JP2015105233A - Fullerene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic photoelectric conversion element excellent in photoelectric conversion efficiency.SOLUTION: A fullerene derivative is provided, in which one or more methanofullerene structures formed by bridging two carbon atoms constituting a fullerene ring are included and a carbon atom constituting the methanofullerene structure is replaced by an aryl group, a heteroaryl group, or the like. A composition comprising the fullerene derivative and an electron-donating compound that is a polymeric compound is provided. An organic photoelectric conversion element including the composition is also provided.

Description

  The present invention relates to a fullerene derivative, and further relates to a composition containing such a fullerene derivative and an organic photoelectric conversion device including a layer containing such fullerene derivative or composition.

  Application of organic semiconductor materials having a charge transporting property (electron transporting property or hole transporting property) to organic photoelectric conversion elements used in organic solar cells, optical sensors, and the like has been studied. For example, fullerene derivatives that are organic semiconductor materials are being studied for application to organic solar cells. As such a fullerene derivative, for example, [6,6] -phenyl C61-butyric acid methyl ester (hereinafter referred to as [60] -PCBM) is known (see Non-Patent Document 1).

Advanced Functional Materials Vol.13 (2003) 85p

  However, an organic photoelectric conversion element including a layer containing [60] -PCBM has a problem that the photoelectric conversion efficiency is not necessarily high enough.

  Then, an object of this invention is to provide the fullerene derivative which can implement | achieve the outstanding photoelectric conversion efficiency, when it uses for an organic photoelectric conversion element.

（式（１）中、環Ｆはフラーレン環を表す。ｎ個のＣ１は環Ｆを構成する２個の炭素原子を架橋してメタノフラーレン構造を構成する炭素原子を表す。置換基Ｒをｍ個有するＡｒ^１は置換基Ｒをｍ個有するアリール基又は置換基Ｒをｍ個有するヘテロアリール基を表す。置換基Ｒは下記式（２）で表される構造を有する。Ａｒ^２は、置換基を有していてもよいアリール基（ただし、該置換基からは前記置換基Ｒは除かれる。）又は置換基を有していてもよいヘテロアリール基を表す。ｍ及びｎはそれぞれ独立に１以上の整数を表す。）

（式（２）中、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に水素原子又は１価の置換基を表す。ｐ及びｑはそれぞれ独立に１以上の整数を表す。）
［２］置換基Ｒを有する前記Ａｒ^１が置換基Ｒをｍ個有するアリール基であり、Ａｒ^２がアリール基である、［１］に記載のフラーレン誘導体。
［３］［１］又は［２］に記載のフラーレン誘導体と電子供与性化合物とを含む組成物。
［４］前記電子供与性化合物が高分子化合物である、［３］に記載の組成物。
［５］［１］又は［２］に記載のフラーレン誘導体を含む層を備える有機光電変換素子。
［６］［３］又は［４］に記載の組成物を含む層を備える有機光電変換素子。 That is, the present invention provides the following [1] to [6].
[1] A fullerene derivative represented by the following formula (1).

(In formula (1), ring F represents a fullerene ring. N C1s represent carbon atoms constituting a methanofullerene structure by bridging two carbon atoms constituting ring F. .Ar ² Ar ¹ is having the structure. substituent R representing a heteroaryl group having m pieces an aryl group or a substituent R having the m substituents R represented by the following formula (2) into individual organic is substituted An aryl group which may have a group (however, the substituent R is excluded from the substituent) or a heteroaryl group which may have a substituent, m and n are each independently Represents an integer of 1 or more.)

(In formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent substituent. P and q each independently represent an integer of 1 or more.)
[2] The fullerene derivative according to [1], wherein Ar ¹ having substituent R is an aryl group having m substituents R, and Ar ² is an aryl group.
[3] A composition comprising the fullerene derivative according to [1] or [2] and an electron donating compound.
[4] The composition according to [3], wherein the electron donating compound is a polymer compound.
[5] An organic photoelectric conversion device comprising a layer containing the fullerene derivative according to [1] or [2].
[6] An organic photoelectric conversion device comprising a layer containing the composition according to [3] or [4].

  If the fullerene derivative of this invention is used, the organic photoelectric conversion element which shows the outstanding photoelectric conversion efficiency can be provided.

  Hereinafter, the present invention will be described in detail.

<Fullerene derivative>
The fullerene derivative of the present invention is a fullerene derivative represented by the following formula (1).

In formula (1), ring F represents a fullerene ring. The fullerene from which the ring F which is a fullerene ring is derived is not particularly limited, and may be any of C ₆₀ fullerene, C ₇₀ fullerene, C ₈₂ fullerene, C ₈₄ fullerene and the like. Ring F is preferably a fullerene ring derived from C ₆₀ fullerene.

  In the formula (1), n C1s represent carbon atoms constituting a methanofullerene structure by bridging two carbon atoms constituting the ring F.

In formula (1), n is an integer of 1 or more. That is, the fullerene derivative of the present invention is a methanofullerene derivative in which Ar ¹ and Ar ² having a substituent R are bonded to C1 (for example, bis (methano) fullerene derivative, tris (methano) fullerene derivative, tetrakis (methano) Including a fullerene derivative).

In Formula (1), Ar ¹ bonded to C ¹ represents an aryl group having m substituents R or a heteroaryl group having m substituents R. When two or more Ar ¹ are present, the two or more Ar ¹ may be different from each other. Ar ¹ is preferably an aryl group having m substituents R.

The aryl group having m substituents R that is Ar ¹ is the remaining atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon in which m hydrogen atoms are substituted with the substituent R, and the benzene ring is And a group having a structure in which two or more independent benzene rings or two or more condensed rings are bonded directly or via a group such as vinylene. The number of carbon atoms in the aryl group portion excluding the substituent R is usually 6 to 60, and preferably 6 to 30.

  Examples of the aryl group having m substituents R include a phenyl group having m substituents R, a 1-naphthyl group having m substituents R, and a 2-naphthyl group having m substituents R. .

The heteroaryl group having m substituents R which is Ar ¹ refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound in which m hydrogen atoms are substituted with the substituent R. The number of carbon atoms in the heteroaryl group portion excluding the substituent R is usually about 4 to 60, and preferably 4 to 20.

  Here, the heterocyclic compound is not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a silicon atom as an element constituting the cyclic structure among organic compounds having a cyclic structure. A compound containing a heteroatom in the ring. As this heteroaryl group, an aromatic heteroaryl group is preferable.

Specific examples of the heteroaryl group having m substituents R that are Ar ¹ include thienyl groups (2-thienyl group, 3-thienyl group) having m substituents R, and pyrrolyl having m substituents R. Group, furyl group having m substituents R, pyridyl group having m substituents R, piperidyl group having m substituents R, quinolyl group having m substituents R, and isoquinolyl having m substituents R Groups.

  In formula (1), n is preferably 1 from the viewpoint of photoelectric conversion efficiency. M is preferably 1. More preferably, n and m are both 1.

  The substituent R has a structure represented by the following formula (2).

In formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent substituent. p and q each independently represents an integer of 1 or more.

As monovalent substituents represented by R ¹ , R ² and R ³ , an alkyl group optionally having a halogen atom, an aryl group, a heteroaryl group, a halogen atom and an alkoxy optionally having a halogen atom Groups.

R ¹ , R ² , and R ³ are preferably a hydrogen atom or an alkyl group that may have a halogen atom, and more preferably a hydrogen atom. R ³ is preferably an alkyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. When used in an organic photoelectric conversion element, the photoelectric conversion efficiency can be further increased, so that the halogen atom is preferably a fluorine atom.
Examples of the aryl group and heteroaryl group include groups capable of constituting Ar ² described later.

  The number of carbon atoms of the alkyl group is usually 1-20. The alkyl group may be linear, branched, or cyclic. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, sec-butyl group, 3-methylbutyl group, pentyl group, hexyl group and 2-ethylhexyl. Group, heptyl group, octyl group, nonyl group, decyl group and lauryl group.

  The alkyl group may have a halogen atom, and the halogen atom is preferably a fluorine atom. Examples of the alkyl group having a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

  The number of carbon atoms of the alkoxy group is usually 1-20. The alkyl group portion in the alkoxy group may be a chain or a ring. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, Examples include heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group.

  The alkoxy group may have a halogen atom, and the halogen atom is preferably a fluorine atom. Examples of the alkoxy group having a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.

  In formula (2), q is preferably 1 to 4, and more preferably 2 to 3. Further, p is preferably 1 to 4, and more preferably 2 to 3.

  The substituent R preferably has a structure represented by the following formula (3).

In formula (3), R ¹ , R ² , R ³ and q are as defined above. R ⁴ and R ⁵ have the same meanings as R ¹ , R ² and R ^3, and each independently represents a hydrogen atom or a monovalent substituent.

In formula (1), Ar ² is an aryl group which may have a substituent (however, the substituent R is excluded from this substituent) or a heteroaryl group which may have a substituent. Represents. When two or more Ar ² exist, two or more Ar ² may be different from each other. Ar ² is preferably an aryl group.

  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 are Both embodiments are included when substituted by a substituent.

The aryl group represented by Ar ² is an atomic group obtained by removing one hydrogen atom from an unsubstituted aromatic hydrocarbon, a group having a benzene ring, a group having a condensed ring, an independent benzene ring or A group in which two or more fused rings are bonded directly or via a group such as vinylene is also included. The number of carbon atoms of the aryl group is usually 6 to 60, and preferably 6 to 30. The number of carbon atoms of the aryl group does not include the number of carbon atoms of the substituent.
Examples of the aryl group represented by Ar ² include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

The heteroaryl group represented by Ar ² refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound. The number of carbon atoms in the heteroaryl group is usually about 4 to 60, preferably 4 to 20. The number of carbon atoms in the heteroaryl group does not include the number of carbon atoms in the substituent. The heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring are not only carbon atoms but also hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, silicon atoms, etc. A compound containing an atom in the ring. As the heteroaryl group, an aromatic heteroaryl group is preferable.

  Specific examples of the heteroaryl group include a thienyl group (2-thienyl group, 3-thienyl group), pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, and isoquinolyl group.

The substituent which the aryl group which may have a substituent represented by Ar ² or the heteroaryl group which may have a substituent may have R ¹ and R ² which have already been described. , R ³ is the same as the monovalent substituent. However, the substituent R is excluded from the substituent that the aryl group may have. In other words, the “aryl group optionally having substituent (s)” does not have the substituent R.

  Specific examples of the fullerene derivative represented by the formula (1) include the following compounds.

<Method for producing fullerene derivative>
The fullerene derivative of the present invention can be produced, for example, by reacting fullerene and a compound represented by the following formula (A).

In formula (A), Ar ¹ , Ar ² , and substituent R are as defined above.
The number of carbon atoms of fullerene used for the reaction of the fullerene and the compound represented by the formula (A) is not particularly limited. The fullerene that can be used may be any of C ₆₀ fullerene, C ₇₀ fullerene, C ₈₂ fullerene, C ₈₄ fullerene, etc., but C ₆₀ fullerene is preferably used.

  Preferable examples of the compound represented by the formula (A) include a compound represented by the following formula (B).

  Fullerene and the compound represented by the formula (A) can be reacted under solvent-free conditions, but are preferably reacted in a solvent.

  As a solvent that can be used for the reaction, an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, carbon disulfide, or the like can be used. Among these, it is preferable to use an aromatic hydrocarbon solvent or a halogenated aromatic hydrocarbon solvent.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, trimethylbenzene, cumene, ethylbenzene, tetralin and the like. Examples of the halogenated aromatic hydrocarbon solvent include chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene and the like. The solvent is preferably chlorobenzene or dichlorobenzene, and particularly preferably dichlorobenzene.

  The reaction between the fullerene and the compound represented by the formula (A) is usually performed at about the boiling point of the solvent used from 0 ° C., and preferably performed at about 50 ° C. to about the boiling point of the solvent.

  In the reaction of fullerene and the compound represented by the above formula (A), it is preferable that an alkoxide and a Lewis base compound coexist because the conversion rate can be improved.

  Examples of alkoxides that can be used include sodium methoxide, sodium ethoxide, sodium butoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, potassium butoxide, potassium phenoxide and the like. Among these, sodium methoxide, sodium ethoxide, sodium butoxide, and sodium phenoxide are preferable, and sodium methoxide is particularly preferable.

  Examples of Lewis base compounds that can be used include pyridine, piperidine, pyrimidine, quinoline, triethylamine, triphenylamine, and the like, preferably pyridine and piperidine, and particularly preferably pyridine.

  The reaction of fullerene and the compound represented by the formula (A) can be carried out in the atmosphere. However, the reaction can be carried out in an inert gas from the viewpoint of reducing by-products and improving the conversion rate. preferable. Examples of the inert gas include nitrogen gas and argon gas.

  The reaction of the fullerene and the compound represented by the formula (A) may be performed while irradiating light. The conversion can be improved by reacting while irradiating light. The light used for irradiating light preferably contains light having a wavelength in the ultraviolet region.

  After the reaction, the reaction product is allowed to cool to room temperature, and the solvent is distilled off under reduced pressure to obtain a reaction mixture.

  The reaction mixture usually contains the fullerene derivative of the present invention, reaction by-products, unreacted raw materials, and the like. The reaction mixture can be separated and purified by silica gel column chromatography to obtain a fullerene derivative.

  As a purification method for obtaining a high-purity fullerene derivative, for example, a method of purifying by silica gel column chromatography using carbon disulfide and acetate as developing solvents, and an aromatic hydrocarbon and acetate as developing solvents. The method of refine | purifying with the used silica gel column chromatography is mentioned. As a purification method for obtaining a high-purity fullerene derivative, a method for purification by silica gel column chromatography using an aromatic hydrocarbon and an acetate as a developing solvent is preferable. As silica gel column chromatography, silica gel flash column chromatography is preferable.

  The number of structures bonded to the fullerene ring can be adjusted by appropriately adjusting the reaction conditions such as the amount of compound (A) and fullerene used as raw materials, reaction time, reaction temperature, etc. By adjusting, a fullerene derivative having a desired number of structures bonded to the fullerene ring can be selectively obtained.

  Compound (A) can be produced, for example, according to the method described in Journal of Organic Chemistry (60 volumes, pages 532-538, 1995).

<Composition>
The fullerene derivative of the present invention can be used as an electron accepting compound or an electron donating compound, but is preferably used as an electron accepting compound. The fullerene derivative of the present invention can be suitably used, for example, as an electron accepting material for an organic photoelectric conversion element.

When the fullerene derivative of the present invention is used as an electron-accepting material for an organic photoelectric conversion element, only the fullerene derivative of the present invention can be used alone. It is preferable.
The electron donating compound that can be contained in the composition is preferably a polymer compound.

<Organic photoelectric conversion element>
The organic photoelectric conversion element using the fullerene derivative of the present invention has a pair of electrodes and a layer containing the fullerene derivative of the present invention between the pair of electrodes. When the fullerene derivative of the present invention is used as an electron-accepting compound, the organic photoelectric conversion element may include a layer containing only the fullerene derivative of the present invention as described above, and the fullerene derivative and the electron-donating compound of the present invention. And a layer containing a composition containing.

As an organic photoelectric conversion element using the fullerene derivative of the present invention,
1. A pair of electrodes, at least one of which is transparent or translucent, a first organic layer provided between the pair of electrodes and containing the fullerene derivative of the present invention as an electron-accepting compound, and the first organic layer 1. an organic photoelectric conversion device having a second organic layer containing an electron donating compound provided so as to be bonded; An organic photoelectric device having a pair of electrodes, at least one of which is transparent or translucent, and at least one organic layer provided between the pair of electrodes and containing the fullerene derivative of the present invention and an electron-donating compound as an electron-accepting compound A conversion element is preferred.

  From the viewpoint of including many heterojunction interfaces, the above-mentioned 2. The organic photoelectric conversion element of the structure is more preferable.

  Moreover, you may provide an additional layer in the organic photoelectric conversion element of this invention between the at least one electrode of a pair of electrodes, and the organic layer in this organic photoelectric conversion element. Examples of the additional layer include a charge transport layer and a buffer layer that transport holes or electrons. Examples of the material used for the buffer layer include halides or oxides of alkali metals or alkaline earth metals, and specifically lithium fluoride. In addition, fine particles of an inorganic semiconductor such as titanium oxide can be used.

  2. In the organic photoelectric conversion device, the amount of the fullerene derivative in the organic layer is preferably 10 parts by weight to 1000 parts by weight, and 50 parts by weight to 500 parts by weight with respect to 100 parts by weight of the electron donating compound. It is more preferable.

  The layer (organic layer) containing the fullerene derivative of the present invention is preferably a layer containing a composition containing the fullerene derivative of the present invention, and a layer containing a composition containing the fullerene derivative of the present invention and an electron donating compound. It is more preferable that The thickness of the organic layer is usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.

  The electron donating compound may be a low molecular compound or a high molecular compound. Examples of the low molecular weight compound include phthalocyanine, metal phthalocyanine, porphyrin, metal porphyrin, oligothiophene, tetracene, pentacene, and rubrene.

Examples of the polymer compound include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, Examples include polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and polyfluorene and derivatives thereof.
The electron donating compound is preferably a polymer compound from the viewpoint of coatability.

  Since the photoelectric conversion efficiency of the organic photoelectric conversion element can be increased, the electron donating compound is selected from the group consisting of a structural unit represented by the following formula (4) and a structural unit represented by the following formula (5). The polymer compound having a structural unit is preferably a polymer compound having a structural unit represented by the following formula (4).

In formula (4) and formula (5), R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, halogen The alkyl group which may have an atom, the alkoxy group which may have a halogen atom, or the aryl group which may have a substituent is represented.

In formula (4), the definition and specific examples of the alkyl group which may have a halogen atom and the alkoxy group which may have a halogen atom represented by R ⁶ and R ⁷ are as described above for R ^1. Definitions and specific examples of the alkyl group which may have a halogen atom represented by R ² and R ³ , the aryl group which may have a substituent and the alkoxy group which may have a halogen atom Is the same. The definition and specific examples of the aryl group optionally having substituents represented by R ⁶ and R ⁷ are the definition of the aryl group optionally having substituents represented by Ar ² and The same as the specific example. The “substituent” that the “aryl group optionally having substituent (s)” represented by R ⁶ and R ⁷ may have includes the substituent R.

In formula (4), since the photoelectric conversion efficiency of the organic photoelectric conversion element can be increased, it is preferable that at least one of R ⁶ and R ⁷ is an alkyl group having 1 to 20 carbon atoms, More preferably, it is an alkyl group of several 4-8.

In formula (5), R ^{8 to} R ¹⁵ , an alkyl group which may have a halogen atom, an aryl group which may have a substituent, and an alkoxy which may have a halogen atom The definitions and specific examples of the group include an alkyl group which may have a halogen atom represented by the aforementioned R ¹ , R ² and R ³ , an aryl group which may have a substituent, and a halogen atom. The definition and specific examples of the alkoxy group which may be used are the same. The definition and specific examples of the aryl group which may have a substituent represented by R ^{8 to} R ¹⁵ include the definition of the aryl group which may have a substituent represented by Ar ² and The same as the specific example. The “substituent” that the “aryl group optionally having substituent (s)” represented by R ^{8 to} R ¹⁵ may have includes the substituent R.

In formula (5), R ^{8 to} R ¹⁵ are preferably hydrogen atoms from the viewpoint of ease of monomer synthesis. Further, it can be increased photoelectric conversion efficiency when used in an organic photoelectric conversion element, R ⁸ and R ⁹ is an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms Is preferable, and an alkyl group having 5 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms is more preferable.

  Specific examples of the polymer compound used as the electron donating compound include a polymer compound composed of a repeating unit represented by the following formula (6).

  The production method of the layer containing the composition containing the fullerene derivative of the present invention and the layer containing the composition containing the fullerene derivative of the present invention and the electron donating compound is not particularly limited. For example, the fullerene derivative of the present invention The method by the film-forming from the solution containing is mentioned.

  Examples of solvents used for film formation from solution include toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene and other hydrocarbon solvents, carbon tetrachloride, chloroform, Halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran Can be mentioned. The fullerene derivative can usually be dissolved in the solvent in an amount of 0.1% by weight or more.

  The solution may further contain a polymer compound. Specific examples of the solvent used in the solution include the solvents described above. From the viewpoint of the solubility of the polymer compound, hydrocarbons are preferable, and toluene, xylene, and mesitylene are more preferable.

  For film formation from solution, 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 method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.

  The organic photoelectric conversion element of the present invention is usually formed on a substrate. This substrate may be any substrate that does not chemically change when an electrode is formed and a layer containing an organic substance (for example, the fullerene derivative of the present invention or a composition containing the fullerene derivative) is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.

  Examples of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Examples of the material of the transparent or translucent electrode include indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO), indium zinc oxide (IZO), NESA, gold, platinum, silver, and copper. ITO, IZO and tin oxide are preferred. Examples of the electrode forming method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Moreover, you may use organic transparent electrically conductive films, such as a polyaniline and its derivative (s), polythiophene, and its derivative (s) as a transparent or translucent electrode.

  As an opaque electrode material, a metal, a conductive polymer, or the like can be used. One of the pair of electrodes is preferably made of a material having a low work function. Examples of materials having a low work function include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. And alloys of two or more of these metals, one or more of these metals and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin And alloys with one or more metals, graphite, and graphite intercalation compounds. Examples of alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys.

  The organic photoelectric conversion element can be operated as an organic thin film solar cell by generating photovoltaic power between the electrodes by irradiating light such as sunlight on the transparent or translucent electrode side. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

  Moreover, the organic photoelectric conversion element can flow a photocurrent by irradiating light to the transparent or translucent electrode side in the state which applied the voltage between electrodes. In this way, the organic photoelectric conversion element can be operated as an organic light sensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

  Examples are given below to illustrate the present invention in more detail. The present invention is not limited to the following examples.

Reagents and solvents were either commercial products used as they were, or distilled and purified in the presence of a desiccant. As C ₆₀ fullerene, a product manufactured by Frontier Carbon Co. was used.
¹ H NMR and ¹³ C NMR spectra were measured with JEOL MH500, and tetramethylsilane (TMS) was used as an internal standard. Infrared absorption spectra were measured using FT-IR 8000. MALDI-TOF MS spectra were measured with a BRUKER AutoFLEX-T2.

Synthesis Example 1 Synthesis of Compound B Compound B was synthesized using Compound A according to the following scheme.

  Bromobenzene (5.65 g, 36 mmol) and tetrahydrofuran (THF) (60 mL) were placed in a two-necked flask (capacity 100 mL) in which the internal gas was replaced with argon gas. N-Butyllithium (11.5 mL, 30 mmol) was slowly added at −78 ° C. with a syringe and stirred for 30 minutes. Compound A (6.73 g, 30 mmol) was added at −78 ° C., and the mixture was stirred at −78 ° C. for 1 hour. Water was added to stop the reaction, and the mixture was extracted with ethyl acetate. The obtained extract was dried over anhydrous sodium sulfate, and then isolated and purified with a C-300E column (elution solvent; hexane: ethyl acetate = 5: 1 and 1: 1 (volume ratio)) to obtain the target compound B. 7.97 g (26 mmol, 88% yield) was obtained.

The measurement results of ¹ H NMR and ¹³ C NMR of the obtained compound B are shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ 3.24 (1H, brs), 3.30 (3H, s), 3.49 (2H, t, J = 4.6 Hz) 3.63 (2H, t, J = 4.6 Hz), 4.03 (2H, t, J = 5.2 Hz), 5.66 (1H, d, J = 1.7 Hz), 5.81 (2H, d, J = 8.6 Hz), 7.19 (2H, d, J = 8.6 Hz), 7.20 (1H, t, J = 8.6 Hz), 7.27 (1H, t, J = 13.1 Hz), 7.28 (2H, d, J = 13.8 Hz); ¹³ C NMR (125 MHz, ppm, CDCl ₃ ) δ 58.72, 67.05, 69.41, 70.33 71.58, 75.18, 114.17, 126.18, 126.9. , 127.61, 128.06, 136.38, 144.04, 157.76;

Synthesis Example 2 Synthesis of Compound C Compound C was synthesized using Compound B according to the following scheme.

Compound B (7.97 g, 26 mmol), spherical silica gel (39 g), and dichloromethane (130 mL) were placed in a two-necked eggplant flask (capacity 300 mL) equipped with a calcium chloride tube. With stirring at room temperature, pyridinium dichromate (14.67 g, 39.0 mmol) was added. After stirring for 12 hours, the powdered solid was removed by filtration through celite. The obtained filtrate was washed with an aqueous CuSO ₄ solution and dried over anhydrous sodium sulfate. The product was isolated and purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 5: 1 and 1: 1 (volume ratio)) to obtain 7.97 g (25.6 mmol, yield 99%) of the desired compound C. .

The measurement results of ¹ H NMR, ¹³ C NMR, IR, and MALDI-TOF-MS of the obtained compound C are shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ 3.33 (3H, s), 3.53 (2H, t, J = 4.6 Hz), 3.67 (2H, t, J = 4.0 Hz), 3.83 (2H, t, J = 4.6 Hz), 4.16 (2H, t, J = 4.6 Hz), 6.95 (2H, d, J = 8. 6 Hz), 7.42 (2H, t, J = 7.4 Hz), 7.51 (1H, t, J = 7.4 Hz), 7.71 (2H, d, J = 7.5 Hz), 7. 78 (2H, d, J = 8.6 Hz); ¹³ C NMR (125 MHz, ppm, CDCl ₃ ) δ 58.20, 66.91, 68.73, 69.95, 71.14, 113.44, 127.50, 128.92, 129.34, 131.19, 131.7 ^{, 137.48, 161.76, 194.36; IR} (Neat, cm -1); 2927, 2879, 1653, 1601, 1508, 1447, 1316, 1282, 1258, 1173, 1148, 1110, 1058, 939, 923, 848, 742, 703; HRMS (DART MS) m / z: theor: 301.1440 found: 301.4322 ([M + H] ⁺ detected)

Synthesis Example 3 Synthesis of Compound D Compound D was synthesized using Compound C according to the following scheme.

  A Dean-Stark trap was attached to an eggplant flask (capacity 30 mL) in which the internal gas was replaced with argon, and Compound C (3.00 g, 10.0 mmol), tosylhydrazine (2.79 g, 15.0 mmol), benzene ( 20 mL). The reaction was carried out for 12 hours while refluxing at 100 ° C. The solvent was removed from the obtained reaction solution under reduced pressure, and the residue was purified by a neutral silica gel column (elution solvent; hexane: ethyl acetate = 5: 1, 2: 1 and 1: 1 (volume ratio)) to obtain the target compound D 4.32 g (9.2 mmol, yield 92%) was obtained.

The measurement results of ¹ H NMR, ¹³ C NMR, IR, and MALDI-TOF-MS of the obtained compound D are shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ; ¹³ C NMR (125 MHz, ppm, CDCl ₃ ) δ; IR (KBr, cm ⁻¹ ); HRMS (DART MS) m / z: theor: 469.1797 found: 469.1790 ([M + H] ⁺ .detected)

Example 1 Synthesis of Compound E Compound E was synthesized using Compound D according to the following scheme.

The obtained compound D (258 mg, 0.55 mmol), NaOMe (30 mg, 0.05 mmol), pyridine (7.5 mL) were placed in an eggplant flask (capacity 30 mL) in which the internal gas was replaced with argon gas. Stir for minutes. The obtained reaction solution was added to a solution of C ₆₀ fullerene (360 mg, 0.50 mmol) prepared in a two-necked eggplant flask (volume: 100 mL) in o-dichlorobenzene (38 mL), and freeze deaeration was repeated three times. For 12 hours. After removing the solvent under reduced pressure and washing with methanol 5 times, silica gel column (elution solvent; toluene: ethyl acetate = 1: 0, 10: 1 (volume ratio)), preparative TLC (developing solvent; CS ₂ : acetic acid) Purification with ethyl = 10: 1 (volume ratio)) gave 235 mg (0.23 mmol, 47% yield) of the desired compound E as a fullerene derivative.

The measurement results of ¹ H NMR, ¹³ C NMR, IR, and MALDI-TOF-MS of the obtained compound E are shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ 3.33 (3H, s), 3.51 (2H, t, J = 4.5 Hz), 3.66 (2H, t, J = 4.6 Hz), 3.82 (2H, t, J = 5.2 Hz), 4.11 (2H, t, J = 5.1 Hz), 6.93 (2H, d, J = 8. 6 Hz), 7.32 (1H, t, J = 7.4 Hz), 7.42 (2H, t, J = 7.4 Hz), 7.93 (2H, d, J = 8.6 Hz), 8. 01 (2H, d, J = 6.9 Hz); ¹³ C NMR (125 MHz, ppm, CDCl ₃ ) δ 57.38, 58.71, 67.19, 69.51, 70.64, 71.83 78.80, 114.48, 127.77, 128.51, 130.49, 30.78, 131.72, 137.91, 138.01, 138.92, 140.59, 141.82, 141.90, 142.64, 142.71, 143.54, 144.01, 144. 03, 144.30, 144.34, 144.41, 144.82, 144.88, 145.05, 147.89, 158.16; IR (KBr, cm ⁻¹ ); HRMS (MALDI TOF MS: matrix : SA) m / z: theor: 1004.1414 found: 1004.1413 ([M] ^{+ ·} detected)

[Example 2] Production and evaluation of organic photoelectric conversion device Regioregular poly (3-hexylthiophene) (manufactured by Aldrich, lot number: MKBD3325V) was dissolved in chlorobenzene at a concentration of 1 wt%. Compound E was added to the resulting liquid at an equal weight with respect to the weight of regioregular poly (3-hexylthiophene). The obtained liquid was filtered through a Teflon (registered trademark) filter having a pore diameter of 1.0 μm to prepare a coating solution.
Regioregular poly (3-hexylthiophene) acts as an electron donating compound, and compound E, which is a fullerene derivative, acts as an electron accepting compound.

A glass substrate on which an ITO film having a thickness of 150 nm was formed by a sputtering method was subjected to surface treatment by ozone UV treatment using an ultraviolet-ozone cleaning apparatus. Next, the said coating solution was apply | coated to the board | substrate with which the ITO film | membrane was formed by the spin coat method, and the active layer of the organic photoelectric conversion element was obtained. The thickness of the active layer was about 100 nm. Thereafter, baking was performed for 10 minutes at 130 ° C. in a nitrogen gas atmosphere. Then, lithium fluoride was vapor-deposited with a thickness of 4 nm by a vacuum vapor deposition machine, and then Al was vapor-deposited with a thickness of 100 nm. The degree of vacuum at the time of vapor deposition was 1 × 10 ^{−3 to} 9 × 10 ⁻³ Pa. Moreover, the shape of the obtained organic photoelectric conversion element was a square of 2 mm × 2 mm. The characteristics (photoelectric conversion efficiency, short-circuit current density (Jsc), open-circuit voltage (Voc), and fill factor (FF)) of the obtained organic thin film solar cell are solar simulators (trade name OTENTO-SUNII: AM1 manufactured by Spectrometer Co., Ltd.). A constant light was irradiated using a 5 G filter and an irradiance of 100 mW / cm ² ), and the generated current and voltage were measured. The results are shown in Table 1.

[Comparative Example 1] Production and Evaluation of Organic Photoelectric Conversion Element An organic photoelectric conversion element was produced in the same manner as in Example 2 except that [60] -PCBM was used instead of Compound E. The characteristics were determined. The results are shown in Table 1. [60] -PCBM used the trade name E100 (manufactured by Frontier Carbon, lot number: 9B0024-A).

Synthesis Example 4 Synthesis of Compound G Compound G was synthesized using Compound F according to the following scheme.

  Bromobenzene (1.88 g, 12 mmol) and 20 mL of THF were added to a two-necked flask (capacity: 100 mL) in which the internal gas was replaced with argon gas. N-Butyllithium (3.8 mL, 10 mmol) was slowly added at −78 ° C. with a syringe and stirred for 30 minutes. Compound F (2.20 g, 10 mmol) was added at −78 ° C., and the mixture was stirred at −78 ° C. for 1 hour. Thereafter, water was added to stop the reaction, and the target compound G was extracted with ethyl acetate. After drying over anhydrous sodium sulfate, it was isolated and purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 10: 1, 5: 1 (volume ratio)) to obtain 2.35 g (7.9 mmol, 7.9 mmol, (Yield 79%) Obtained as a colorless and transparent liquid.

The measurement results of ¹ H NMR, ¹³ C NMR, IR, and elemental analysis of the obtained compound G are shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ 0.88 (3H, t, J = 7.4 Hz), 1.24-1.33 (6H, m), 1.38 (2H , Quin, J = 5.7 Hz), 1.67 (2H, quin, J = 7.5 Hz), 3.78 (2H, t, J = 6.3 Hz), 5.43 (2H, d, J = 4.0 Hz), 6.70 (2H, d, J = 8.6 Hz), 7.05 (2H, d, J = 8.6 Hz), 7.09-7.19 (5H, m); ¹³ C NMR (125 MHz, ppm, CDCl ₃ ) δ 13.86, 22.37, 25.76, 28.83, 29.00, 31.55, 67.58, 75.08, 113.69, 113.95 , 126.21, 126.73, 127.66, ^{27.88, 135.90, 144.00, 158.05;} IR (Neat, cm -1) 3307, 2855, 2925, 1612, 1511, 1454, 1305, 1244, 1169, 1033, 792, 700; Elemental Analysis _{: Calcd for C 20 H 26 O} 2: C: 80.50%, H: 8.78%. Found: C: 80.57%, H: 8.83%.

(Synthesis Example 5) Synthesis of Compound H Compound H was synthesized from Compound G.

Compound G (2.35 g, 7.9 mmol), spherical silica gel (12 g), and dichloromethane (40 mL) were placed in a two-necked eggplant flask (capacity 100 mL) equipped with a calcium chloride tube. With stirring at room temperature, pyridinium dichromate (4.46 g, 11.9 mmol) was added. After stirring for 4 hours, the powdered solid was filtered off through celite. The obtained filtrate was washed with an aqueous CuSO ₄ solution and dried over anhydrous sodium sulfate. Isolation and purification by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 10: 1, 5: 1 (volume ratio)) gave 2.32 g (7.8 mmol, yield 99%) of the target compound H. It was.

The measurement results of ¹ H NMR, ¹³ C NMR, IR, and elemental analysis of the obtained compound H are shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ 0.90 (3H, t, J = 6.8 Hz), 1.31-1.40 (6H, m), 1.47 (2H , Quin, J = 7.5 Hz), 1.81 (2H, quin, J = 6.9 Hz), 4.03 (2H, t, J = 6.8 Hz), 6.95 (2H, d, J = 8.6 Hz), 7.46 (2H, t, J = 8.0 Hz), 7.55 (1H, t, J = 7.5 Hz), 7.75 (2H, d, J = 7.5 Hz) ), 7.82 (2H, d, J = 8.6 Hz); ¹³ C NMR (125 MHz, ppm, CDCl ₃ ) δ 14.04, 22.56, 25.90, 28.97, 29.06 31.70, 68.22, 113.94, 128.11, 129. 65, 129.79, 131.77, 132.51, 138.29, 162.83, 195.50; IR (KBr, cm ⁻¹ ); Elemental Analysis: Calcd for C ₂₀ H ₂₄ O ₂ : C: 81 .04%, H: 8.16%. Found: C: 81.09%, H: 8.19%.

Synthesis Example 6 Synthesis of Compound J Compound J was synthesized using Compound H according to the following scheme.

  A Dean-Stark trap was attached to an eggplant flask (capacity 10 mL) in which the internal gas was replaced with argon gas, and Compound H (1.48 g), tosylhydrazine (1.40 g, 7.5 mmol), and benzene (10 mL) were added. It was. The reaction was carried out for 24 hours while refluxing at 100 ° C. The solvent was removed under reduced pressure, and the residue was purified by neutral silica gel column chromatography (H: A = 10: 1, 5: 1) to obtain 2.69 g (5.80 mmol) of the target compound J.

Comparative Example 2 Synthesis of Compound K Compound K was synthesized using Compound J according to the following scheme.

Compound J (255 mg, 0.55 mmol), NaOMe (30 mg, 0.55 mmol), and pyridine (7.5 mL) were placed in an eggplant flask (capacity 10 mL) in which the internal gas was replaced with argon gas, and the mixture was stirred at room temperature for 30 minutes. . The reaction solution was added to a solution of C ₆₀ fullerene (360 mg, 0.50 mmol) in o-dichlorobenzene (38 mL) in a two-necked eggplant flask (capacity 100 mL), and freeze degassing was repeated three times at 90 ° C. for 12 hours. Stir. The solvent was removed under reduced pressure, washed 3 times with methanol, and then purified by silica gel column chromatography (elution solvent: toluene) and thin layer silica gel chromatography (elution solvent: CS ₂ ) to obtain 248 mg (0.25 mmol) of the target compound K. Yield 50%).

The measurement results of ¹ H NMR, ¹³ C NMR, IR, and MALDI-TOF-MS of the obtained compound K are shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ 0.89 (3H, t, J = 6.9 Hz), 1.27-1.38 (6H, m), 1.45 (2H , Quin, J = 6.9 Hz), 1.77 (2H, quin, J = 6.9 Hz), 3.93 (2H, t, J = 6.9 Hz), 5.90 (2H, d, J = 8.6 Hz), 7.32 (1H, t, J = 7.4 Hz), 7.41 (2H, t, J = 7.5 Hz), 7.91 (2H, d, J = 8.6 Hz) ), 8.01 (2H, d, J = 7.5 Hz); ¹³ C NMR (125 MHz, ppm, CDCl ₃ ) δ 14.22, 22.83, 26.15, 29.19, 29.38, 31.88, 57.51, 67.76, 78.92, 114.41 , 127.76, 128.52, 130.51, 131.70, 137.93, 138.05, 139.05, 140.61, 141.85, 141.87, 141.95, 141.97, 142 .67, 142.73, 143.57, 144.03, 144.04, 144.32, 144.42, 144.83, 144.85, 144.89, 144.09, 147.98, 148.00 IR (KBr, cm ⁻¹ ); HRMS (MALDI TOF MS: matrix: SA) m / z: theor: 1000.1827 found: 1000.1826 ([M] ^{+ ·} detected)

Comparative Example 3 Production and Evaluation of Organic Photoelectric Conversion Element An organic photoelectric conversion element was produced in the same manner as in Example 2 except that Compound K was used instead of Compound E in Example 2. The characteristics of were investigated. The results are shown in Table 1 below.

Synthesis Example 7 Synthesis of Compound N Compound N was synthesized using Compound L and Compound M according to the following scheme.

  Compound L (2.75 g, 10 mmol) and THF (50 mL) were placed in a two-necked flask (capacity: 100 mL) in which the internal gas was replaced with argon gas. N-Butyllithium (2.6 M, 3.8 mL, 10 mmol) was slowly added at −78 ° C. with a syringe and stirred for 30 minutes. Compound M (2.24 g, 10 mmol) was added at −78 ° C., and the mixture was stirred at −78 ° C. for 1 hour. Water was added to stop the reaction, and the mixture was extracted with ethyl acetate. The obtained extract was dried over anhydrous sodium sulfate and then isolated and purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 5: 1 and 1: 1 (volume ratio)) to obtain the target compound N 3 0.03 g (7.2 mmol, yield 72%) was obtained.

The measurement result of ¹ H NMR of the obtained compound N is shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ 3.38 (6H, s), 3.57 (4H, t, J = 2.9 Hz), 3.71 (4H, t, J = 1.1 Hz), 3.85 (4H, t, J = 4.0 Hz), 4.13 (4H, t, J = 4.0 Hz), 6.87 (4H, d, J = 8. 6 Hz), 7.25 (4H, d, J = 8.6 Hz)

Synthesis Example 8 Synthesis of Compound P Compound P was synthesized from compound O as follows.

  Compound O (3.03 g, 7.2 mmol), spherical silica gel (11 g), and dichloromethane (20 mL) were placed in a two-necked eggplant flask equipped with a calcium chloride tube (volume: 100 mL). With stirring at room temperature, pyridinium dichromate (4.06 g, 10.8 mmol) was added. After stirring for 24 hours, the powdered solid was removed by filtration through celite. Isolation and purification by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 1: 1 and 0: 1 (volume ratio)) gave 2.45 g (5.9 mmol, yield 81%) of the target compound P. .

The measurement result of ¹ H NMR of the obtained compound P is shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ 3.41 (6H, s), 3.60 (4H, t, J = 2.9 Hz), 3.74 (4H, t, J = 3.5 Hz), 3.90 (4H, t, J = 4.6 Hz), 4.23 (4H, t, J = 4.1 Hz), 6.97 (4H, d, J = 8. 6 Hz), 7.76 (4H, d, J = 9.2 Hz)

Synthesis Example 9 Synthesis of Compound R Compound R was synthesized from compound Q as follows.

  A Dean-Stark trap was attached to an eggplant flask (capacity 30 mL) in which the internal gas was replaced with argon, and Compound Q (2.45 g, 5.9 mmol), tosylhydrazine (1.65 g, 8.9 mmol), methanol (10 mL) ). The reaction was carried out for 12 hours while refluxing at 80 ° C. The solvent was removed from the obtained reaction solution under reduced pressure, and purification was performed by neutral silica gel column chromatography (elution solvent; hexane: ethyl acetate = 1: 1 and ethyl acetate: methanol = 0: 1, 20: 1 (volume ratio)). As a result, 3.45 g (5.9 mmol) of the target compound R was obtained.

The measurement result of ESI MS of the obtained compound R is shown below.
ESI MS: m / z: theor: 587.2422 found: 587.2407 ([M + H] ^{+ ·} detected)

[Comparative Example 4] Synthesis of Compound T Compound T was synthesized using Compound S as follows.

The obtained compound S (323 mg, 0.55 mmol), NaOMe (30 mg, 0.05 mmol), pyridine (7.5 mL) were placed in an eggplant flask (capacity 10 mL) in which the internal gas was replaced with argon gas. Stir for minutes. The obtained reaction solution was added to a solution of C ₆₀ fullerene (360 mg, 0.50 mmol) prepared in a two-necked eggplant flask (capacity 100 mL) in o-dichlorobenzene (38 mL), and freeze degassing was repeated three times. For 12 hours. The solvent was removed under reduced pressure, washed 5 times with methanol, and purified by silica gel column chromatography (elution solvent; toluene: ethyl acetate = 1: 0, 1: 1 (volume ratio)) to obtain 220 mg of black powder. Subsequently, 220 mg of the obtained black powder was dissolved in o-dichlorobenzene (5 mL) and stirred at 140 ° C. for 5 hours. The solvent was removed under reduced pressure, and purification was performed by reprecipitation three times in diethyl ether to obtain 201 mg (0.18 mmol, yield 90%) of the target compound T.

The measurement results of ¹ H NMR and MALDI-TOF-MS of the obtained compound T are shown below.
¹ H NMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ 3.34 (6H, s), 3.52 (4H, t, J = 5.2 Hz), 3.67 (4H, t, J = 4.6 Hz), 3.82 (4H, t, J = 5.2 Hz), 4.11 (4H, t, J = 4.6 Hz), 6.92 (4H, d, J = 9. 2 Hz), 7.89 (4H, d, J = 9.2 Hz); MALDI-TOF-MS: (matrix: SA) m / z: theor: 1122.2042 found: ([M] ^{+ ·} detected)

Comparative Example 5 Production and Evaluation of Organic Photoelectric Conversion Element An organic photoelectric conversion element was produced in the same manner as in Example 2 except that Compound T was used instead of Compound E in Example 2. The characteristics of were investigated. The results are shown in Table 1 below.

As is clear from Table 1, when compound E which is a fullerene derivative according to the present invention is used, when [60] -PCBM is used, when compound K having a different substituent R is used, Ar ¹ and Ar ² which is an aryl group are used. Compared to the case of using the compound T in which a group corresponding to the substituent R is introduced into both, it is possible to realize superior characteristics in all of the short circuit current density, the open circuit voltage, and the fill factor, and as a result, excellent The photoelectric conversion efficiency could be realized.

Claims (6)

A fullerene derivative represented by the following formula (1).

(In formula (1), ring F represents a fullerene ring. N C1s represent carbon atoms constituting a methanofullerene structure by bridging two carbon atoms constituting ring F. .Ar ² Ar ¹ is having the structure. substituent R representing a heteroaryl group having m pieces an aryl group or a substituent R having the m substituents R represented by the following formula (2) into individual organic is substituted An aryl group which may have a group (however, the substituent R is excluded from the substituent) or a heteroaryl group which may have a substituent, m and n are each independently Represents an integer of 1 or more.)

(In formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent substituent. P and q each independently represent an integer of 1 or more.) The fullerene derivative according to claim 1, wherein Ar ¹ having substituent R is an aryl group having m substituents R, and Ar ² is an aryl group.   A composition comprising the fullerene derivative according to claim 1 and an electron donating compound.   The composition according to claim 3, wherein the electron donating compound is a polymer compound.   An organic photoelectric conversion element provided with the layer containing the fullerene derivative of Claim 1 or 2.   An organic photoelectric conversion element provided with the layer containing the composition of Claim 3 or 4.