity sensors and motion sensors, beacons, GPS, etc. It can be used in combination with many electronic devices such as machines, auxiliary lights, and remote controls.

Since the photoelectric conversion element and the photoelectric conversion element module of the present invention can generate power even with light of low illuminance, it can generate power even in a room or in a dim shadow, and thus has a wide application range. In addition, unlike a dry battery, there is no liquid leakage, and unlike a button battery, it is not accidentally ingested and is highly safe. Furthermore, it can be used as an auxiliary power source for prolonging the continuous use time of rechargeable or dry battery type electric appliances. Thus, by combining the photoelectric conversion element of the present invention, and the photoelectric conversion element module, and a device that operates by the power generated by the photoelectric conversion, it is lightweight and easy to use, and has a high degree of freedom in installation, It can be transformed into an electronic device that does not require replacement, is highly safe, and is effective in reducing environmental impact.

FIG. 15 shows a basic configuration diagram of an electronic device in which a photoelectric conversion element and/or a photoelectric conversion element module of the present invention and a device which operates by electric power generated by photoelectric conversion by the photoelectric conversion element are combined. When the photoelectric conversion element is irradiated with light, the power is generated and the electric power can be taken out. The circuit of the device can be operated by the electric power.

However, since the output of the photoelectric conversion element changes depending on the ambient illuminance, the electronic device shown in FIG. 15 may not be able to operate stably. In this case, as shown in FIG. 16, in order to supply a stable voltage to the circuit side, it is possible and effective to incorporate a power supply IC for the photoelectric conversion element between the photoelectric conversion element and the circuit of the device. ..
However, the photoelectric conversion element can generate electricity if it is irradiated with light having sufficient illuminance, but if the illuminance for generating electricity is insufficient, desired electric power cannot be obtained, which is also a drawback of the photoelectric conversion element. In this case, as shown in FIG. 17, 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. Even when is too low, or when the photoelectric conversion element is not exposed to light, the electric power stored in the power storage device can be supplied to the device circuit, and stable operation can be achieved.
As described above, in the electronic device in which the photoelectric conversion element and/or the photoelectric conversion element module of the present invention and the device circuit are combined, by combining the power supply IC and the power storage device, it is possible to operate in an environment without a power supply. It is not necessary to replace the battery, it can be driven stably, and the advantages of the photoelectric conversion element can be maximized.

On the other hand, the photoelectric conversion element and/or the photoelectric conversion element module of the present invention can be used as a power supply module and is useful. For example, as shown in FIG. 18, when the photoelectric conversion element and/or the photoelectric conversion element module of the present invention and the power supply IC for the photoelectric conversion element are connected, the power generated by the photoelectric conversion of the photoelectric conversion element is supplied to the power supply IC. It is possible to configure a DC power supply module capable of supplying a constant voltage level.
Further, as shown in FIG. 19, by adding an electricity storage device to the power supply IC, it becomes possible to charge the electricity storage device with the electric power generated by the photoelectric conversion element, and when the illuminance is too low, or when the photoelectric conversion element is used. It is possible to configure a power supply module capable of supplying electric power even in a state where no light is applied to the power supply module.
The power supply module of the present invention shown in FIG. 18 and FIG. 19 can be used as a power supply module without changing the battery unlike the conventional primary battery.

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>
First, on an ITO coated glass in which an ITO conductive film as a first electrode is sputtered on a glass substrate as a first substrate, a dense layer of titanium oxide is formed as a hole blocking layer by reactive sputtering with oxygen gas. Layers were formed.
Next, 3 g of titanium oxide (trade name: P90, manufactured by Nippon Aerosil Co., Ltd.), 0.2 g of acetylacetone, and 0.3 g of polyoxyethylene octyl phenyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) as a surfactant, A bead mill treatment was carried out for 12 hours with 5.5 g of water and 1.0 g of ethanol to prepare a titanium oxide dispersion liquid. 1.2 g of polyethylene glycol (trade name: polyethylene glycol 20,000, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the prepared titanium oxide dispersion liquid to prepare a paste. The prepared paste was applied onto the hole blocking layer (average thickness: 1.5 μm), dried at 50° C., and then baked in air at 500° C. for 30 minutes to form a porous electron transport layer. ..
The glass substrate on which the electron transport layer was formed was prepared by using a photosensitizing compound represented by the structural formula (3) (trade name: D358, manufactured by Mitsubishi Paper Mills, Ltd.) in acetonitrile/t-butanol (volume ratio 1:1). It was dipped in the solution and allowed to stand in the dark for 1 hour to adsorb the photosensitizing compound on the surface of the electron transport layer. Next, an alkali metal salt (manufactured by Kanto Chemical Co., Inc.) 19 represented by the following structural formula (6) was added to 16.5 mL of a chlorobenzene solution containing 186.5 mg of the hole transport material represented by D-7 (manufactured by Merck Ltd.). 0.0 mg, the basic compound represented by C-1 (37.5 mg), and the oxidizing agent represented by the structural formula (F-21) 12.5 mg (trade name: FK269, manufactured by Sigma-Aldrich Japan Co., Ltd.) were added. And dissolved to prepare a hole transport layer coating solution.

Next, a hole transport layer was formed on the electron transport layer adsorbing the photosensitizing compound by spin coating using the coating solution for the hole transport layer (average thickness: 600 nm). A second electrode (average thickness: 100 nm) was formed by vacuum-depositing silver thereon.
Next, the hole transport layer on the outer peripheral portion of the glass substrate on which the electron transport layer is not formed is removed, and an epoxy resin A (UV curable type, containing inorganic filler, commercial product Name: TB3118, manufactured by ThreeBond Holdings Co., Ltd. was applied using a dispenser (trade name: 2300N, manufactured by San-Ai Tech Co., Ltd.). Next, a mixed gas of nitrogen and oxygen (oxygen concentration: 5.0% by volume, dew point: −30° C.) was introduced into the glove box, and the mixture gas was transferred into the mixture gas and the second substrate was placed on the epoxy resin A. Then, the epoxy resin A was cured by irradiation with ultraviolet rays to seal the power generation region, and the photoelectric conversion element of Example 1 was produced (FIG. 1).

(Example 2)
A photoelectric conversion element of Example 2 was produced in the same manner as in Example 1 except that the photosensitizing compound in Example 1 was changed to the photosensitizing compound represented by the structural formula (2).

(Example 3)
A photoelectric conversion element of Example 3 was produced in the same manner as in Example 1, except that the photosensitizing compound represented by B-5 was used instead of the photosensitizing compound in Example 1.

(Example 4)
A photoelectric conversion element of Example 4 was produced in the same manner as in Example 3, except that the basic compound in Example 3 was changed to the basic compound represented by C-5.

(Example 5)
A photoelectric conversion element of Example 5 was produced in the same manner as in Example 3, except that the basic compound in Example 3 was changed to the basic compound represented by C-7.

(Example 6)
A photoelectric conversion element of Example 6 was produced in the same manner as in Example 3, except that the basic compound in Example 3 was changed to the basic compound represented by C-9.

(Example 7)
A photoelectric conversion element of Example 7 was produced in the same manner as in Example 3 except that the hole transporting material in Example 3 was changed to the hole transporting material represented by D-10.

(Example 8)
A photoelectric conversion element of Example 8 was produced in the same manner as in Example 3 except that the cobalt complex represented by the structural formula (F-11) was used as the oxidizing agent.

(Example 9)
A photoelectric conversion element of Example 9 was produced in the same manner as in Example 3 except that the cobalt complex represented by the following structural formula (7) was used as the oxidizing agent.

(Example 10)
In the same manner as in Example 8 except that the sealing member was changed to epoxy resin B (UV curable type, containing inorganic filler, trade name: WorldRock No. 5910, manufactured by Kyoritsu Chemical Industry Co., Ltd.). A photoelectric conversion element of Example 10 was produced.

(Example 11)
Example 11 Example 11 was repeated except that the sealing member was changed to epoxy resin C (UV curable type, containing inorganic filler, trade name: TB3124, manufactured by Three Bond Holdings Co., Ltd.). The photoelectric conversion element of was produced.

(Example 12)
In Example 8, the sealing member was made of epoxy resin D (UV curable type, containing inorganic filler, trade name: XNR5516Z, manufactured by Nagase Chemtech Co., Ltd.) and gap agent (monodispersed silica particles, manufactured by Ube Eximo Co., Ltd., particle size) The photoelectric conversion element of Example 12 was produced in the same manner as in Example 8 except that the mixture was changed to a mixture having a thickness of 30 μm.

(Comparative Example 1)
A photoelectric conversion element of Comparative Example 1 was produced in the same manner as in Example 1, except that the basic compound in Example 1 was changed to the basic compound represented by the following structural formula (8).

(Comparative example 2)
A photoelectric conversion element of Comparative Example 2 was produced in the same manner as in Example 1 except that the basic compound in Example 1 was changed to the basic compound represented by the following structural formula (9).

(Comparative example 3)
A photoelectric conversion element of Comparative Example 3 was produced in the same manner as in Example 1 except that the basic compound in Example 1 was changed to the basic compound represented by the following structural formula (10).

(Comparative Example 4)
Comparative Example 4 was performed in the same manner as in Example 8 except that the sealing member in Example 8 was changed to acrylic resin A (UV curable type, containing inorganic filler, trade name: TB3035B, manufactured by Three Bond Holdings Co., Ltd.). The photoelectric conversion element of was produced.

(Comparative example 5)
Comparative Example 5 was carried out in the same manner as in Example 8 except that the sealing member was changed to acrylic resin B (UV curable type, containing inorganic filler, trade name: Nichiban UM, Nichiban Co., Ltd.). A photoelectric conversion element was produced.

(Comparative example 6)
A photoelectric conversion element of Comparative Example 6 was produced in the same manner as in Example 8 except that sealing was not performed in Example 8.

Next, with respect to each of the produced photoelectric conversion elements, the “initial value maintenance ratio after high temperature storage” and the “initial value maintenance ratio after continuous irradiation with low illuminance light” were evaluated as follows. The results are shown in Table 1.

[Initial value maintenance ratio after high temperature storage and initial value maintenance ratio after continuous irradiation of low illumination light]
For each photoelectric conversion element produced, under irradiation of a white LED adjusted to 200 lux, a solar cell evaluation system (DC voltage/current source/monitor, 6241A, manufactured by ADC Co., Ltd.) was used to evaluate IV characteristics, The initial maximum output power P _max1 (μW/cm ² ) was determined.
Next, the photoelectric conversion element was stored in a high temperature environment of 50° C. (dryer, device name: DKM400, manufactured by Yamato Scientific Co., Ltd.) for 500 hours, then returned to a normal temperature environment and evaluated for IV characteristics again, and after high temperature storage Of the maximum output power P _max2 (μW/cm ² ) of By dividing the obtained P _max2 by the initial value P _max1 , the “initial value maintenance rate after high temperature storage” (P _max2 /P _max1 ) was obtained.
Then, the photoelectric conversion element was irradiated with white LEDs adjusted to 200 lux for 500 hours, and then the IV characteristics were evaluated, and the maximum output power P _max3 (μW/cm ² ) after continuous irradiation of 200 lux was obtained. By dividing the obtained P _max3 by the initial value P _max1 , the “initial value maintenance ratio after continuous irradiation with low illuminance light” (P _max3 /P _max1 ) was obtained.

(Example 13)
<Production of photoelectric conversion element module>
First, on a glass substrate as a first substrate, indium-doped tin oxide (ITO) and niobium-doped tin oxide (NTO) as a first electrode are sequentially sputtered, and then a dense layer of titanium oxide as a hole blocking layer is formed. Various layers were formed by reactive sputtering with oxygen gas. Next, the first electrode and a part of the hole blocking layer formed on the substrate were subjected to etching treatment by laser processing.
Next, 3 g of titanium oxide (trade name: ST-21, manufactured by Ishihara Sangyo Co., Ltd.), 0.2 g of acetylacetone, and polyoxyethylene octylphenyl ether as a surfactant (manufactured by Wako Pure Chemical Industries, Ltd.) 0 The titanium oxide dispersion liquid was prepared by subjecting 0.3 g of the mixture to 5.5 g of water and 1.0 g of ethanol and subjecting it to a bees mill treatment for 12 hours. 1.2 g of polyethylene glycol (trade name: polyethylene glycol 20,000, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the prepared titanium oxide dispersion liquid to prepare a paste. The prepared paste was applied onto the hole blocking layer (average thickness: 1.5 μm), dried at 50° C., and then baked in air at 550° C. for 30 minutes to form a porous electron transport layer. ..
The glass substrate on which the electron transport layer was formed was mixed with 120 mg of the photosensitizing compound represented by B-5 and 150 mg of chenodeoxycholic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in acetonitrile/t-butanol (volume ratio 1:1). The solution was added and immersed in the stirred solution, and allowed to stand in the dark for 1 hour to adsorb the photosensitizing compound on the surface of the electron transport layer.
Next, in 16.5 mL of a chlorobenzene solution containing 186.5 mg of the hole transport material (manufactured by Merck Ltd.) represented by D-7, the alkali metal salt represented by the structural formula (6) (manufactured by Kanto Chemical Co., Inc.) 19 0.0 mg, the basic compound represented by C-1 (37.5 mg), and the oxidizing agent represented by the structural formula (F-11) 12.5 mg (trade name: FK209, manufactured by Sigma-Aldrich Japan Co., Ltd.) were added. And dissolved to prepare a hole transport layer coating solution.
Next, a hole transport layer was formed on the electron transport layer having the photosensitizing compound adsorbed thereon by die coating using the coating solution for the hole transport layer (average thickness: 500 nm). After that, the end portion of the glass substrate on which the sealing member was provided was etched by laser processing, and a through hole for connecting the photoelectric conversion elements in series was formed by laser processing. Furthermore, silver was vacuum-deposited thereon to form a second electrode (average thickness: 100 nm). At this time, silver was also vapor-deposited on the inner wall of the through hole, and it was confirmed that adjacent photoelectric conversion elements were connected in series.
Next, an epoxy resin B (ultraviolet curing type, containing inorganic filler, trade name: World Rock No. 5910, manufactured by Kyoritsu Chemical Industry Co., Ltd.) is dispensed (commodity) so that the power generation region is surrounded by the end portion of the glass substrate. Name: 2300N, manufactured by Sanei Tech Co., Ltd.). After that, a mixed gas of nitrogen and oxygen (oxygen concentration: 0.6% by volume, dew point: −20° C.) was introduced into the glove box, and transferred into it to form a second substrate on the epoxy resin B. After mounting the cover glass of No. 3, the epoxy resin B was cured by ultraviolet irradiation, the power generation region was sealed, and the photoelectric conversion element module of Example 13 in which 6 cells were connected in series was manufactured ( 6 and 7). 6 and 7 are schematic views in which the directions of observation are different from each other.

(Example 14)
Example 13 is the same as Example 13 except that the oxygen concentration in the glove box during sealing is set to 3.0% by volume (oxygen is 3.0% by volume nitrogen mixed gas). 14 photoelectric conversion element modules were produced.

(Example 15)
Example 13 is the same as Example 13 except that the oxygen concentration in the glove box during sealing is set to 5.0% by volume (oxygen is 5.0% by volume nitrogen mixed gas). Fifteen photoelectric conversion element modules were produced.

(Example 16)
Example 13 Example 13 was repeated in the same manner as Example 13 except that the oxygen concentration in the glove box during sealing was set to 10.0 vol% (nitrogen mixed gas containing 10.0 vol% oxygen). Sixteen photoelectric conversion element modules were produced.

(Example 17)
Example 13 Example 13 is the same as Example 13 except that the oxygen concentration in the glove box at the time of sealing is set to 15.0% by volume (oxygen is 15.0% by volume nitrogen mixed gas). Seventeen photoelectric conversion element modules were produced.

(Example 18)
A photoelectric conversion element module of Example 18 is manufactured in the same manner as in Example 13 except that the oxygen concentration in the glove box during sealing is set to 21.0% by volume (high-purity air). did.

(Example 19)
Example 13 Example 13 is the same as Example 13 except that the oxygen concentration in the glove box at the time of sealing is set to 30.0% by volume (oxygen is 30.0% by volume nitrogen mixed gas). Nineteen photoelectric conversion element modules were produced.

Next, the "initial value maintenance ratio after high temperature storage" and the "initial value maintenance ratio after continuous irradiation with low illuminance light" were evaluated for the produced photoelectric conversion element module as follows. The results are shown in Table 2.

[Initial value maintenance ratio after high temperature storage and initial value maintenance ratio after continuous irradiation of low illumination light]
About the produced photoelectric conversion element module, IV characteristics were evaluated using a solar cell evaluation system (As-510-PV03, manufactured by NF Circuit Design Block Co., Ltd.) under irradiation of white LED adjusted to 200 lux, and the initial maximum value was obtained. The output power P _max1 (μW/cm ² ) was determined.
Next, the photoelectric conversion element module is stored in a high temperature environment of 50° C. (dryer, device name: DKM400, manufactured by Yamato Scientific Co., Ltd.) for 500 hours, then returned to a normal temperature environment, the IV characteristics are evaluated again, and high temperature storage is performed. The maximum output power P _max2 (μW/cm ² ) after that was determined. By dividing the obtained P _max2 by the initial value P _max1 , the “initial value maintenance rate after high temperature storage” (P _max2 /P _max1 ) was obtained.
Thereafter, the photoelectric conversion element module was irradiated with white LEDs adjusted to 1500 lux for 500 hours, and then the IV characteristics were evaluated under the irradiation of white LEDs adjusted to 200 lux, and the maximum after continuous irradiation with 1500 lux for 500 hours was performed. The output power P _max3 (μW/cm ² ) was determined. By dividing the obtained P _max3 by the initial value P _max1 , the “initial value maintenance ratio after continuous irradiation with low illuminance light” (P _max3 /P _max1 ) was obtained.

As can be seen from the evaluation results of Table 1 and Table 2, the photoelectric conversion element and the photoelectric conversion element module of the present invention are continuously irradiated with 200 lux or 1500 lux even after being stored at high temperature for a long time. However, the initial maximum output power P _max1 has a high maintenance rate and high power generation stability.
On the other hand, when using a basic compound other than the basic compound specified in the present invention, when using a resin other than the epoxy resin as the sealing member, after high temperature storage, and at least one of the maintenance rate after continuous irradiation Was significantly reduced. This is because when the photoelectric conversion element and the photoelectric conversion element module are stored for a long time in a high temperature environment, the gas generated from the sealing member increases, the sealing property of the sealing member decreases, etc. It is considered that the characteristics were deteriorated by continuous irradiation.

Aspects of the present invention are as follows, for example.
<1> A photoelectric conversion element having at least a first electrode, a hole blocking layer, an electron transport layer having a photosensitizing compound, a hole transport layer, and a second electrode,
At least the electron transport layer, the hole transport layer, and the second electrode have a sealing member containing an epoxy resin that shields the photoelectric conversion element from the external environment,
The photoelectric conversion element is characterized in that the hole transport layer contains at least one of a tertiary amine compound represented by the following general formula (1) and general formula (2).
However, the general formula (1), and in the general formula (2), Ar ₁ and Ar ₂ have substituents represent also aryl groups, wherein Ar ₁ and the Ar ₂ are also the same They may be different or may be bonded to each other.
<2> having a pair of substrates,
A photoelectric conversion element having at least the first electrode, the hole blocking layer, the electron transport layer, the hole transport layer, and the second electrode between the pair of substrates,
Furthermore, the photoelectric conversion element according to <1>, wherein the sealing member is sandwiched between the pair of substrates.
<3> The photoelectric conversion element according to any one of <1> to <2>, which has a void portion inside the photoelectric conversion element shielded from the external environment.
<4> The photoelectric conversion element according to <3>, wherein the void portion contains oxygen.
<5> The sealing member is the photoelectric conversion element according to any one of <1> to <4>, which includes an inorganic filler.
<6> The hole transport layer is the photoelectric conversion element according to any one of <1> to <5>, which includes a metal complex.
<7> The photoelectric conversion device according to <6>, wherein the metal complex is a trivalent cobalt complex.
<8> The hole transport layer is the photoelectric conversion element according to any one of <1> to <7>, which contains a lithium salt.
<9> A plurality of photoelectric conversion elements are arranged adjacent to each other and have photoelectric conversion element arrangement regions connected in series or in parallel,
A photoelectric conversion element module, wherein the plurality of photoelectric conversion elements have at least a first electrode, a hole blocking layer, an electron transport layer having a photosensitizing compound, a hole transport layer, and a second electrode. ,
At least the electron transporting layer, the hole transporting layer, and the second electrode have a sealing member containing an epoxy resin that shields the photoelectric conversion element module from the external environment,
The photoelectric conversion element module is characterized in that the hole transport layer contains at least one of a tertiary amine compound represented by the following general formula (1) and general formula (2).
However, the general formula (1), and in the general formula (2), Ar ₁ and Ar ₂ have substituents represent also aryl groups, wherein Ar ₁ and the Ar ₂ are also the same They may be different or may be bonded to each other.
<10> having a pair of substrates,
A photoelectric conversion element module having at least the first electrode, the hole blocking layer, the electron transport layer, the hole transport layer, and the second electrode between the pair of substrates,
Furthermore, the photoelectric conversion element module according to <9>, in which the sealing member is sandwiched between the pair of substrates.
<11> In at least two photoelectric conversion element modules adjacent to each other,
One of the first electrodes in the photoelectric conversion element,
The second electrode in the other photoelectric conversion element,
The photoelectric conversion element module according to any one of <9> to <10>, wherein the photoelectric conversion element module is electrically connected by a conductive portion penetrating at least the hole transport layer to the hole blocking layer.
<12> The photoelectric conversion element module according to any one of <9> to <11>, having a void inside the photoelectric conversion element shielded from the external environment.
<13> The photoelectric conversion element module according to <12>, wherein the void portion contains oxygen.
<14> The photoelectric conversion element module according to any one of <9> to <13>, wherein the sealing member has an inorganic filler.
<15> The hole transport layer is the photoelectric conversion element module according to any one of <9> to <14>, which has a metal complex.
<16> The photoelectric conversion element module according to <15>, wherein the metal complex is a trivalent cobalt complex.
<17> The photoelectric conversion element module according to any one of <9> to <16>, in which the hole transport layer contains a lithium salt.
<18> The photoelectric conversion element and/or the photoelectric conversion element module according to any one of <1> to <17>,
A device that operates by electric power generated by photoelectric conversion of the photoelectric conversion element and/or the photoelectric conversion element module,
It is an electronic device characterized by having.
<19> A photoelectric conversion element and/or a photoelectric conversion element module according to any one of <1> to <17>,
A storage battery that stores electric power generated by photoelectric conversion of the photoelectric conversion element and/or the photoelectric conversion element module,
A device that operates by electric power generated by photoelectric conversion of the photoelectric conversion element and/or photoelectric conversion element module and/or electric power stored in the storage battery,
It is an electronic device characterized by having.
<20> The photoelectric conversion element and/or the photoelectric conversion element module according to any one of <1> to <17>,
Power supply IC,
Is a power supply module.

The photoelectric conversion element according to any one of <1> to <8>, the photoelectric conversion element module according to any of <9> to <17>, and the photoelectric conversion element module according to any of <18> to <19>. According to the electronic device and the power supply module according to <20>, the problems of the related art can be solved and the object of the present invention can be achieved.

1 1st board|substrate 2, 2a, 2b 1st electrode 3 Hole blocking layer 4 Electron transport layer 5 Photosensitizing compound 6 Hole transport layer 7, 7a, 7b 2nd electrode 8 Sealing member 9 2nd board|substrate 10 Void part 11 Penetration part 12 Sealing member 101 Photoelectric conversion element 102 Photoelectric conversion element module

JP, 2016-178288, A

Claims (20)

A photoelectric conversion element comprising at least a first electrode, a hole blocking layer, an electron transport layer having a photosensitizing compound, a hole transport layer, and a second electrode,
At least the electron transporting layer, the hole transporting layer, and the second electrode have a sealing member containing an epoxy resin that shields the photoelectric conversion element from the external environment,
The photoelectric conversion element, wherein the hole transport layer contains at least one of a tertiary amine compound represented by the following general formula (1) and general formula (2).
However, the general formula (1), and in the general formula (2), Ar ₁ and Ar ₂ have substituents represent also aryl groups, wherein Ar ₁ and the Ar ₂ are also the same They may be different or may be bonded to each other. Having a pair of substrates,
A photoelectric conversion element having at least the first electrode, the hole blocking layer, the electron transport layer, the hole transport layer, and the second electrode between the pair of substrates,
Furthermore, the photoelectric conversion element according to claim 1, wherein the sealing member is sandwiched between the pair of substrates. The photoelectric conversion element according to claim 1, which has a void portion inside the photoelectric conversion element shielded from the external environment. The photoelectric conversion element according to claim 3, wherein the void portion contains oxygen. The photoelectric conversion element according to claim 1, wherein the sealing member has an inorganic filler. The photoelectric conversion element according to claim 1, wherein the hole transport layer has a metal complex. The photoelectric conversion element according to claim 6, wherein the metal complex is a trivalent cobalt complex. The photoelectric conversion element according to claim 1, wherein the hole transport layer contains a lithium salt. A plurality of photoelectric conversion elements are arranged adjacent to each other, and has a photoelectric conversion element arrangement region connected in series or in parallel,
A photoelectric conversion element module, wherein the plurality of photoelectric conversion elements have at least a first electrode, a hole blocking layer, an electron transport layer having a photosensitizing compound, a hole transport layer, and a second electrode. ,
At least the electron transporting layer, the hole transporting layer, and the second electrode have a sealing member containing an epoxy resin that shields the photoelectric conversion element module from the external environment,
The photoelectric conversion element module, wherein the hole transport layer comprises at least one of a tertiary amine compound represented by the following general formula (1) and general formula (2).
However, the general formula (1), and in the general formula (2), Ar ₁ and Ar ₂ have substituents represent also aryl groups, wherein Ar ₁ and the Ar ₂ are also the same They may be different or may be bonded to each other. Having a pair of substrates,
A photoelectric conversion element module comprising at least the first electrode, the hole blocking layer, the electron transport layer, the hole transport layer, and the second electrode between the pair of substrates,
Furthermore, the photoelectric conversion element module according to claim 9, wherein the sealing member is sandwiched between the pair of substrates. In at least two photoelectric conversion element modules adjacent to each other,
One of the first electrodes in the photoelectric conversion element,
The second electrode in the other photoelectric conversion element,
The photoelectric conversion element module according to claim 9, wherein the photoelectric conversion element module is electrically connected by a conductive portion penetrating at least the hole transport layer to the hole blocking layer. The photoelectric conversion element module according to any one of claims 9 to 11, which has a void inside the photoelectric conversion element shielded from the external environment. The photoelectric conversion element module according to claim 12, wherein the void portion contains oxygen. The photoelectric conversion element module according to claim 9, wherein the sealing member has an inorganic filler. The photoelectric conversion element module according to claim 9, wherein the hole transport layer has a metal complex. The photoelectric conversion element module according to claim 15, wherein the metal complex is a trivalent cobalt complex. The photoelectric conversion element module according to claim 9, wherein the hole transport layer contains a lithium salt. A photoelectric conversion element and/or a photoelectric conversion element module according to any one of claims 1 to 17,
A device that operates by electric power generated by photoelectric conversion of the photoelectric conversion element and/or the photoelectric conversion element module,
An electronic device comprising: A photoelectric conversion element and/or a photoelectric conversion element module according to any one of claims 1 to 17,
A storage battery that stores electric power generated by photoelectric conversion of the photoelectric conversion element and/or the photoelectric conversion element module,
A device that operates by electric power generated by photoelectric conversion of the photoelectric conversion element and/or photoelectric conversion element module and/or electric power stored in the storage battery,
An electronic device comprising: A photoelectric conversion element and/or a photoelectric conversion element module according to any one of claims 1 to 17,
Power supply IC,
A power supply module comprising: