JP2017147315A - Method for manufacturing photoelectric conversion element, and photoelectric conversion element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a photoelectric conversion element with high endurance against light irradiation; and a method for manufacturing the photoelectric conversion element.SOLUTION: A method for manufacturing a photoelectric conversion element having a positive electrode, an active layer including a perovskite compound, an electron transport layer, and a negative electrode comprises the step of forming the electron transport layer which includes: the step of using a composition including a metal oxide precursor, and fullerene or a fullerene derivative to form a layer between the active layer and the negative electrode; or using a composition including a metal oxide precursor to form a layer on a side close to the active layer between the active layer and the negative electrode, and the step of using a composition including fullerene or a fullerene derivative to form a layer on a side close to the negative electrode between the active layer and the negative electrode.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a photoelectric conversion element and a photoelectric conversion element.

  In recent years, a method for producing a photoelectric conversion element having an active layer containing a perovskite compound has been proposed.

For example, a method for producing a photoelectric conversion element having an anode, an active layer containing a perovskite compound, an electron transport layer and a cathode in this order, a step of forming an anode, a step of forming an active layer containing a perovskite compound, Having a step of forming an electron transport layer and a step of forming a cathode in this order,
Forming the electron transport layer,
A process for producing a photoelectric conversion element, comprising a step of forming a layer using a composition containing a fullerene or a fullerene derivative and a step of forming a layer using a composition containing a metal oxide precursor in this order Has been reported (Non-patent Document 1).

Wei Chen, 10 others, “Efficient and stable large-area perovskite solar cells with organic charge extraction layers”, Science, 2015, Vol. 350, Issue 6263, p. 944-948

  However, the photoelectric conversion element described in Non-Patent Document 1 described above does not always have sufficient durability.

  The objective of this invention is providing the manufacturing method of the photoelectric conversion element which has high durability with respect to light irradiation, and its photoelectric conversion element.

That is, the present invention provides the following [1] to [7].
[1] A method for producing a photoelectric conversion element having an anode, an active layer containing a perovskite compound, an electron transport layer, and a cathode,
Forming the electron transport layer,
Forming a layer between the active layer and the cathode using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing a metal oxide precursor on the side close to the active layer between the active layer and the cathode; and a fullerene or fullerene derivative on the side close to the cathode between the active layer and the cathode. The manufacturing method of a photoelectric conversion element which is a process which has a process of forming a layer using the composition containing.
[2] A method for producing a photoelectric conversion element having an anode, an active layer containing a perovskite compound, an electron transport layer, and a cathode in this order,
A step of forming an anode, a step of forming an active layer containing a perovskite compound, a step of forming an electron transport layer, and a step of forming a cathode in this order,
Forming the electron transport layer,
Forming a layer using a composition comprising a metal oxide precursor and fullerene or a fullerene derivative, or
A method for producing a photoelectric conversion element, comprising: a step of forming a layer using a composition containing a metal oxide precursor; and a step of forming a layer using a composition containing fullerene or a fullerene derivative in this order. .
[3] The method for producing a photoelectric conversion element according to [1] or [2], wherein the metal oxide precursor is a titanium oxide precursor.
[4] The method for producing a photoelectric conversion element according to any one of [1] to [3], wherein the metal oxide precursor is a metal alkoxide.
[5] A photoelectric conversion element obtained by the method for manufacturing a photoelectric conversion element according to any one of [1] to [4].
[6] A solar cell module including the photoelectric conversion element according to [5].
[7] An organic photosensor comprising the photoelectric conversion element according to [5].

  ADVANTAGE OF THE INVENTION According to this invention, durability of a photoelectric conversion element can be improved more. In the present invention, the high durability of the photoelectric conversion element means that the value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) is high.

  Hereinafter, the present invention will be described in detail.

<Explanation of common terms>
Hereinafter, terms commonly used in the present specification have the following meanings unless otherwise specified.

  In the present specification, “which may have a substituent” means that all hydrogen atoms constituting the compound or group are unsubstituted and a part or all of one or more hydrogen atoms. Including both embodiments where is substituted by a substituent. The number of carbon atoms of the group which may have a substituent does not include the number of carbon atoms of the substituent.

  Examples of the substituent include alkyl group, cycloalkyl group, halogenated alkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, aryl Alkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue, dialkylamino group, diaryl Examples thereof include an amino group, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxy group, a substituted carboxy group, a cyano group, and a polymerizable substituent.

  The polymerizable substituent represents a substituent capable of forming a compound by forming a bond between two or more molecules by causing a polymerization reaction. Examples of such a group include a group having a carbon-carbon multiple bond (for example, a vinyl group, an ethynyl group, a butenyl group, an acryloyl group, a group in which one hydrogen atom is removed from an acrylate ester, and one hydrogen atom from acrylamide. Removed groups, methacryloyl groups, groups in which one hydrogen atom has been removed from methacrylic acid ester, groups in which one hydrogen atom has been removed from methacrylamide, groups in which one hydrogen atom has been removed from allene, allyl groups, A vinyloxy group, a vinylamino group, a furyl group, a pyrrolyl group, a thienyl group, a group in which one hydrogen atom is removed from silole, a group having a benzocyclobutene structure, etc.), a small ring (for example, cyclopropyl) Group, cyclobutyl group, epoxy group, group having oxetane structure, group having diketene structure, group having episulfide structure, etc. Group having the group having a lactone structure, a group having a lactam structure, or a group containing a siloxane derivative. In addition to the above groups, combinations of groups capable of forming an ester bond or an amide bond can also be used. Examples of such group combinations include a combination of a hydrocarbyloxycarbonyl group and an amino group, and a combination of a hydrocarbyloxycarbonyl group and a hydroxy group.

<1> Method for producing photoelectric conversion element The method for producing a photoelectric conversion element of the present invention comprises:
A method for producing a photoelectric conversion element having an anode, an active layer containing a perovskite compound, an electron transport layer, and a cathode,
Forming the electron transport layer,
Forming a layer between the active layer and the cathode using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing a metal oxide precursor on the side close to the active layer between the active layer and the cathode; and a side between the active layer and the cathode close to the cathode And a step of forming a layer using a composition containing fullerene or a fullerene derivative.

As a manufacturing method of the photoelectric conversion element of the present invention, for example,
(A) a step of forming an anode, a step of forming an active layer containing a perovskite compound, a step of forming an electron transport layer, and a step of forming a cathode in this order,
Forming the electron transport layer,
Forming a layer using a composition comprising a metal oxide precursor and fullerene or a fullerene derivative, or
A method for producing a photoelectric conversion element, comprising: a step of forming a layer using a composition containing a metal oxide precursor; and a step of forming a layer using a composition containing fullerene or a fullerene derivative in this order. And (b) a step of forming a cathode, a step of forming an electron transport layer, a step of forming an active layer containing a perovskite compound, and a step of forming an anode in this order,
Forming the electron transport layer,
Forming a layer using a composition comprising a metal oxide precursor and fullerene or a fullerene derivative, or
A process for producing a photoelectric conversion element, comprising a step of forming a layer using a composition containing a fullerene or a fullerene derivative and a step of forming a layer using a composition containing a metal oxide precursor in this order ,
Is mentioned.

From the viewpoint of durability of the obtained photoelectric conversion element, the step of forming the electron transport layer is
A step of forming a layer using a composition containing a metal oxide precursor on the side close to the active layer between the active layer and the cathode; and a side between the active layer and the cathode close to the cathode And a step of forming a layer using a composition containing fullerene or a fullerene derivative in this order.

The manufacturing method of the photoelectric conversion element of the invention may further include a step of forming a hole injection layer, a hole transport layer, an electron injection layer, a sealing layer and / or a UV cut layer.
The hole injection layer can be formed between the anode and the active layer or between the anode and the hole transport layer.
The hole transport layer can be formed between the hole injection layer and the active layer.
The electron injection layer can be formed between the cathode and the electron transport layer.

As a manufacturing method of the photoelectric conversion element of the present invention, for example,
(A-1) A method for producing a photoelectric conversion element having an anode, an active layer containing a perovskite compound, an electron transport layer, and a cathode in this order,
A step of forming an anode, a step of forming an active layer containing a perovskite compound on the anode, a step of forming an electron transport layer on the active layer, and a cathode on the electron transport layer Process in this order,
Forming the electron transport layer,
Forming a layer on the active layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
Forming a layer on the active layer using a composition containing a metal oxide precursor; and forming a layer on the layer formed on the active layer using a composition containing fullerene or a fullerene derivative. A process for forming a photoelectric conversion element, which is a process having the steps of forming in this order,
(A-2) A method for producing a photoelectric conversion element having an anode, a hole injection layer, an active layer containing a perovskite compound, an electron transport layer, and a cathode in this order,
A step of forming an anode, a step of forming a hole injection layer on the anode, a step of forming an active layer containing a perovskite compound on the hole injection layer, and an electron transport on the active layer A step of forming a layer, and a step of forming a cathode on the electron transport layer in this order,
Forming the electron transport layer,
Forming a layer on the active layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
Forming a layer on the active layer using a composition containing a metal oxide precursor; and forming a layer on the layer formed on the active layer using a composition containing fullerene or a fullerene derivative. A process for forming a photoelectric conversion element, which is a process having the steps of forming in this order,
(A-3) A method for producing a photoelectric conversion element having an anode, a hole injection layer, a hole transport layer, an active layer containing a perovskite compound, an electron transport layer, and a cathode in this order,
A step of forming an anode, a step of forming a hole injection layer on the anode, a step of forming a hole transport layer on the hole injection layer, and a perovskite compound on the hole transport layer A step of forming an active layer containing, a step of forming an electron transport layer on the active layer, and a step of forming a cathode on the electron transport layer, in this order,
Forming the electron transport layer,
Forming a layer on the active layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
Forming a layer on the active layer using a composition containing a metal oxide precursor; and forming a layer on the layer formed on the active layer using a composition containing fullerene or a fullerene derivative. A process for forming a photoelectric conversion element, which is a process having the steps of forming in this order,
(A-4) A method for producing a photoelectric conversion element having an anode, an active layer containing a perovskite compound, an electron transport layer, an electron injection layer, and a cathode in this order,
A step of forming an anode; a step of forming an active layer containing a perovskite compound on the anode; a step of forming an electron transport layer on the active layer; and an electron injection layer on the electron transport layer. And a step of forming a cathode on the electron injection layer in this order,
Forming the electron transport layer,
Forming a layer on the active layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
Forming a layer on the active layer using a composition containing a metal oxide precursor; and forming a layer on the layer formed on the active layer using a composition containing fullerene or a fullerene derivative. A process for forming a photoelectric conversion element, which is a process having the steps of forming in this order,
(A-5) A method for producing a photoelectric conversion element having an anode, a hole injection layer, an active layer containing a perovskite compound, an electron transport layer, an electron injection layer, and a cathode in this order,
A step of forming an anode, a step of forming a hole injection layer on the anode, a step of forming an active layer containing a perovskite compound on the hole injection layer, and an electron transport on the active layer A step of forming a layer, a step of forming an electron injection layer on the electron transport layer, and a step of forming a cathode on the electron injection layer in this order,
Forming the electron transport layer,
Forming a layer on the active layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
Forming a layer on the active layer using a composition containing a metal oxide precursor; and forming a layer on the layer formed on the active layer using a composition containing fullerene or a fullerene derivative. A process for forming a photoelectric conversion element, which is a process having the steps of forming in this order,
(A-6) A method for producing a photoelectric conversion element having an anode, a hole injection layer, a hole transport layer, an active layer containing a perovskite compound, an electron transport layer, an electron injection layer, and a cathode in this order,
A step of forming an anode, a step of forming a hole injection layer on the anode, a step of forming a hole transport layer on the hole injection layer, and a perovskite compound on the hole transport layer A step of forming an active layer including: a step of forming an electron transport layer on the active layer; a step of forming an electron injection layer on the electron transport layer; and a cathode on the electron injection layer. And the process of forming in this order,
Forming the electron transport layer,
Forming a layer on the active layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
Forming a layer on the active layer using a composition containing a metal oxide precursor; and forming a layer on the layer formed on the active layer using a composition containing fullerene or a fullerene derivative. A process for forming a photoelectric conversion element, which is a process having the steps of forming in this order,
(B-1) A method for producing a photoelectric conversion element having a cathode, an electron transport layer, an active layer containing a perovskite compound, and an anode in this order,
A step of forming a cathode, a step of forming an electron transport layer on the cathode, a step of forming an active layer containing a perovskite compound on the electron transport layer, and an anode on the active layer Process in this order,
Forming the electron transport layer,
Forming a layer on the cathode using a composition comprising a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing fullerene or a fullerene derivative on a cathode, and a layer using a composition containing a metal oxide precursor on the layer formed on the cathode. A method for producing a photoelectric conversion element, which is a step having steps in this order,
(B-2) A method for producing a photoelectric conversion element having a cathode, an electron transport layer, an active layer containing a perovskite compound, a hole injection layer, and an anode in this order,
A step of forming a cathode, a step of forming an electron transport layer on the cathode, a step of forming an active layer containing a perovskite compound on the electron transport layer, and a hole injection layer on the active layer And a step of forming an anode on the hole injection layer in this order,
Forming the electron transport layer,
Forming a layer on the cathode using a composition comprising a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing fullerene or a fullerene derivative on a cathode, and a layer using a composition containing a metal oxide precursor on the layer formed on the cathode. A method for producing a photoelectric conversion element, which is a step having steps in this order,
(B-3) A method for producing a photoelectric conversion element having a cathode, an electron transport layer, an active layer containing a perovskite compound, a hole transport layer, a hole injection layer, and an anode in this order,
A step of forming a cathode, a step of forming an electron transport layer on the cathode, a step of forming an active layer containing a perovskite compound on the electron transport layer, and a hole transport layer on the active layer A step of forming a hole injection layer on the hole transport layer, and a step of forming an anode on the hole injection layer in this order,
Forming the electron transport layer,
Forming a layer on the cathode using a composition comprising a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing fullerene or a fullerene derivative on a cathode, and a layer using a composition containing a metal oxide precursor on the layer formed on the cathode. A method for producing a photoelectric conversion element, which is a step having steps in this order,
(B-4) A method for producing a photoelectric conversion element having a cathode, an electron injection layer, an electron transport layer, an active layer containing a perovskite compound, and an anode in this order,
A step of forming a cathode, a step of forming an electron injection layer on the cathode, a step of forming an electron transport layer on the electron injection layer, and an active layer containing a perovskite compound on the electron transport layer And a step of forming an anode on the active layer in this order,
Forming the electron transport layer,
Forming a layer on the electron injection layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing fullerene or a fullerene derivative on the electron injection layer, and a composition containing a metal oxide precursor on the layer formed on the electron injection layer. A method for producing a photoelectric conversion element, which is a step having a step of forming a layer in this order,
(B-5) A method for producing a photoelectric conversion element having a cathode, an electron injection layer, an electron transport layer, an active layer containing a perovskite compound, a hole injection layer, and an anode in this order,
A step of forming a cathode, a step of forming an electron injection layer on the cathode, a step of forming an electron transport layer on the electron injection layer, and an active layer containing a perovskite compound on the electron transport layer Forming a positive hole injection layer on the active layer, and forming an anode on the positive hole injection layer in this order,
Forming the electron transport layer,
Forming a layer on the electron injection layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing fullerene or a fullerene derivative on the electron injection layer, and a composition containing a metal oxide precursor on the layer formed on the electron injection layer. And (b-6) a cathode, an electron injection layer, an electron transport layer, an active layer containing a perovskite compound, a hole transport layer, a positive layer, and a step of forming a layer in this order. A method for producing a photoelectric conversion element having a hole injection layer and an anode in this order,
A step of forming a cathode, a step of forming an electron injection layer on the cathode, a step of forming an electron transport layer on the electron injection layer, and an active layer containing a perovskite compound on the electron transport layer Forming a hole transport layer on the active layer, forming a hole injection layer on the hole transport layer, and forming an anode on the hole injection layer. And the process of forming in this order,
Forming the electron transport layer,
Forming a layer on the electron injection layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing fullerene or a fullerene derivative on the electron injection layer, and a composition containing a metal oxide precursor on the layer formed on the electron injection layer. A method for producing a photoelectric conversion element, which is a step having a step of forming a layer in this order,
Is mentioned.

  The steps of forming an anode, forming a hole injection layer, forming a hole transport layer, forming an active layer containing a perovskite compound, forming an electron transport layer, and forming an electron injection layer are as follows: The step of forming, the step of forming the cathode, the step of forming the sealing layer, and the step of forming the UV cut layer will be described in detail.

(Anode formation process)
There is no restriction | limiting in particular in the formation method of an anode. The anode can be formed by depositing an anode material described later on a support substrate by a vacuum deposition method, a sputtering method, an ion plating method, a plating method, or the like.
When organic materials such as polyaniline and its derivatives, polythiophene and its derivatives are used as the anode material, the anode is formed by a coating method using a coating liquid containing organic materials, metal ink, metal paste, or a molten low melting point metal. May be. The anode may be subjected to surface treatment such as ozone UV treatment, corona treatment, ultrasonic treatment or the like.

(Hole injection layer formation process)
The method for forming the hole injection layer is not particularly limited, but it is preferably formed by a coating method from the viewpoint of simplifying the production process. When using the coating method, for example, it can be formed by coating a coating solution containing a material of a hole injection layer described later and a solvent.

  The coating liquid for forming the hole injection layer is not limited to a solution, and may be a dispersion such as an emulsion (emulsion) or a suspension (suspension).

  As the coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, Examples of the coating method include an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, and a capillary coating method. Among these, a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.

Examples of the solvent contained in the coating liquid containing the material for the hole injection layer and the solvent include water, alcohol, ketone, and hydrocarbon.
Specific examples of the alcohol include methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, butoxyethanol, methoxybutanol and the like.
Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone and the like.
Specific examples of the hydrocarbon include n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, tetralin, chlorobenzene, orthodichlorobenzene and the like.

  The solvent may contain 2 or more types, and may contain 2 or more types of the solvent illustrated above. The solvent is preferably 1 to 10,000 times by weight, more preferably 10 to 1,000 times by weight, relative to the material of the hole injection layer.

  After application by the application method, it is preferable to remove the solvent by subjecting the hole injection layer to heat treatment, air drying treatment, reduced pressure treatment or the like.

(Hole transport layer formation process)
Although the formation method of a positive hole transport layer is not specifically limited, From a viewpoint of simplification of a manufacturing process, forming by a coating method is preferable. In the case of using the coating method, for example, it can be formed by coating a coating solution containing a material for a hole transport layer described later and a solvent.

  The coating liquid for forming the hole transport layer is not limited to a solution, and may be a dispersion such as an emulsion (emulsion) or a suspension (suspension).

Examples of the coating method and the preferable coating method include the same coating methods as those used when forming the hole injection layer.
Examples of the solvent and preferable solvent include the same solvents as those used for the coating liquid for the hole injection layer.

  Similarly to the step of forming the hole injection layer, it is preferable to remove the solvent by applying a heat treatment, an air drying treatment, a reduced pressure treatment or the like to the hole transport layer after coating by a coating method.

(Formation process of active layer)
The method for forming the active layer is not particularly limited, but is preferably formed by a coating method from the viewpoint of simplifying the manufacturing process.
The coating liquid for forming the active layer may be a solution or not a solution, and may be a dispersion such as an emulsion (emulsion) or a suspension (suspension).
The coating solution that can be used in the coating method may be a coating solution containing a perovskite compound or a coating solution containing a precursor that can be converted into a perovskite compound by a self-organization reaction after the formation of the active layer. Examples of such a precursor include CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbBr ₃ , (CH ₃ (CH ₂ ) _n CHCH ₃ NH ₃ ) ₂ PbI ₄ (n is an integer of 5 to 8). .), (C ₆ H ₅ C ₂ H ₄ NH ₃ ) ₂ PbBr ₄ .

An active layer containing a perovskite compound is formed by coating a coating solution containing a metal halide on the hole transport layer, and then forming a coating solution containing ammonium halide on the formed metal halide film, an amine halide. Alternatively, a method of further applying a coating solution containing formamidine hydrohalide, or a solution containing ammonium halide, formaldehyde or formamidine hydrohalide as a metal halide film formed It can also be formed by a method of immersing in the substrate.
More specifically, it can also be formed by applying a coating solution containing lead iodide on the hole transport layer and then applying a coating solution containing methylammonium iodide on the lead iodide film. it can.

  Examples of the method for applying the coating solution containing the perovskite compound, the coating solution containing the metal halide, the coating solution containing the ammonium halide, and the coating solution containing the halogenated amine include spin coating, casting, and microgravure. Coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing method, nozzle coating And coating methods such as a capillary coating method and the like. Among these, a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.

As a solvent for preparing a coating liquid for forming the active layer, esters (eg, methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc.) , Ketones (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc.), ethers (eg, diethyl ether, methyl-tert-butyl ether) , Diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole, etc.), alcohols ( , Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2- Fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, etc.), glycol ethers (cellosolves) (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, etc.), amide solvents (eg, N, N-dimethylformamide, acetamide, N, N-dimethylacetate) Imide), nitrile solvents (eg, acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile, etc.), carboat solvents (eg, ethylene carbonate, propylene carbonate, etc.), halogenated hydrocarbons (eg, methylene chloride, dichloromethane) , Chloroform, etc.), hydrocarbons (eg, n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, etc.), dimethyl sulfoxide and the like.
The compounds constituting these solvents may have a branched structure or a cyclic structure, and functional groups of esters, ketones, ethers and alcohols (that is, —O—, — (C═O) —, Two or more of -COO- and -OH) may be included. The hydrogen atom in the hydrocarbon moiety of the esters, ketones, ethers and alcohols may be substituted with a halogen atom (particularly a fluorine atom). Moreover, the coating liquid for forming the said active layer may contain 2 or more types of solvent, and may contain 2 or more types of solvent illustrated above.
With respect to the metal halide, ammonium halide, and halogenated amine, the solvent is preferably 1 to 10,000 times by weight, and more preferably 10 to 1000 times by weight.

  After the application of the coating solution, it is preferable to remove the solvent in forming the active layer. Examples of the method for removing the solvent include heat treatment, air drying treatment, and decompression treatment.

(Formation process of electron transport layer)
The step of forming the electron transport layer includes
Forming a layer between the active layer and the cathode using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing a metal oxide precursor on the side close to the active layer between the active layer and the cathode; and a fullerene or fullerene derivative on the side close to the cathode between the active layer and the cathode. And a step of forming a layer using the composition containing the same.

（Ａ） The metal oxide precursor means a compound that is in the pre-stage of the metal oxide in the reaction for synthesizing the metal oxide, that is, a compound that passes through the process of synthesizing the metal oxide. For example, the metal oxide precursor means a compound represented by the following formula (A).

(A)

In the formula (A ₁ ), A ₁ represents a metal atom.
R represents an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an amino group, or an alkanoyl group having 1 to 20 carbon atoms. A plurality of R may be the same as or different from each other.
Q represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. Plural Qs may be the same or different from each other.
m ₁ and n ₁ each represent an integer of 0 or more and not more than the valence that the metal atom represented by A ₁ can take, and the value of (m ₁ + n ₁ ) represents the metal represented by A ₁ Represents the valence that an atom can take.

Wherein (A), examples of the metal atom represented by A _1, titanium, zinc, tin, indium, zirconium, aluminum, tungsten, niobium, gallium, silicon, germanium are preferred, titanium is more preferable.

As a metal oxide precursor represented by the formula (A), m ₁ = 0, R is an alkoxy group having 1 to 20 carbon atoms, metal alkoxide is rich in reactivity, hydrolysis and polymerization It is preferable because a polymer made of a metal-oxygen bond is easily generated upon reaction.
The metal alkoxide is preferably a titanium alkoxide or a zinc alkoxide.

For example, in the formula (A), as the metal oxide precursor in which A ₁ is a titanium atom, titanium (IV) tert-butoxide, titanium (IV) butoxide, titanium (IV) isopropoxide, titanium (IV) propoxy , Titanium (IV) 2-ethylhexyl oxide, titanium (IV) ethoxide, titanium (IV) methoxide, titanium (IV) oxyacetylacetonate, titanium diisopropoxide bis (acetylacetonate) and chlorotriisopropoxytitanium ( Halogenation of titanium alkoxides such as IV), titanium bromide (IV), titanium chloride (III), titanium chloride (IV), titanium fluoride (III), titanium fluoride (IV) and titanium iodide (IV) Titanium, titanium (IV) diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate), tetrakis Diethylamide) titanium (IV), tetrakis (dimethylamido) titanium (IV), tetrakis (ethylmethylamido) titanium (IV) and bis (diethylamide) bis (dimethylamide), and the like titanium (IV).

For example, as the metal oxide precursor in which A ₁ in formula (A) is a zinc atom, zinc (II) methoxide, zinc (II) ethoxide, zinc (II) propoxide, zinc (II) isopropoxide, Zinc (II) butoxide, zinc (II) isobutoxide, zinc (II) tert-butoxide, zinc acetate, zinc (II) acetylacetonate and the like can be mentioned.

For example, as the metal oxide precursor in which A ₁ in formula (A) is a niobium atom, niobium (V) methoxide, niobium (V) ethoxide, niobium (V) propoxide, niobium (V) isopropoxide, Niobium (V) butoxide, niobium (V) isobutoxide, niobium (V) tert butoxide and the like.

Examples of the metal oxide precursor in which A ₁ in formula (A) is a tin atom include tin (IV) methoxide, tin (IV) ethoxide, tin (IV) propoxide, tin (IV) isopropoxide, tin ( IV) butoxide, tin (IV) isobutoxide, tin (IV) tert-butoxide, tin (IV) butoxide and the like.

Examples of the fullerene or fullerene derivative contained in the composition used in the step of forming the electron transport layer include C ₆₀ fullerene, C ₇₀ or more fullerene, carbon nanotube, and derivatives thereof. Specific examples of the C ₆₀ fullerene derivative include the following fullerene derivatives.

  As a fullerene derivative, the fullerene derivative represented by a following formula (B) is preferable from a viewpoint of improving durability.

（Ｂ）

(B)

In formula (B), the A ring represents a fullerene skeleton.
R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group which may be substituted with a halogen atom, a cycloalkyl group which may be substituted with a halogen atom, or a substituent. An aryl group which may have a substituent, an arylalkyl group which may have a substituent, a monovalent heterocyclic group which may have a substituent or the following formula (B-1) Represents a group.
n represents an integer of 1 or more.

（Ｂ−１）

(B-1)

In formula (B-1), m represents an integer of 1 to 6.
q represents the integer of 1-4.
X represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group which may have a substituent.
When there are a plurality of m, the plurality of m may be the same as or different from each other.

  In formula (B), n is preferably 1 or 2.

In the fullerene derivative represented by the formula (B), R ²¹ is preferably a group represented by the formula (B-1).

  In formula (B-1), m is preferably 2, and q is preferably 2.

  In formula (B-1), X is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a hydrogen atom or a methyl group. More preferably.

In the formula (B), examples of the fullerene skeleton represented by the A ring include a fullerene skeleton derived from a C ₆₀ fullerene and a fullerene skeleton derived from a fullerene having a carbon atom number of C ₇₀ fullerene or more.

  In the formula (B), the fullerene skeleton represented by the A ring may be a fullerene skeleton to which a predetermined group is added. When the fullerene skeleton represented by the A ring has a plurality of groups, the plurality of groups may be bonded to each other. Examples of the group that the fullerene skeleton represented by the A ring may have include an indan-1,3-diyl group and a methylene group that may have a substituent.

  In the formula (B), preferred examples of the substituent in the methylene group which may have a substituent that the fullerene skeleton represented by the A ring may have include an aryl group, a heteroaryl group, and a hydrocarbyloxycarbonyl. An alkyl group is mentioned.

  In the formula (B), the methylene group which may have a substituent which the fullerene skeleton represented by the A ring may have is preferably a methylene group having an aryl group and a hydrocarbyloxycarbonylalkyl group, and a phenyl group And a methylene group having an alkoxycarbonylpropyl group is more preferable, and a methylene group having a phenyl group and a methoxycarbonylpropyl group is more preferable.

In formula (B), the fullerene skeleton represented by the A ring is a fullerene skeleton derived from phenyl C ₆₁ butyric acid methyl ester (C ₆₀ PCBM) and a fullerene skeleton derived from phenyl C ₇₁ butyric acid methyl ester (C ₇₀ PCBM). There may be.

In the formula (B), examples of the halogen atom represented by R ²¹ , R ²² , R ^23, and R ²⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the formula (B), the alkyl group in the “alkyl group optionally substituted with a halogen atom” represented by R ²¹ , R ²² , R ²³ and R ²⁴ is linear or branched. There may be. The number of carbon atoms of the “alkyl group optionally substituted with a halogen atom” represented by R ²¹ , R ²² , R ²³ and R ²⁴ is usually 1 to 30, and preferably 1 to 20.

In the formula (B), the number of carbon atoms of the “cycloalkyl group optionally substituted with a halogen atom” represented by R ²¹ , R ²² , R ²³ and R ²⁴ is usually from 3 to 30, and 3 It is preferably ~ 20.

In formula (B), represented by R ²¹ , R ²² , R ²³ and R ²⁴ , “an alkyl group which may be substituted with a halogen atom” or “a cycloalkyl group which may be substituted with a halogen atom” Examples of the halogen atom in are the same as the examples of the halogen atom represented by R ²¹ , R ²² , R ²³ and R ²⁴ .

In the formula (B), the aryl group in the “aryl group optionally having substituents” represented by R ²¹ , R ²² , R ²³ and R ²⁴ is bonded to an aromatic ring from an aromatic hydrocarbon. Means a group in which one hydrogen atom is removed. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 16, and more preferably 6 to 10.

  Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The hydrogen atom in the aryl group may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, a halogen atom, a halogenated alkyl group, a halogenated cycloalkyl group, an alkoxy group, a cyclo Examples include an alkoxy group, a dialkylamino group, a diarylamino group, a silyl group, and a substituted silyl group. As the aryl group having a substituent, for example, 3-methylphenyl group, trimethylsilylphenyl group, 2-methoxyphenyl group, 4-methoxyphenyl group, 2,4,5-trimethoxyphenyl group, 4- (diphenylamino) -Phenyl group, 2- (dimethylamino) -phenyl group, 3-fluorophenyl group, and 4- (trifluoromethyl) -phenyl group.

The number of carbon atoms of the arylalkyl group in the “arylalkyl group optionally having substituent (s)” represented by R ²¹ , R ²² , R ²³ and R ²⁴ is usually 7 to 61, and 7 to 17 It is preferable that it is, and it is more preferable that it is 7-11. Specific examples of the arylalkyl group include benzyl group, phenylethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group and the like.

The number of carbon atoms of the monovalent heterocyclic group in the “monovalent heterocyclic group optionally having substituent (s)” represented by R ²¹ , R ²² , R ²³ and R ²⁴ is usually 1-30. Yes, preferably 1-20. Examples of the monovalent heterocyclic group in the “monovalent heterocyclic group optionally having substituent (s)” represented by R ²¹ , R ²² , R ²³ and R ²⁴ include a thienyl group, 2,2 A '-bithiophen-5-yl group is mentioned.
When a plurality of R ²⁴ are present, the plurality of R ²⁴ may be bonded to each other. When there are a plurality of R ^{24 s} , that is, when n represents an integer of 2 or more, examples of the substituent to which a plurality of R ²⁴ are bonded to each other include a divalent group represented by the following formula (B-2). Groups.

（Ｂ−２）

(B-2)

In formula (B-2), p represents an integer of 1 to 5.
p is preferably an integer of 2 to 4, and more preferably 3. The divalent group represented by the formula (B-2) may have a substituent.

Specific structures of the fullerene derivative represented by the formula (B) include the following structures. The ring structures with numerical values “60” and “70” in the following structures represent a C ₆₀ fullerene skeleton and a C ₇₀ fullerene skeleton, respectively.

  In the electron transport layer of the photoelectric conversion element obtained by the production method of the present invention, only one type of fullerene derivative represented by the formula (B) may be used, or two or more types may be used.

  The fullerene derivative represented by the formula (B) described above can be produced by any conventionally known suitable method. For example, it can be produced by a method using a 1,3-dipolar cycloaddition reaction between an iminium cation generated by decarboxylation from an imine formed from a glycine derivative and an aldehyde, and fullerene. Such methods are disclosed in, for example, JP 2009-67708 A, JP 2009-84264 A, JP 2011-241205 A, JP 2011-77486 A, and the like.

  In producing the fullerene derivative represented by the formula (B), by appropriately adjusting the reaction conditions such as reaction time and reaction temperature, and the amount of reaction raw materials (for example, glycine derivative, aldehyde, and fullerene) used, The number of “n” in the fullerene derivative represented by the formula (B) can be adjusted.

  Even if the manufacturing method of the photoelectric conversion element of this invention has a process of forming another electron carrying layer using compositions other than the composition containing a metal oxide precursor and fullerene or a fullerene derivative. Good.

  When the manufacturing method of the photoelectric conversion element of this invention has the process of forming another electron carrying layer, an electron transporting material can be used for formation of this another electron carrying layer. The electron transporting material may be an organic compound or an inorganic compound. The electron transport material which is an organic compound may be a low molecular compound or a high molecular compound.

Among the organic compounds, low molecular compounds include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, Fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, fullerenes and derivatives thereof, bathocuproine, etc. Examples thereof include phenanthrene derivatives.
Among the organic polymer compounds, the polymer compounds include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, Examples include polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, and the like.
Among these, fullerene or a derivative thereof is particularly preferable as the electron transporting material. Examples of fullerene or a derivative thereof include those described above.

Examples of the electron transport material of the inorganic compound include zinc oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, ITO (indium tin oxide), FTO (fluorine-doped tin oxide), and GZO (gallium-doped zinc oxide). ), ATO (antimony-doped tin oxide), and AZO (aluminum-doped zinc oxide). Among these, zinc oxide, gallium-doped zinc oxide, or aluminum-doped zinc oxide is preferable.
When forming the electron transport layer, it is preferable to form a coating solution containing particulate zinc oxide, gallium-doped zinc oxide, or aluminum-doped zinc oxide to form the electron transport layer. As such an electron transport material, it is preferable to use so-called zinc oxide, gallium-doped zinc oxide, or aluminum-doped zinc oxide nanoparticles, and electrons consisting of only zinc oxide, gallium-doped zinc oxide, or aluminum-doped zinc oxide nanoparticles. More preferably, the electron transport layer is formed using a transport material. The average particle diameter corresponding to the spheres of zinc oxide, gallium-doped zinc oxide or aluminum-doped zinc oxide is preferably 1 nm to 1000 nm, and more preferably 10 nm to 100 nm. The average particle diameter is measured by a laser light scattering method or an X-ray diffraction method.

  The ratio of the metal oxide precursor used in the step of forming the electron transport layer and the fullerene or fullerene derivative is such that the fullerene or fullerene derivative is 1% by weight to 10,000% by weight with respect to the weight of the metal oxide precursor. It is preferably 10% by weight to 1000% by weight.

  Examples of the method for forming the electron transport layer include a vacuum deposition method and a coating method, and it is preferably formed by a coating method.

  The coating liquid for forming the electron transport layer may be a solution or not a solution, and may be a dispersion such as an emulsion (emulsion) or a suspension (suspension).

Forming the electron transport layer,
When it is a step of forming a layer using a composition containing a metal oxide precursor and fullerene or a fullerene derivative between the active layer and the cathode,
An electron carrying layer can be produced using the coating liquid containing a metal oxide precursor, fullerene or a fullerene derivative, and a solvent, for example.
Forming the electron transport layer,
A step of forming a layer using a composition containing a metal oxide precursor on the side close to the active layer between the active layer and the cathode; and a fullerene or fullerene derivative on the side close to the cathode between the active layer and the cathode. And a step of forming a layer using the composition including the steps in this order,
In the step of forming each layer, the electron transport layer can be produced using, for example, a coating liquid containing a metal oxide precursor and a solvent, or a coating liquid containing fullerene or a fullerene derivative and a solvent.
Examples of the coating method include the same methods as the coating method exemplified in the step of forming the active layer.

Examples of the solvent contained in the coating solution used for forming the electron transport layer include alcohols, ketones, and hydrocarbons.
Specific examples of the alcohol include methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, butoxyethanol, methoxybutanol and the like.
Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone and the like.
Specific examples of the hydrocarbon include n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, tetralin, chlorobenzene, orthodichlorobenzene and the like.
The coating liquid used for forming the electron transport layer may contain two or more kinds of solvents, and may contain two or more kinds of the solvents exemplified above. The solvent is preferably 1 to 10,000 times by weight, and more preferably 10 to 1000 times by weight with respect to the electron transporting material.

  The coating solution containing a solvent and an electron transporting material is preferably filtered through a Teflon (registered trademark) filter having a pore diameter of 0.5 μm.

  In forming the electron transport layer by applying the coating solution, it is preferable to remove the solvent. Examples of the method for removing the solvent include the same method as the method for removing the solvent described in the step of forming the active layer.

(Step of forming the electron injection layer)
The method for forming the electron injection layer is not particularly limited. The electron injection layer can be formed by, for example, a vacuum deposition method, a coating method, or the like, and is preferably formed by a coating method.

  The coating liquid for forming the electron injection layer may be a solution, not a solution, or a dispersion such as an emulsion (emulsion) or a suspension (suspension).

The electron injection layer can be formed, for example, by applying a coating solution containing an alkaline earth metal oxide described later and a solvent on the electron transport layer.
Examples of the coating method include the same methods as the coating method exemplified in the step of forming the active layer.
It is preferable to use a coating solution that causes little damage to the layer to which the coating solution is applied. Specifically, a coating solution that is difficult to dissolve the layer to which the coating solution is applied is preferable.

Examples of the solvent contained in the coating solution include the same solvents as those exemplified in the active layer forming step.
The coating liquid used in the present invention may contain two or more kinds of solvents, and may contain two or more kinds of solvents. The solvent is preferably 1 to 10,000 times by weight and more preferably 10 to 1000 times by weight with respect to the material for forming the electron injection layer described later.

  The coating liquid containing a solvent and an alkaline earth metal oxide described later is preferably filtered with a Teflon (registered trademark) filter having a pore size of 0.5 μm.

(Cathode formation process)
There is no restriction | limiting in particular in the formation method of a cathode. The cathode can be formed by vacuum deposition, sputtering, ion plating, plating, coating, or the like. When the material of the cathode is polyaniline and derivatives thereof, polythiophene and derivatives thereof, nanoparticles (nanowires), emulsions (emulsions) or suspensions (suspensions) containing nanotubes, the cathode is preferably formed by a coating method. be able to. When the cathode material includes a conductive substance, the cathode may be formed by a coating method using a coating liquid containing a conductive material, a metal ink, a metal paste, a molten low melting point metal, or the like. Examples of the coating method for the coating solution include the same methods as those exemplified in the step of forming the active layer.

  Examples of the conductive substance that can be contained in the above emulsion or suspension include metals such as gold and silver, oxides such as ITO, and carbon nanotubes. The cathode may be composed only of nanoparticles or nanofibers. In the cathode, nanoparticles or nanofibers may be dispersed in a predetermined medium such as a conductive polymer.

Examples of the solvent of the coating solution used when forming the cathode by a coating method include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, s-butylbesen, and t-butylbenzene. Halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, trichlorobenzene, etc. Examples include halogenated unsaturated hydrocarbon solvents, ether solvents such as tetrahydrofuran and tetrahydropyran, water, and alcohols.
Specific examples of the alcohol include methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, butoxyethanol, methoxybutanol and the like.
Moreover, the coating liquid used for this invention may contain 2 or more types of solvent, and may contain 2 or more types of solvent illustrated above.

(Sealing layer formation process)
In the method for manufacturing a photoelectric conversion element, the sealing layer may be formed on the electrode far from the support substrate or on the outside of the electrode so as not to contact the electrode. The sealing layer can be formed by any method according to the type of the material. For example, a vapor deposition method, a spin coating method, a dip method, or a spray method can be used. A previously formed layer structure may be pasted with a sealing material (adhesive).

(Formation process of UV cut layer)
For example, when taking in light from the support substrate side, a UV cut layer can be formed by disposing a UV cut film on the surface of the support substrate opposite to the surface on which the electrodes are formed.
When capturing light from the electrode farther from the support substrate, when forming the sealing layer after forming the electrode far from the support substrate, before forming the sealing layer, between the electrode and the sealing layer A UV cut layer may be formed by disposing a UV cut film, or after forming the electrode and the sealing layer, a UV cut layer may be formed by disposing a UV cut film outside the sealing layer. May be.

<2> Photoelectric conversion element The photoelectric conversion element obtained by the manufacturing method of this invention is demonstrated below.
The photoelectric conversion element obtained by the production method of the present invention is
An anode, an active layer containing a perovskite compound, an electron transport layer and a cathode;
A layer formed by using a composition containing a metal oxide precursor and a fullerene or a fullerene derivative between an active layer and a cathode;
A layer is formed using a composition containing a metal oxide precursor on the side close to the active layer between the active layer and the cathode, and a composition containing fullerene or a fullerene derivative is used on the side close to the cathode of the active layer and the cathode. It is a layer obtained by forming a layer.
The photoelectric conversion element obtained by the production method of the invention may further have a support substrate, a hole injection layer, a hole transport layer, an electron injection layer, a sealing layer and / or a UV cut layer.
Hereinafter, the support substrate, the anode, the hole injection layer, the hole transport layer, the active layer containing the perovskite compound, the electron transport layer, the electron injection layer, the cathode, the sealing layer, and the UV cut layer will be described in detail. However, the photoelectric conversion element obtained by the manufacturing method of the present invention is not limited to the photoelectric conversion element having all these layers.

(Support substrate)
The photoelectric conversion element obtained by the production method of the present invention is usually formed on a support substrate. As the support substrate, a substrate that is not chemically changed when a photoelectric conversion element is manufactured is preferably used. Examples of the support substrate include a glass substrate, a plastic substrate, a polymer film, and a silicon plate. Although the light transmittance of a support substrate is not specifically limited, In the case of the photoelectric conversion element which takes in light from the support substrate side, a board | substrate with high light transmittance is used suitably for a support substrate. On the other hand, when producing a photoelectric conversion element on a support substrate with low light transmittance, light cannot be taken in from the electrode side closer to the support substrate. Therefore, it is preferable to use an electrode with high light transmittance as the electrode far from the support substrate. By using the electrode, light can be taken in from an electrode farther from the support substrate side even if a support substrate with low light transmittance is used.

(anode)
The anode can take the form of a single layer or a stack of multiple layers. As an anode material, conductive metal oxides, metals, and organic substances such as conductive polymers can be used. Specifically, indium oxide, zinc oxide, tin oxide, indium tin oxide (Indium Tin Oxide: abbreviated as ITO), fluorinated tin oxide (FLUORINE Tin Oxide: abbreviated as FTO), indium zinc oxide (Indium Zinc Oxide: Abbreviation IZO), gold, platinum, silver, copper, aluminum, polyaniline and derivatives thereof, and polythiophene and derivatives thereof. Among these, a thin film of ITO, FTO, IZO, or tin oxide is preferably used for the anode.
At least one of the anode and the cathode described later is preferably transparent or translucent. Examples of transparent or translucent electrode materials include conductive metal oxides, metals, etc. If these materials are not transparent, they should be thin enough to transmit light. Or it can be set as a transparent or semi-transparent electrode by setting it as a grid | lattice form.
Specific examples of the transparent or translucent electrode material include indium oxide, zinc oxide, tin oxide, ITO, IZO and NESA, gold, platinum, silver and copper, which are composites thereof. The material of the bright or translucent electrode preferably contains one or more selected from the group consisting of tin oxide, ITO, and IZO.

(Hole injection layer)
In the photoelectric conversion element obtained by the production method of the present invention, a hole injection layer is preferably provided between the anode and the active layer.
The hole injection layer has a function of promoting hole injection into the anode. The hole injection layer is preferably provided in contact with the anode. The material for the hole injection layer is preferably a material that can make the formed hole injection layer insoluble in water.
The material that can make the formed hole injection layer insoluble in water may be either an organic material or an inorganic material. In addition, two or more materials that can make the formed hole injection layer insoluble in water may be used in combination.

  Materials for the hole injection layer that can make the formed hole injection layer insoluble in water include polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, and repeating units having an aromatic amine residue. Examples thereof include polymer compounds such as polymer compounds, low molecular compounds such as aniline, thiophene, pyrrole, and aromatic amine compounds, and inorganic compounds such as CuSCN and CuI. Among the polymer compounds that are materials that can make the formed hole injection layer insoluble in water, from the viewpoint of extending the lifetime of the obtained photoelectric conversion element, a repeating unit having an aromatic amine residue It is preferable that it is a high molecular compound containing.

Specific examples of the aromatic amine compound include the following.

The aromatic amine compound preferably includes a phenyl group having at least three substituents.
Examples of the substituent that the phenyl group contained in the aromatic amine compound may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an amino group, and a silyl group.

Specific examples of the aromatic amine compound containing a phenyl group having at least three substituents include the following.

In the polymer compound containing a repeating unit having an aromatic amine residue, the repeating unit having an aromatic amine residue is a repeating unit obtained by removing two hydrogen atoms from the aromatic amine compound. The polymer compound containing a repeating unit having an aromatic amine residue preferably contains a phenyl group having at least three substituents.
Examples of the repeating unit having an aromatic amine residue include a repeating unit represented by the following formula (1 ′).

In Formula (1 ′), Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represent an arylene group (A1) or a divalent heterocyclic group (B1). E ₁ ′, E ₂ ′ and E ₃ ′ each independently represent an aryl group (A2 ′) or a monovalent heterocyclic group (B2 ′). a and b each independently represent 0 or 1, and 0 ≦ a + b ≦ 1.

  Arylene group (A1): The arylene group (A1) is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, a divalent group having a benzene ring or a condensed ring, and an independent benzene ring or condensed. A divalent group in which two or more rings are bonded directly or through a group such as vinylene is also included. The arylene group (A1) may have a substituent. Examples of the substituent that the arylene group (A1) may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, and an arylalkyl group. , Arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group, imine residue Amide group, acid imide group, monovalent heterocyclic group, carboxy group, substituted carboxy group, cyano group, etc., alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, Aryl group, aryloxy group Arylthio group, a substituted amino group, substituted silyl group, substituted silyloxy group, monovalent heterocyclic group are preferable. The number of carbon atoms of the arylene group which does not have a substituent is about 6-60 normally, Preferably it is 6-20.

Divalent heterocyclic group (B1): The divalent heterocyclic group (B1) is the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and the divalent heterocyclic group (B1) is It may have a substituent.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring are not only carbon atoms, but also oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, arsenic atoms, etc. A group containing a hetero atom in the ring. Examples of the substituent that the divalent heterocyclic group (B1) may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, and an arylthio group. , Arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, halogen atom, acyl group, acyloxy group , Imino group, amide group, imide group, monovalent heterocyclic group, carboxy group, substituted carboxy group, cyano group, etc., alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio Group, aryl group, aryloxy group, Riruchio group, a substituted amino group, substituted silyl group, substituted silyloxy group, monovalent heterocyclic group are preferable. The number of carbon atoms of the divalent heterocyclic group having no substituent is usually about 3 to 60.

  Aryl group (A2 ′): The aryl group (A2 ′) may have a substituent. Examples of the substituent that the aryl group (A2 ′) may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, and an arylalkyl. Groups, arylalkoxy groups, arylalkylthio groups, arylalkenyl groups, arylalkynyl groups, amino groups, substituted amino groups, silyl groups, substituted silyl groups, silyloxy groups, substituted silyloxy groups, monovalent heterocyclic groups, halogen atoms, etc. Can be mentioned. The number of carbon atoms of the aryl group not having a substituent is usually about 6 to 30, and preferably 6 to 20.

  Monovalent heterocyclic group (B2 ′): The monovalent heterocyclic group (B2 ′) may have a substituent. Examples of the substituent that the monovalent heterocyclic group (B2 ′) may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, and an arylthio group. Group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, monovalent heterocyclic group, A halogen atom etc. are mentioned. The number of carbon atoms of the monovalent heterocyclic group having no substituent is usually about 1-30.

  As the repeating unit represented by the formula (1 ′), a repeating unit represented by the following formula (1) is preferable.

In formula (1), Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ represent the same meaning as described above. E ₁ , E ₂ and E ₃ each independently represent an aryl group (A2) or a monovalent heterocyclic group (B2) defined as follows. a and b represent the same meaning as described above.

  Aryl group (A2): The aryl group (A2) is an alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy Selected from the group consisting of a group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a monovalent heterocyclic group, and a halogen atom An aryl group having three or more substituents. The number of carbon atoms of the aryl group (A2) is usually about 6 to 40, preferably 6 to 30.

  Monovalent heterocyclic group (B2): The monovalent heterocyclic group (B2) is an alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, alkylthio group, cycloalkylthio group, aryl group, aryloxy group, arylthio group. Group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, monovalent heterocyclic group and A monovalent heterocyclic group having one or more substituents selected from the group consisting of halogen atoms, and the sum of the number of substituents and the number of heteroatoms in the heterocyclic ring is 3 or more. The number of carbon atoms of the monovalent heterocyclic group (B2) is usually about 1 to 40.

  The aryl group (A2) is preferably a phenyl group having 3 or more substituents, a naphthyl group having 3 or more substituents, or an anthracenyl group having 3 or more substituents. A group represented by the formula (2) is more preferable.

In formula (2), Re, Rf and Rg are each independently an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group. Represents an arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, monovalent heterocyclic group or halogen atom.

The polymer compound containing a repeating unit having an aromatic amine residue may further have a repeating unit represented by the following formula (3), formula (4), formula (5) or formula (6). .

−Ar ₁₂ − (3)

—Ar ₁₂ —X ₁ — (Ar ₁₃ —X ₂ ) _c —Ar ₁₄ — (4)

-Ar ₁₂ -X _2- (5)

-X _2- (6)

In formulas (3) to (6), Ar ₁₂ , Ar ₁₃ and Ar ₁₄ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure. X ₁ represents —CR ₂ ═CR ₃ —, —C≡C—, or (SiR ₅ R ₆ ) _d —. X ₂ represents —CR ₂ ═CR ₃ —, —C≡C—, —N (R ₄ ) —, or (SiR ₅ R ₆ ) _d —. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, a carboxy group, a substituted carboxy group or a cyano group. R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or an arylalkyl group. c represents an integer of 0-2. d represents an integer of 1 to 12. When a plurality of Ar ₁₃ , R ₂ , R ₃ , R ₅ and R ₆ are present, they may be the same or different. )

Examples of the repeating unit represented by the formula (1 ′) (including examples of the repeating unit represented by the formula (1)) include Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently having a substituent. It is a phenylene group that does not have, and includes a repeating unit of a = 1 and b = 0, and specific examples thereof include a repeating unit represented by the following formula.

As examples of the repeating unit represented by the formula (1 ′) (including examples of the repeating unit represented by the formula (1)), Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are each independently a substituent. A repeating unit having a = 0 and b = 1, and specific examples thereof include a repeating unit represented by the following formula.

  In the above formulae, Me represents a methyl group, Pr represents a propyl group, Bu represents a butyl group, MeO represents a methoxy group, and BuO represents a butyloxy group.

(Hole transport layer)
The hole transport layer is provided between the hole injection layer and the active layer and has a function of an electron block. By providing the hole transport layer, a more efficient photoelectric conversion element can be obtained. Examples of the hole transport layer include a low molecular compound having an aromatic amine residue and a polymer compound containing a repeating unit having an amine residue. When a low molecular compound having an aromatic amine residue or a polymer compound having an aromatic amine residue as a repeating unit is used for the hole injection layer, such a hole transport layer may not be provided. .

(Active layer)
The active layer includes a perovskite compound. The active layer may contain other components in addition to the perovskite compound. Examples of other components that can be included in the active layer include an electron-donating compound, an electron-accepting compound, an ultraviolet absorber, an antioxidant, and a sensitizer for sensitizing the function of generating charge by absorbed light, Examples thereof include a light stabilizer for increasing stability to ultraviolet light and a binder for enhancing mechanical properties.
The perovskite compound is preferably a perovskite compound having an organic-inorganic hybrid structure. The perovskite compound is preferably a compound represented by any one of the following formulas (7) to (9).

CH ₃ NH ₃ M ¹ X ₃ (7)

In formula (7), M ₁ is a divalent metal, and X is independently F, Cl, Br or I.
Examples of the divalent metal represented by M ¹ include Cu, Ni, Mn, Fe, Co, Pd, Ge, Sn, Pb, and Eu.

(R ¹ NH ₃ ) ₂ M ¹ X ₄ (8)

In Formula (8), R ¹ is an alkyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an aryl having 7 to 40 carbon atoms. An alkyl group, an aryl group having 6 to 30 carbon atoms, and a monovalent heterocyclic group having 1 to 30 carbon atoms, and M ¹ and X are as defined above.

HC (= NH) NH ₂ M ¹ X ₃ (9)

In formula (9), M ¹ and X are as defined above.

In formula (8), the alkyl group represented by R ¹ may be linear or branched, and the alkyl group represented by R ¹ may have 2 to 30 carbon atoms. preferable.
Examples of the alkyl group represented by R ¹ include an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, an isooctyl group, a nonyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. , Pentadecyl group, octadecyl group, icosanyl group, docosanyl group, triacontanyl group, and tetracontanyl group.

The cycloalkyl group represented by R ¹ preferably has 3 to 30 carbon atoms.
Examples of the cycloalkyl group represented by R ¹ include a cyclopentyl group and a cyclohexyl group.

The number of carbon atoms of the alkenyl group represented by R ¹ is preferably 2-20.
Examples of the alkenyl group represented by R ¹ include a vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, oleyl group, and allyl group.

The number of carbon atoms of the arylalkyl group represented by R ¹ is preferably 7-30.
Examples of the arylalkyl group represented by R ¹ include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.

The number of carbon atoms of the aryl group represented by R ¹ is preferably 6-20. Examples of the aryl group represented by R ¹ include a phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, and indenyl group. , Pyrenyl group, biphenylyl group and the like.

The number of carbon atoms of the monovalent heterocyclic group represented by R ¹ is preferably 1-20. Examples of the monovalent heterocyclic group represented by R ¹ include pyrrolidyl group, imidazolidinyl group, morpholyl group, oxazolyl group, oxazolidinyl group, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, Examples thereof include a triazinyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, a quinazolinyl group, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group, and a phthalazinyl group.

  Only one perovskite compound may be used as the material for the active layer, or a plurality of perovskite compounds may be used.

The perovskite compound in the present invention is preferably a compound represented by the formula (7). Of the compounds represented by formula (7), CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbBr ₃ , CH ₃ NH ₃ SnI ₃ , CH ₃ NH ₃ SnCl ₃ , CH ₃ NH More preferably, it is ₃ SnBr ₃ or the like.

(Electron transport layer)
The photoelectric conversion element obtained by the manufacturing method of this invention has an electron carrying layer formed using the composition containing a metal oxide precursor and fullerene or a fullerene derivative.
The photoelectric conversion element obtained by the production method of the present invention may have another electron transport layer including a metal oxide precursor and a composition other than the composition containing fullerene or a fullerene derivative.

(Electron injection layer)
The photoelectric conversion element obtained by the production method of the present invention may have a layer containing an alkaline earth metal oxide as the electron injection layer. The alkaline earth metal oxide is preferably one or more selected from the group consisting of CaO, BaO and SrO, more preferably BaO and / or SrO, and even more preferably BaO.

(cathode)
The cathode can take the form of a single layer or a stack of multiple layers. A metal, a conductive polymer, etc. can be used for the material of a cathode.
Examples of the cathode material include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, gold, Metals such as silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, alloys containing two or more metals selected from the group consisting of these metals, graphite, and graphite intercalation compounds are used.
Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy and the like.

  Examples of the material for the cathode having high light transmittance include conductive metal oxides and metals. When the transmittance of these materials is not high, a cathode having high light transmittance can be obtained by forming a thin film with a thickness enough to transmit light or a lattice structure. Specifically, indium tin oxide (ITO), indium zinc oxide (IZO), NESA, gold, platinum, silver, and copper, which are indium oxide, zinc oxide, tin oxide, and composites thereof, are used. The cathode material is preferable because it contains one or more selected from the group consisting of ITO, IZO and tin oxide.

(Sealing layer)
A sealing layer may be provided on the electrode side farther from the support substrate. The sealing layer can be formed of a material having a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of the material of the sealing layer include organic materials such as resins such as polyethylene trifluoride, polytrifluoroethylene chloride (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer. Examples thereof include inorganic materials such as materials, silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

(UV cut layer)
The photoelectric conversion element obtained by the production method of the present invention may have a UV cut layer. Examples of the material for the UV cut layer include a UV cut film having a light transmittance of 50% or less at a wavelength of 442 nm or less. The transmittance of light having a wavelength of 482 nm or less in the UV cut film is preferably 50% or less. The restriction on the long wavelength side of the wavelength at which the light transmittance is 50% or less is preferably shorter than the absorption edge of the absorption wavelength of the active layer containing the perovskite compound.
As a material for the UV cut layer, a commercially available UV cut film can be appropriately used. As the UV cut film, two or more kinds of UV cut films may be used in an overlapping manner.

<3> Use of photoelectric conversion element The photoelectric conversion element obtained by the production method of the present invention can be operated as a solar cell by generating photovoltaic power between the electrodes by irradiating light such as sunlight. . Moreover, it can also be used as a thin film solar cell module by integrating a plurality of solar cells.

  In addition, the photoelectric conversion element obtained by the manufacturing method of the present invention operates as an organic photosensor by irradiating light to a transparent or translucent electrode with a voltage applied between the electrodes, so that a photocurrent flows. be able to. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

(Preparation of Composition 1)
Composition 1 was prepared by dissolving 460 mg of lead iodide in 1.25 mL of N, N-dimethylformamide and completely dissolving it by stirring at 70 ° C.

(Preparation of composition 2)
Composition 2 was prepared by completely dissolving 55 mg of methylammonium iodide in 1 mL of 2-propanol.

(Preparation of composition 3)
By mixing 2 parts by weight of [6,6] -phenyl C61-butyric acid methyl ester (C60PCBM) (E100 manufactured by Frontier Carbon Co.) as a fullerene derivative and 100 parts by weight of chlorobenzene as a solvent, Composition 3 was prepared.

(Production of Composition 4)
0.5 part by weight of a polymer compound having the following repeating unit (Poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine], average Mn 7,000-10,000, manufactured by Sigma-Aldrich), The composition 4 shown below was prepared by mixing and completely dissolving 100 parts by weight of chlorobenzene as a solvent.

(Preparation of composition 5)
1 part by weight of [6,6] -phenyl C61-butyric acid methyl ester (C60PCBM) (E100 manufactured by Frontier Carbon Co.) as a fullerene derivative and 1 part by weight of titanium tetraisopropoxide (manufactured by Sigma-Aldrich) as a solvent and 100 The composition 5 was prepared by mixing with a weight part chlorobenzene and making it completely dissolve.

(Preparation of composition 6)
As a fullerene derivative, 2 parts by weight of [6,6] -phenyl C61-butyric acid methyl ester (C60PCBM) (E100 manufactured by Frontier Carbon), 0.2 parts by weight of titanium tetraisopropoxide (manufactured by Sigma-Aldrich) and a solvent As a result, 100 parts by weight of chlorobenzene was mixed and completely dissolved to prepare composition 6.

(Preparation of composition 7)
As a fullerene derivative, 0.2 part by weight of [6,6] -phenyl C61-butyric acid methyl ester (C60PCBM) (E100 manufactured by Frontier Carbon), 2 parts by weight of titanium tetraisopropoxide (manufactured by Sigma-Aldrich), and a solvent As a result, 100 parts by weight of chlorobenzene was mixed and completely dissolved to prepare composition 7.

(Preparation of composition 8)
Composition 8 was prepared by mixing and completely dissolving 2 parts by weight of titanium (IV) isopropoxide (manufactured by Sigma-Aldrich) and 100 parts by weight of chlorobenzene as a solvent.

(Preparation of composition 9)
Composition 9 was prepared by mixing 1 part by weight of titanium (IV) isopropoxide (manufactured by Sigma-Aldrich) with 100 parts by weight of isopropanol as a solvent and completely dissolving them.

Example 1
(Production and evaluation of solar cells)
A glass substrate on which an ITO thin film that functions as an anode of a solar cell was formed was prepared. The ITO thin film was formed by the sputtering method, and the thickness was 150 nm. The glass substrate having the ITO thin film was subjected to ozone UV treatment to treat the surface of the ITO thin film. Composition 4 was applied by spin coating, and heated at 120 ° C. for 10 minutes in the atmosphere to form a hole injection layer having a thickness of about 10 nm. The substrate on which the hole injection layer was formed was sufficiently heated to 70 ° C. with a hot plate, and then the heated substrate was placed on a spin coater, and the composition 1 that was stirred and heated at 70 ° C. on this hole injection layer by spin coating. The film was applied by spin coating at a rotational speed of 2000 rpm and air-dried in a nitrogen atmosphere to obtain a lead iodide coating film. Thereafter, the composition 2 was dropped on the lead iodide coating film, spin-coated at 6000 rpm, and dried in air at 100 ° C. for 10 minutes to form an active layer. The thickness of the active layer was about 350 nm.

Next, the composition 5 was formed on the active layer by spin coating to form an electron transport layer having a thickness of about 50 nm. Thereafter, BaO (manufactured by Sigma-Aldrich) was vapor-deposited with a film thickness of 2 nm by a vacuum vapor deposition machine, and then gold was vapor-deposited with a film thickness of 60 nm. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻³ Pa. Thereafter, in a nitrogen gas atmosphere, a solar cell was manufactured by bonding and sealing the sealing glass to the cathode side surface of the photoelectric conversion element by UV curing using a UV curable epoxy resin. The shape of the solar cell thus obtained was a 2 mm × 2 mm square.

After pasting a UV cut film (LR2CLAR made by 3M) to the obtained solar cell, using a solar simulator (trade name YSS-80A: AM1.5G filter, irradiance 100 mW / cm ² manufactured by Yamashita Denso). The initial photoelectric conversion efficiency (initial efficiency) was measured by irradiating constant light and measuring the generated current and voltage. The initial photoelectric conversion efficiency was 15.0%. Thereafter, the solar cell with a UV cut film (photoelectric conversion element) was held in a weather resistance tester (Ci4000 manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a constant temperature of 65 ° C. with a light intensity of 1 Sun for 66 hours, and then a solar simulator ( Yamashita Denso, trade name YSS-80A: AM1.5G filter, irradiance of 100 mW / cm ² ) irradiates the solar cell with constant light, measures the generated current and voltage, Conversion efficiency was measured. The value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) was calculated as the retention rate, and is shown in Table 1 together with the composition used for forming the electron transport layer.

Example 2
(Production and evaluation of solar cells)
A solar cell was produced in the same manner as in Example 1 except that the composition 5 in Example 1 was changed to the composition 6 to obtain an electron transport layer having a film thickness of about 50 nm, and the initial photoelectric conversion efficiency and 66 hours later were obtained. The photoelectric conversion efficiency was measured. The initial photoelectric conversion efficiency was 17.6%. The value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) was calculated as the retention rate, and is shown in Table 1 together with the composition used for forming the electron transport layer.

Example 3
(Production and evaluation of solar cells)
A solar cell was produced in the same manner as in Example 1 except that the composition 5 in Example 1 was changed to the composition 7 to obtain an electron transport layer having a film thickness of about 50 nm, and the initial photoelectric conversion efficiency and 66 hours later were obtained. The photoelectric conversion efficiency was measured. The initial photoelectric conversion was 6.7%. The value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) was calculated as the retention rate, and is shown in Table 1 together with the composition used for forming the electron transport layer.

Example 4
(Production and evaluation of solar cells)
A glass substrate on which an ITO thin film that functions as an anode of a solar cell was formed was prepared. The ITO thin film was formed by the sputtering method, and the thickness was 150 nm. The glass substrate having the ITO thin film was subjected to ozone UV treatment to treat the surface of the ITO thin film. Composition 4 was applied by spin coating, and heated at 120 ° C. for 10 minutes in the atmosphere to form a hole injection layer having a thickness of about 10 nm. The substrate on which the hole injection layer was formed was sufficiently heated to 70 ° C. with a hot plate, and then the heated substrate was placed on a spin coater, and the composition 1 that was stirred and heated at 70 ° C. on this hole injection layer by spin coating. The film was applied by spin coating at a rotational speed of 2000 rpm and air-dried in a nitrogen atmosphere to obtain a lead iodide coating film. Thereafter, the composition 2 was dropped on the lead iodide coating film, spin-coated at 6000 rpm, and dried in air at 100 ° C. for 10 minutes to form an active layer. The thickness of the active layer was about 350 nm.

  Next, the composition 8 is formed on the active layer by spin coating to form a layer having a thickness of about 20 nm. Further, the composition 3 is formed on the obtained layer by spin coating to obtain a thickness of about 20 nm. An electron transport layer was formed by forming a 50 nm layer.

Thereafter, BaO (manufactured by Sigma-Aldrich) was vapor-deposited with a film thickness of 2 nm by a vacuum vapor deposition machine, and then gold was vapor-deposited with a film thickness of 60 nm. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻³ Pa. Thereafter, in a nitrogen gas atmosphere, a solar cell was manufactured by bonding and sealing the sealing glass to the cathode side surface of the photoelectric conversion element by UV curing using a UV curable epoxy resin. The shape of the solar cell thus obtained was a 2 mm × 2 mm square.

After pasting a UV cut film (LR2CLAR made by 3M) to the obtained solar cell, using a solar simulator (trade name YSS-80A: AM1.5G filter, irradiance 100 mW / cm ² manufactured by Yamashita Denso). The initial photoelectric conversion efficiency (initial efficiency) was measured by irradiating constant light and measuring the generated current and voltage. The initial photoelectric conversion efficiency was 4.1%. Thereafter, the solar cell with a UV cut film (photoelectric conversion element) was held in a weather resistance tester (Ci4000 manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a constant temperature of 65 ° C. with a light intensity of 1 Sun for 66 hours, and then a solar simulator ( Yamashita Denso, trade name YSS-80A: AM1.5G filter, irradiance of 100 mW / cm ² ) irradiates the solar cell with constant light, measures the generated current and voltage, Conversion efficiency was measured. The value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) was calculated as the retention rate, and is shown in Table 1 together with the composition used for forming the electron transport layer.

Example 5
(Production and evaluation of solar cells)
A solar cell was produced in the same manner as in Example 1 except that the UV cut film in Example 1 was not attached, and the initial photoelectric conversion efficiency and the photoelectric conversion efficiency after 66 hours were measured. The initial photoelectric conversion efficiency was 13.6%. The value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) was calculated as a retention rate and shown in Table 2 together with the composition used for forming the electron transport layer.

Comparative Example 1
(Production and evaluation of solar cells)
A solar cell was produced in the same manner as in Example 1 except that the composition 5 in Example 1 was changed to the composition 3 to obtain an electron transport layer having a film thickness of about 50 nm, and the initial photoelectric conversion efficiency and 66 hours later were obtained. The photoelectric conversion efficiency was measured. The initial photoelectric conversion was 16.5%. The value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) was calculated as the retention rate, and is shown in Table 1 together with the composition used for forming the electron transport layer.

Comparative Example 2
(Production and evaluation of solar cells)
A solar cell was fabricated in the same manner as in Example 4 except that the composition 3 in Example 4 was formed by spin coating and the step of forming a layer was not performed, and the initial photoelectric conversion efficiency and 66 hours later were obtained. The photoelectric conversion efficiency was measured. The initial photoelectric conversion efficiency was 3.3%. The value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) was calculated as the retention rate, and is shown in Table 1 together with the composition used for forming the electron transport layer.

Comparative Example 3
(Production and evaluation of solar cells)
A glass substrate on which an ITO thin film that functions as an anode of a solar cell was formed was prepared. The ITO thin film was formed by the sputtering method, and the thickness was 150 nm. The glass substrate having the ITO thin film was subjected to ozone UV treatment to treat the surface of the ITO thin film. Composition 4 was applied by spin coating, and heated at 120 ° C. for 10 minutes in the atmosphere to form a hole injection layer having a thickness of about 10 nm. The substrate on which the hole injection layer was formed was sufficiently heated to 70 ° C. with a hot plate, and then the heated substrate was placed on a spin coater, and the composition 1 that was stirred and heated at 70 ° C. on this hole injection layer by spin coating. The film was applied by spin coating at a rotational speed of 2000 rpm and air-dried in a nitrogen atmosphere to obtain a lead iodide coating film. Thereafter, the composition 2 was dropped on the lead iodide coating film, spin-coated at 6000 rpm, and dried in air at 100 ° C. for 10 minutes to form an active layer. The thickness of the active layer was about 350 nm.

  Next, the composition 3 is formed on the active layer by spin coating to form a layer having a film thickness of about 50 nm. Further, the composition 9 is formed on the obtained layer by spin coating, and the film thickness is about An electron transport layer was formed by forming a 30 nm layer.

Thereafter, BaO (manufactured by Sigma-Aldrich) was vapor-deposited with a film thickness of 2 nm by a vacuum vapor deposition machine, and then gold was vapor-deposited with a film thickness of 60 nm. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻³ Pa. Thereafter, in a nitrogen gas atmosphere, a solar cell was manufactured by bonding and sealing the sealing glass to the cathode side surface of the photoelectric conversion element by UV curing using a UV curable epoxy resin. The shape of the solar cell thus obtained was a 2 mm × 2 mm square.

After pasting a UV cut film (LR2CLAR made by 3M) to the obtained solar cell, using a solar simulator (trade name YSS-80A: AM1.5G filter, irradiance 100 mW / cm ² manufactured by Yamashita Denso). The initial photoelectric conversion efficiency (initial efficiency) was measured by irradiating constant light and measuring the generated current and voltage. The initial photoelectric conversion efficiency was 14.4%. Thereafter, the solar cell with a UV cut film (photoelectric conversion element) was held in a weather resistance tester (Ci4000 manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a constant temperature of 65 ° C. with a light intensity of 1 Sun for 66 hours, and then a solar simulator ( Yamashita Denso, trade name YSS-80A: AM1.5G filter, irradiance of 100 mW / cm ² ) irradiates the solar cell with constant light, measures the generated current and voltage, Conversion efficiency was measured. The value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) was calculated as the retention rate, and is shown in Table 1 together with the composition used for forming the electron transport layer.

Comparative Example 4
(Production and evaluation of solar cells)
A solar cell was produced in the same manner as in Comparative Example 1 except that the UV cut film in Comparative Example 1 was not attached, and the initial photoelectric conversion efficiency and the photoelectric conversion efficiency after 66 hours were measured. The initial photoelectric conversion efficiency was 15.8%. The value of (photoelectric conversion efficiency after 66 hours) / (initial photoelectric conversion efficiency) was calculated as the retention rate, and is shown in Table 2 together with the composition used for forming the electron transport layer.

  As is clear from Tables 1 and 2, the photoelectric conversion element of Example 1-4 and the photoelectric conversion element of Example 5 are respectively compared with the photoelectric conversion element of Comparative Example 1-3 and the photoelectric conversion element of Comparative Example 4. The retention rate was remarkably high and it had high durability against light irradiation.

Claims (7)

A method for producing a photoelectric conversion element having an anode, an active layer containing a perovskite compound, an electron transport layer, and a cathode,
Forming the electron transport layer,
Forming a layer between the active layer and the cathode using a composition containing a metal oxide precursor and fullerene or a fullerene derivative, or
A step of forming a layer using a composition containing a metal oxide precursor on the side close to the active layer between the active layer and the cathode; and a fullerene or fullerene derivative on the side close to the cathode between the active layer and the cathode. The manufacturing method of a photoelectric conversion element which is a process which has a process of forming a layer using the composition containing. A method for producing a photoelectric conversion element having an anode, an active layer containing a perovskite compound, an electron transport layer and a cathode in this order,
A step of forming an anode, a step of forming an active layer containing a perovskite compound, a step of forming an electron transport layer, and a step of forming a cathode in this order,
Forming the electron transport layer,
Forming a layer using a composition comprising a metal oxide precursor and fullerene or a fullerene derivative, or
A method for producing a photoelectric conversion element, comprising: a step of forming a layer using a composition containing a metal oxide precursor; and a step of forming a layer using a composition containing fullerene or a fullerene derivative in this order. .   The manufacturing method of the photoelectric conversion element of Claim 1 or 2 whose said metal oxide precursor is a precursor of a titanium oxide.   The manufacturing method of the photoelectric conversion element as described in any one of Claims 1-3 whose said metal oxide precursor is a metal alkoxide.   The photoelectric conversion element obtained by the manufacturing method of the photoelectric conversion element as described in any one of Claims 1-4.   A solar cell module comprising the photoelectric conversion element according to claim 5.   An organic optical sensor comprising the photoelectric conversion element according to claim 5.