JP6145602B2 - Composition and photoelectric conversion element - Google Patents

Description

  The present invention relates to a composition containing a fullerene derivative, a photoelectric conversion device and an electronic device using the composition.

  Application of organic semiconductor materials having a charge (electron or hole) transport property to photoelectric conversion elements such as solar cells and optical sensors has been studied. For example, solar cells using fullerene derivatives have been studied.

As such fullerene derivatives, for example, [6,6] -phenyl C ₆₁ -butyric acid methyl ester (hereinafter sometimes referred to as “[60] -PCBM”) is known (see Non-Patent Document 1). ).

Advanced Functional Materials, Vol. 13, p. 85, 2003.

  However, the photoelectric conversion element including [60] -PCBM has a problem that the open-circuit voltage is not always sufficient.

  Then, an object of this invention is to provide the novel composition for manufacturing a photoelectric conversion element with a high open end voltage.

（式中、Ｆはフラーレン環を表す。Ｒ^１、Ｒ^２およびＲ^８はそれぞれ独立に水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアルコキシカルボニル基、置換基を有していてもよいアシル基又は置換基を有していてもよいアシルオキシ基を表す。ｎは１〜１０の整数を表す。Ｒ^１が複数個存在する場合、それらは互いに同じであっても異なっていてもよい。Ｒ^２が複数個存在する場合、それらは互いに同じであっても異なっていてもよい。Ａｒ^１は置換基を有していてもよいアリール基、置換基を有していてもよい複素環基、置換基を有していてもよいアルケニル基又は置換基を有していてもよいアルキニル基を表す。） The present invention first provides a composition comprising an electron accepting compound represented by formula (1) and an electron donating compound.

(In the formula, F represents a fullerene ring. R ¹ , R ² and R ⁸ may each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or a substituent. Alkoxy group, aryl group optionally having substituent, aryloxy group optionally having substituent, alkoxycarbonyl group optionally having substituent, and optionally having substituent Represents an acyloxy group which may have an acyl group or a substituent, n represents an integer of 1 to 10. When a plurality of R ¹ are present, they may be the same or different from each other; When a plurality of R ² are present, they may be the same or different from each other Ar ¹ is an aryl group that may have a substituent, or a heterocyclic group that may have a substituent An alkenyl group which may have a substituent Or, it represents an alkynyl group which may have a substituent.)

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７それぞれ独立に水素原子、ハロゲン原子、水酸基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアルコキシカルボニル基、置換基を有していてもよいアシル基、置換基を有していてもよいアシルオキシ基又は置換基を有していてもよい複素環基を表す。） The present invention secondly provides the composition, wherein Ar ¹ in the formula (1) is a group represented by the following formula (1-1).

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, or a substituent. Alkoxy group, aryl group optionally having substituent, aryloxy group optionally having substituent, alkoxycarbonyl group optionally having substituent, and optionally having substituent (Represents an acyl group, an optionally substituted acyloxy group or an optionally substituted heterocyclic group.)

  The present invention thirdly provides the composition described above, wherein F in the formula (1) is C60 fullerene or C70 fullerene.

  Fourth, the present invention provides the composition, wherein the electron donating compound is a conjugated polymer.

  The present invention fifthly provides the composition, wherein the conjugated polymer contains a thiophene ring.

  Sixth, the present invention provides an ink comprising the composition and a solvent.

  Seventh, the present invention has a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, the active layer comprising the composition A photoelectric conversion element including the same is provided.

  Eighthly, the present invention provides an electronic device comprising the electron-accepting compound represented by the formula (1).

  According to the novel composition of the present invention, the open circuit voltage can be improved by applying the composition to a photoelectric conversion element, which is extremely useful.

  In the present specification, the term “which may have a substituent” attached immediately before a group means that the hydrogen atom of the group is not substituted with a substituent, and the hydrogen atom of the group It means both when a part or all of them are substituted with a substituent. The “substituent” will be described later.

  In the present specification, the term “Cm to Cn” (m and n are positive integers satisfying m <n) means that the organic group described immediately after this term has m to n carbon atoms. It represents that. For example, “C1 to C12 alkoxyphenyl group” means that the alkoxy group moiety in the group has 1 to 12 carbon atoms, and “C1 to C12 alkylphenyl group” means an alkyl group moiety in the group. It represents that the number of carbon atoms is 1-12.

<Composition>
The composition of the present invention comprises an electron accepting compound represented by formula (1) and an electron donating compound.

  In formula (1), F represents a fullerene ring. Examples of the fullerene ring include a fullerene having 60 carbon atoms (hereinafter sometimes referred to as “C60 fullerene”), a fullerene having 70 carbon atoms (hereinafter sometimes referred to as “C70 fullerene”), and the number of carbon atoms. 76 fullerenes (hereinafter sometimes referred to as “C76 fullerene”), fullerenes having 84 carbon atoms (hereinafter sometimes referred to as “C84 fullerene”), and the like. From the viewpoint of easy availability, the fullerene ring is preferably a fullerene having 60 carbon atoms or a fullerene having 70 carbon atoms.

R ¹ , R ² and R ⁸ may each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. A good aryl group, an aryloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent or a substituent. Represents a good acyloxy group.

Examples of the halogen atom represented by R ¹ , R ² and R ⁸ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom and a chlorine atom.

The alkyl group represented by R ¹ , R ² and R ⁸ may be linear, branched or cyclic. The carbon atom number of this alkyl group is 1-30 normally, Preferably it is 1-20, More preferably, it is 1-10. The number of carbon atoms does not include the number of carbon atoms of the substituent. The alkyl group may have a substituent, and examples of the substituent include a halogen atom. Specific examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl grave, a pentyl group, and an isopentyl group. 2-methylbutyl group, 1-methylbutyl group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3 , 7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group, eicosyl group, 1- (2'-ethylhexyl) -3-ethylheptyl group, trifluoromethyl group , Pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, -Fluorooctyl group, cyclopentyl group, cyclohexyl group, adamantyl group and the like.

The alkoxy group represented by R ¹ , R ² and R ⁸ may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is usually 1-20, preferably 1-15, more preferably 1-10. The number of carbon atoms does not include the number of carbon atoms of the substituent. The alkoxy group may have a substituent, and examples of the substituent include a halogen atom and an alkoxy group (for example, an alkoxy group having 1 to 20 carbon atoms). Specific examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyl group. Oxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group Perfluorohexyloxy group, perfluorooctyloxy group, methoxymethyloxy group, 2-methoxyethyloxy group and the like.

The aryl group represented by R ¹ , R ² and R ⁸ is a group obtained by removing one hydrogen atom bonded to an aromatic ring from an unsubstituted aromatic hydrocarbon. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 20, and more preferably 6 to 12. The number of carbon atoms does not include the number of carbon atoms of the substituent. The aryl group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, and an alkoxy group. Definitions and specific examples of halogen atoms, alkyl groups, and alkoxy groups used as substituents include definitions and specific examples of the halogen atoms, alkyl groups, and alkoxy groups represented by the aforementioned R ¹ , R ^2, and R ^8. The same. Specific examples of the aryl group which may have a substituent include a phenyl group and a C1-C12 alkoxyphenyl group (preferably a C1-C8 alkoxyphenyl group, more preferably a C1-C6 alkoxyphenyl group. C1- Specific examples of the C12 alkoxy group, C1-C8 alkoxy group, and C1-C6 alkoxy group include the groups described and exemplified as the alkoxy groups represented by the aforementioned R ¹ , R ^2, and R ⁸ . C1-C12 alkylphenyl group (preferably C1-C8 alkylphenyl group, more preferably C1-C6 alkylphenyl group. C1-C12 alkyl group, C1-C8 alkyl group and C1-C6 alkyl group). specific examples of the exemplified as the alkyl group represented by R ^1, R ² and R ⁸ described above Groups and the like. The same applies is less.), 1-naphthyl group, a 2-naphthyl group and a pentafluorophenyl group.

The aryloxy group represented by R ¹ , R ² and R ⁸ usually has 6 to 60 carbon atoms, preferably 6 to 20 and more preferably 6 to 12. The number of carbon atoms does not include the number of carbon atoms of the substituent. The aryloxy group may have a substituent, and as the substituent, the same substituent as the substituent which the aryl group represented by R ¹ , R ² and R ⁸ described above may have. Is mentioned. Specific examples of the aryloxy group which may have a substituent include phenoxy group, C1-C12 alkoxyphenoxy group, C1-C12 alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group and pentafluorophenyl. An oxy group is mentioned.

In the alkoxycarbonyl group represented by R ¹ , R ² and R ⁸ , the alkoxy group portion may be linear, branched or cyclic. The number of carbon atoms in the alkoxy group portion of the alkoxycarbonyl group is usually 1-20, preferably 1-15, more preferably 1-12. The number of carbon atoms does not include the number of carbon atoms of the substituent. The alkoxycarbonyl group may have a substituent, and the substituent is the same as the substituent which the alkoxy group represented by R ¹ , R ² and R ⁸ described above may have. Is mentioned. Specific examples of the alkoxycarbonyl group which may have a substituent include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a perfluoropropoxycarbonyl group, A methoxymethyloxycarbonyl group, 2-methoxyethyloxycarbonyl group, etc. are mentioned.

The acyl group represented by R ¹ , R ² and R ⁸ is a group obtained by removing a hydroxyl group from a carboxylic acid such as an alkyl carboxylic acid and an aryl carboxylic acid. The number of carbon atoms of the acyl group is usually 2-20, preferably 2-15, more preferably 2-10. The number of carbon atoms does not include the number of carbon atoms of the substituent. The acyl group may have a substituent, and examples of the substituent include a halogen atom. Examples of the halogen atom used as a substituent include the halogen atoms represented by the aforementioned R ¹ , R ² and R ⁸ . Examples of the acyl group which may have a substituent include an alkylcarbonyl group, an alkylcarbonyl group having a halogen atom as a substituent, an arylcarbonyl group, and an arylcarbonyl group having a halogen atom as a substituent. Examples include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, trifluoroacetyl group, benzoyl group, pentafluorobenzoyl group and the like.

The acyloxy group represented by R ¹ , R ² and R ⁸ usually has 2 to 20 carbon atoms, preferably 2 to 15 and more preferably 2 to 10 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. The acyloxy group may have a substituent, and examples of the substituent include the same substituent as the substituent that the acyl group represented by R ¹ , R ^2, and R ⁸ may have. Can be mentioned. Examples of the acyloxy group which may have a substituent include an alkylcarbonyloxy group, an alkylcarbonyloxy group having a halogen atom as a substituent, an arylcarbonyloxy group, and an arylcarbonyloxy group having a halogen atom as a substituent. Specific examples include acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, trifluoroacetyloxy group, benzoyloxy group, pentafluorobenzoyloxy group and the like.

R ¹ and R ² are preferably a hydrogen atom, an alkoxy group that may have a substituent, an alkoxycarbonyl group that may have a substituent, or an acyloxy group that may have a substituent. More preferably a hydrogen atom.

R ⁸ preferably has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent or a substituent. An acyloxy group which may be substituted, more preferably a hydrogen atom or an alkyl group which may have a substituent, and still more preferably a hydrogen atom.

In formula (1), n represents an integer of 1 to 10. When a plurality of R ¹ are present, they may be the same as or different from each other. When a plurality of R ² are present, they may be the same as or different from each other. n is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.

In formula (1), Ar ¹ has an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents an alkynyl group which may be substituted.

The aryl group represented by Ar ¹ is a group obtained by removing one hydrogen atom bonded to an aromatic ring from an unsubstituted aromatic hydrocarbon. The aryl group usually has 6 to 60 carbon atoms, preferably 6 to 20, and more preferably 6 to 12. The number of carbon atoms does not include the number of carbon atoms of the substituent. The aryl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, and the like. A heterocyclic group is mentioned. The definitions and specific examples of the halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, alkoxycarbonyl group, acyl group, and acyloxy group used as a substituent are represented by the aforementioned R ¹ , R ^2, and R ^8. The definition and specific examples of the halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, alkoxycarbonyl group, acyl group and acyloxy group are the same. The heterocyclic group used as a substituent is the same as the heterocyclic group represented by Ar ¹ described later. The substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”), and the secondary substituent has the aryl group represented by Ar ¹ described above. The same substituent as the substituent which may be included is mentioned. Specific examples of the aryl group which may have a substituent include a phenyl group, a C1-C12 alkoxyphenyl group (preferably a C1-C8 alkoxyphenyl group, more preferably a C1-C6 alkoxyphenyl group), Examples thereof include a C1-C12 alkylphenyl group (preferably a C1-C8 alkylphenyl group, more preferably a C1-C6 alkylphenyl group), a 1-naphthyl group, a 2-naphthyl group, and a pentafluorophenyl group.

The heterocyclic group represented by Ar ¹ is a group obtained by removing one hydrogen atom bonded to the heterocyclic ring from the heterocyclic compound. Examples of the heterocyclic ring include furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, triazole, thiadiazole, oxadiazole, Tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline, chromene, chroman, isochroman, benzopyran , Quinoline, isoquinoline, quinolidine, benzimidazole, benzothiazole, indazole, naphthyl Quinoxaline, quinazoline, quinazoline, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine, phenazine, etc. . The number of carbon atoms of the heterocyclic group is usually 2 to 60, preferably 3 to 20, and more preferably 3 to 12. The number of carbon atoms does not include the number of carbon atoms of the substituent. The heterocyclic group may have a substituent, and examples of the substituent include the same substituent as the substituent that the aryl group represented by Ar ¹ described above may have. The substituent may further have a secondary substituent, and examples of the secondary substituent include the same substituent as the substituent which the aryl group represented by Ar ¹ described above may have. It is done. The heterocyclic group represented by Ar ¹ is preferably an aromatic heterocyclic group.

The alkenyl group represented by Ar ¹ usually has 2 to 20 carbon atoms, preferably 2 to 15 and more preferably 2 to 10 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. The alkenyl group may have a substituent, and examples of the substituent include the same substituent as the substituent which the aryl group represented by Ar ¹ described above may have. The substituent may further have a secondary substituent, and examples of the secondary substituent include the same substituent as the substituent which the aryl group represented by Ar ¹ described above may have. It is done. As the alkenyl group which may have a substituent, a group obtained by removing one hydrogen atom from a vinyl group in an alkene which may have a substituent is preferable. Specific examples of the alkenyl group which may have a substituent include a vinyl group, a propenyl group, a butenyl group, an α-styryl group, a β-styryl group, an α-acryloyl group, a β-acryloyl group, and a croconyl group. Can be mentioned.

The alkynyl group represented by Ar ¹ usually has 2 to 20 carbon atoms, preferably 2 to 15 and more preferably 2 to 10 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the substituent. The alkynyl group may have a substituent, and examples of the substituent include the same substituent as the substituent which the aryl group represented by Ar ¹ described above may have. The substituent may further have a secondary substituent, and examples of the secondary substituent include the same substituent as the substituent which the aryl group represented by Ar ¹ described above may have. It is done. The alkynyl group which may have a substituent is preferably a group obtained by removing one hydrogen atom from the ethynyl group in the alkyne which may have a substituent. Examples of the alkynyl group which may have a substituent include ethynyl group, 1-propynyl group, 1-butynyl group, 2-phenyl-1-butynyl group and the like.

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７はそれぞれ独立に水素原子、ハロゲン原子、水酸基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアルコキシカルボニル基、置換基を有していてもよいアシル基、置換基を有していてもよいアシルオキシ基又は置換基を有していてもよい複素環基を表す。） Ar ¹ is preferably an aryl group which may have a substituent, and more preferably a group represented by the following formula (1-1).

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may each independently have a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, or a substituent. A good alkoxy group, an aryl group which may have a substituent, an aryloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, or a substituent Represents a good acyl group, an acyloxy group which may have a substituent, or a heterocyclic group which may have a substituent.)

Definitions and specific examples of halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkoxycarbonyl groups, acyl groups, and acyloxy groups represented by R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as follows: The definitions and specific examples of the halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, alkoxycarbonyl group, acyl group, and acyloxy group represented by R ¹ , R ^2, and R ⁸ described above are the same. The definition and specific examples of the heterocyclic group represented by R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as the definition and specific examples of the heterocyclic group represented by Ar ¹ described above. Has a halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, alkoxycarbonyl group, acyl group, acyloxy group and heterocyclic group represented by R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ Examples of the substituent which may be included include the same substituents as the substituent which the aryl group represented by Ar ¹ may have.

（式中、Ｒ^１、Ｒ^２、Ａｒ^１およびｎは前述と同じ意味を表す。＊は結合手を表す。）
で表される基が結合するフラーレン骨格上の炭素原子と、Ｒ^８が結合するフラーレン骨格上の炭素原子とが、最短で数えて１結合介して位置するか、３結合介して位置する構造を有する。 The electron-accepting compound represented by the formula (1) is represented by the following formula (1-A):

(In the formula, R ¹ , R ² , Ar ¹ and n represent the same meaning as described above. * Represents a bond.)
A structure in which the carbon atom on the fullerene skeleton to which the group represented by formula (I) is bonded and the carbon atom on the fullerene skeleton to which R ⁸ is bonded are located through one bond or three bonds, at the shortest. Have.

In a preferred embodiment, the group represented by the formula (1-A) and the group represented by R ⁸ are each two adjacent carbon atoms in one six-membered ring constituting the fullerene skeleton. It binds to (ortho position) or two carbon atoms (para position) existing at a position between two carbon atoms.

When R ⁸ is a hydrogen atom, the group represented by the formula (1-A) and the group represented by R ⁸ are each two adjacent groups in one 6-membered ring constituting the fullerene skeleton. Bonds to a carbon atom (ortho position).

When R ⁸ is different from a hydrogen atom, the electron-accepting compound represented by the formula (1) is a mixture of the following compound (A) and the following compound (B).
Compound (A): two carbon atoms (ortho positions) adjacent to each other in one six-membered ring in which the group represented by the formula (1-A) and the group represented by R ⁸ constitute a fullerene skeleton. Compound (B): A group represented by the formula (1-A) and a group represented by R ⁸ each have two carbon atoms in one six-membered ring constituting the fullerene skeleton. Compound bonded to two carbon atoms (para position) existing in the intervening position

（式中、Ｒ^１、Ｒ^２、Ｒ^８、Ａｒ^１およびｎは前述と同じ意味を表す。） The fullerene ring F is C60 fullerene, and the group represented by the formula (1-A) and the group represented by R ⁸ are each adjacent to each other in two adjacent six-membered rings constituting the fullerene skeleton. Examples of the electron-accepting compound represented by the formula (1) bonded to the carbon atom (ortho position) include a compound represented by the following formula (2).

(Wherein R ¹ , R ² , R ⁸ , Ar ¹ and n represent the same meaning as described above.)

（式中、Ｒ^１、Ｒ^２、Ｒ^８、Ａｒ^１およびｎは前述と同じ意味を表す。） The fullerene ring F is C60 fullerene, and the group represented by the formula (1-A) and the group represented by R ⁸ each have two carbon atoms in one six-membered ring constituting the fullerene skeleton. Examples of the electron-accepting compound represented by the formula (1) that is bonded to two carbon atoms (para-positions) present at positions where atoms are interposed include compounds represented by the following formula (3).

(Wherein R ¹ , R ² , R ⁸ , Ar ¹ and n represent the same meaning as described above.)

（式中、Ｒ^１、Ｒ^２、Ｒ^８、Ａｒ^１およびｎは前述と同じ意味を表す。） The fullerene ring F is C70 fullerene, and the group represented by the formula (1-A) and the group represented by R ⁸ are each adjacent to each other in two adjacent six-membered rings constituting the fullerene skeleton. Examples of the electron-accepting compound represented by the formula (1) bonded to the carbon atom (ortho position) include compounds represented by the following formulas (4-1) and (4-2) and isomers thereof. The body is mentioned.

(Wherein R ¹ , R ² , R ⁸ , Ar ¹ and n represent the same meaning as described above.)

（式中、Ｒ^１、Ｒ^２、Ｒ^８、Ａｒ^１およびｎは前述と同じ意味を表す。） The fullerene ring F is C70 fullerene, and the group represented by the formula (1-A) and the group represented by R ⁸ each have two carbon atoms in one six-membered ring constituting the fullerene skeleton. Examples of the electron-accepting compound represented by the formula (1) bonded to two carbon atoms (para-positions) present at the positions where the atoms are interposed include, for example, the following formulas (5-1) and (5-2): ) And isomers thereof.

(Wherein R ¹ , R ² , R ⁸ , Ar ¹ and n represent the same meaning as described above.)

  Examples of the electron-accepting compound represented by the formula (1) include compounds represented by the following formulas 1 to 69 (compounds in which the fullerene ring F is C60 fullerene) and compounds represented by the formulas 101 to 169. (A compound in which the fullerene ring F is a C70 fullerene).

  Among the compounds represented by Formula 1 to Formula 66 and Formula 101 to Formula 166, Formula 1, Formula 2, Formula 3, Formula 16, Formula 17, Formula 18, Formula 31, Formula 32, Formula 33, and Formula 37 are preferable. , Formula 38, Formula 39, Formula 64, Formula 65, Formula 66, Formula 101, Formula 102, Formula 103, Formula 116, Formula 117, Formula 118, Formula 131, Formula 132, Formula 133, Formula 137, Formula 138, Formula 139, Formula 164, Formula 165 or Formula 166, more preferably Formula 1, Formula 2, Formula 3, Formula 16, Formula 17, Formula 18, Formula 64, Formula 65, Formula 66, Formula 101 , Formula 102, Formula 103, Formula 116, Formula 117, Formula 118, Formula 164, Formula 165, or Formula 166, and more preferably Formula 1, Formula 16, Formula 17, Formula 66, Formula 101, A compound represented by Formula 116, Formula 117, or Formula 166; Properly is a compound represented by the formula 66.

（式中、Ｆ、Ｒ^１、Ｒ^２、Ａｒ^１およびｎは前述と同じ意味を表す。） The manufacturing method of the compound represented by Formula (6) which is one aspect | mode of the electron-accepting compound represented by Formula (1) is demonstrated.

(In the formula, F, R ¹ , R ² , Ar ¹ and n have the same meaning as described above.)

（式中、Ｒ^１、Ｒ^２、Ａｒ^１およびｎは前述と同じ意味を表す。Ｘはハロゲン原子を表す。） Although the manufacturing method of the compound represented by Formula (6) which is one aspect | mode of the electron-accepting compound represented by Formula (1) is not specifically limited, From a viewpoint of synthetic | combination ease, C60 fullerene, C70 fullerene, etc. A method of reacting fullerene and a compound represented by the following formula (1-1-1) in the presence of a metal catalyst is preferable.

(In the formula, R ¹ , R ² , Ar ¹ and n represent the same meaning as described above. X represents a halogen atom.)

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は前述と同じ意味を表す。Ｘはハロゲン原子を表す。） As the compound represented by the formula (1-1-1), a compound represented by the following formula (1-1-2) is preferable.

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ represent the same meaning as described above. X represents a halogen atom.)

  Examples of the metal catalyst include a cobalt catalyst, a nickel catalyst, an iron catalyst, a palladium catalyst, an iridium catalyst, a rhodium catalyst, and a ruthenium catalyst. Among these, a cobalt catalyst, a rhodium catalyst, and a nickel catalyst are preferable, and a cobalt catalyst is more preferable. Examples of the cobalt catalyst include dichlorobis (diphenylphosphinoethane) cobalt, dibromobis (diphenylphosphinoethane) cobalt, diiodobis (diphenylphosphinoethane) cobalt, dichlorobis (diphenylphosphinoferrocene) cobalt, dichlorobis (diphenylphosphinomethane). Examples thereof include cobalt, preferably dichlorobis (diphenylphosphinoethane) cobalt, dibromobis (diphenylphosphinoethane) cobalt, and diiodobis (diphenylphosphinoethane) cobalt, more preferably dichlorobis (diphenylphosphinoethane) cobalt. .

  When the fullerene and the compound represented by the formula (1-1-1) are reacted in the presence of a metal catalyst, a promoter may be used. Examples of the cocatalyst include manganese, iron, zinc, copper, and the like, preferably manganese, iron, and zinc, and particularly preferably manganese.

  When the fullerene and the compound represented by the formula (1-1-1) are reacted in the presence of a metal catalyst, the reaction may be performed without a solvent, but the reaction may be performed using a solvent. Any solvent may be used as long as it dissolves fullerene and the compound represented by the formula (1-1-1). For example, aromatic compounds such as benzene, toluene, xylene, ethylbenzene, cumene, trimethylbenzene, tetralin, and cyclohexylbenzene are used. Group hydrocarbon solvents, halogenated aromatic hydrocarbon solvents such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, chloronaphthalene, carbon disulfide and the like. Among these, halogenated aromatic hydrocarbon solvents are preferable, and o-dichlorobenzene is more preferable.

  When the fullerene and the compound represented by the formula (1-1-1) are reacted in the presence of the metal catalyst, the temperature is in the range of −50 ° C. to the boiling point of the solvent, preferably 0. It is 50 degreeC.

  The time for reacting the fullerene and the compound represented by the formula (1-1-1) in the presence of the metal catalyst is usually about 1 minute to 1000 hours, preferably 1 hour to 100 hours, more Preferably it is 20 hours-70 hours.

  By subjecting the reaction product obtained by the above reaction to normal post-treatment (for example, treatment by diluting with addition of water followed by extraction with an organic solvent and distilling off the solvent in the organic layer), the formula (6 ) Can be obtained. Isolation and purification of the reaction product can be performed by a method such as fractionation by chromatography or recrystallization.

The electron-accepting compound represented by Formula (6) can be manufactured by the method demonstrated above. The compound represented by Formula (6) is a compound in which R ⁸ is a hydrogen atom in the electron-accepting compound represented by Formula (1). A compound in which R ⁸ is a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an acyl group or an acyloxy group is obtained by bringing the electron-accepting compound represented by the formula (6) into contact with a base. And then reacting with the corresponding electrophile.

For example, an electron-accepting compound represented by formula (1) in which R ⁸ is an alkyl group can be reacted with an alkyl halide after contacting the electron-accepting compound represented by formula (6) with a base. Can be manufactured.

  Examples of the base include tert-butoxy potassium, tert-butoxy lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamide and the like.

  The electron-accepting compound represented by formula (6) and the base may be contacted without a solvent, but are preferably contacted in a solvent. As the solvent, aliphatic hydrocarbon solvents such as hexane, cyclohexane and octane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether and tetrahydrofuran are preferably used.

  The temperature at which the electron-accepting compound represented by formula (6) is brought into contact with the base is usually −100 ° C. to 100 ° C., preferably −80 ° C. to 0 ° C.

  The contact time when the electron-accepting compound represented by formula (6) is contacted with the base is usually 1 minute to 10 hours, preferably 5 minutes to 5 hours, more preferably 30 minutes to 2 hours. is there.

  Examples of the alkyl halide used as the electrophile include iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 1-iodohexane, 1-iodo-2-ethylhexane and the like. Alkane iodide, bromomethane, bromoethane, 1-bromopropane, 2-bromopropane, 1-bromobutane, 2-bromobutane, 1-bromohexane, 1-bromo-2-ethylhexane and other alkane bromides, chloromethane, chloroethane, Examples include alkane chlorides such as 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chlorohexane, and 1-chloro-2-ethylhexane.

  When reacting with an alkyl halide, the reaction may be performed without a solvent, but it is preferable to perform the reaction using a solvent. As the solvent, aliphatic hydrocarbon solvents such as hexane, cyclohexane and octane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether and tetrahydrofuran are preferably used. The temperature at the time of reacting the alkyl halide is usually −100 ° C. to 100 ° C., preferably −80 ° C. to 30 ° C. The reaction time for reacting the alkyl halide is usually 10 minutes to 100 hours, preferably 1 hour to 50 hours, and more preferably 2 hours to 20 hours.

By subjecting the reaction product obtained by the above reaction to normal post-treatment (for example, treatment by diluting by adding water followed by extraction with an organic solvent and distilling off the solvent in the organic layer, etc.), R ⁸ becomes An electron-accepting compound represented by the formula (1) which is an alkyl group can be obtained. Isolation and purification of the reaction product can be performed by a method such as fractionation by chromatography or recrystallization.

  The electron donating compound contained in the composition of the present invention may be a low molecular compound or a high molecular compound. In the present invention, “low molecular compound” refers to a compound having a molecular weight of less than 3000, and “polymer compound” refers to a compound having an (average) molecular weight of 3000 or more.

  Examples of the electron donating compound that is a low molecular compound include porphyrin complexes and derivatives thereof, phthalocyanine and derivatives thereof, and oligothiophenes containing a thiophene ring.

  Examples of the electron donating compound that is a polymer compound include conjugated polymers. Examples of the conjugated polymer include polycarbazole and derivatives thereof, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, and the like. Is mentioned.

  The polycarbazole derivative means a polymer compound having a carbazole structure. The polyaniline derivative means a polymer compound having an aniline ring. A polythiophene derivative means a polymer compound having a thiophene ring. The polypyrrole derivative means a polymer compound having a pyrrole ring. The polyphenylene vinylene derivative means a polymer compound having a phenylene vinylene structure. The polythienylene vinylene derivative means a polymer compound having a thienylene vinylene structure. The polyfluorene derivative means a polymer compound having a fluorene structure.

  The conjugated polymer used as the electron donating compound preferably contains a thiophene ring. The conjugated polymer is preferably polythiophene and derivatives thereof, more preferably poly (C4-C20 alkylthiophene), and further preferably poly (3-hexylthiophene), poly (3-butylthiophene), poly ( 3-octylthiophene), particularly preferably poly (3-hexylthiophene).

  In the composition of the present invention, the ratio of the electron-accepting compound represented by the formula (1) to the electron-donating compound is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the electron-donating compound. It is more preferably 20 to 500 parts by weight.

  In the composition of the present invention, the electron-accepting compound represented by the formula (1) may be included singly or in combination of two or more. In the composition of the present invention, the electron donating compound may be included singly or in combination of two or more.

  The composition of the present invention may contain other components as required in addition to the electron-accepting compound and the electron-donating compound represented by the formula (1). Examples of the other components include one or more selected from the group consisting of an ultraviolet absorber, an antioxidant, a surfactant, a hygroscopic agent, and a water repellent.

  In the composition of the present invention, the total content of the electron-accepting compound and the electron-donating compound represented by the formula (1) is preferably 90 parts by weight or more with respect to 100 parts by weight of the composition of the present invention. Preferably it is 95 weight part or more, More preferably, it is 98 weight part or more, Most preferably, it is 99 weight part or more.

<Ink>
The ink of the present invention contains the composition of the present invention and a solvent. Any solvent may be used as long as it dissolves the composition of the present invention. For example, unsaturated hydrocarbons such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, and tert-butylbenzene. Solvents, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, and other halogenated saturated hydrocarbon solvents, chlorobenzene, dichlorobenzene, tri Examples thereof include halogenated unsaturated hydrocarbon solvents such as chlorobenzene and ether solvents such as tetrahydrofuran and tetrahydropyran.

  From the viewpoint of film formability, the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. More preferably, it is small.

  In the ink of the present invention, the content of the composition of the present invention is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the ink of the present invention. Part.

<Photoelectric conversion element>
The photoelectric conversion element of the present invention has a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, and the active layer has the formula (1 And a composition containing an electron-donating compound and an electron-donating compound. In the photoelectric conversion element of the present invention, at least one of the first electrode and the second electrode is transparent or translucent.

  The operation mechanism of the photoelectric conversion element will be described. Light energy incident from a transparent or translucent electrode is absorbed by an electron-accepting compound such as a fullerene derivative and / or an electron-donating compound, and excitons in which electrons and holes are combined are generated. When the generated excitons move and reach the junction interface where the electron-accepting compound and the electron-donating compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO energy and LUMO energy at the interface, Electric charges (electrons and holes) that can move independently are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.

  The photoelectric conversion element of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when an electrode is formed and an organic layer such as an active layer 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, and composites thereof (for example, indium tin oxide (ITO), indium zinc oxide (IZO), NESA, etc.) , Gold, platinum, silver, copper and the like, and ITO, IZO and tin oxide are preferable. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like.
As an electrode material, an organic transparent conductive film such as polyaniline and derivatives thereof, polythiophene and derivatives thereof, and the like may be used.

  One electrode may not be transparent or translucent. Examples of the material of the electrode include metals, conductive polymers and the like, and specific examples include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, and zinc. Metals such as yttrium, indium, cerium, samarium, europium, terbium, ytterbium; two or more of these metals; one or more of these metals and gold, silver, platinum, copper, manganese And alloys with one or more metals selected from the group consisting of titanium, cobalt, nickel, tungsten and tin; graphite and graphite intercalation compounds; polyaniline and derivatives thereof; and polythiophene and derivatives thereof. Specific 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. .

  The photoelectric conversion element of the present invention may have an additional intermediate layer other than the active layer as a means for improving the photoelectric conversion efficiency. Examples of the material for the intermediate layer include alkali metals such as lithium fluoride, halides of alkaline earth metals, oxides such as titanium oxide, and PEDOT (poly-3,4-ethylenedioxythiophene).

(Active layer)
The active layer may contain the composition of the present invention alone or in combination of two or more. In order to improve the hole transport property of the active layer, compounds other than the composition of the present invention may be used in the active layer as the electron donating compound and / or the electron accepting compound. The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

  In the active layer, the content of the composition of the present invention is preferably 95 to 100 parts by weight, more preferably 98 to 100 parts by weight with respect to 100 parts by weight of the active layer.

  The thickness of the active layer is usually preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, further preferably 5 nm to 500 nm, and particularly preferably 20 nm to 250 nm.

  The method for producing the active layer is not particularly limited, and examples thereof include film formation from the ink of the present invention and film formation by vacuum vapor deposition.

<Method for producing photoelectric conversion element>
A preferred method for producing a photoelectric conversion element is a method for producing a photoelectric conversion element having a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode. A manufacturing method comprising a step of applying the ink of the present invention on the first electrode by a coating method to form an active layer, and a step of forming a second electrode on the active layer.

  When forming a film using the ink of the present invention, for example, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method Application methods such as dip coating, spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet printing, dispenser printing, nozzle coating, capillary coating, etc. can be used. The slit coating method, capillary coating method, gravure coating method, micro gravure coating method, bar coating method, knife coating method, nozzle coating method, ink jet printing method and spin coating method are preferred.

<Organic thin film transistor>
The composition of the present invention can also be used for organic thin film transistors. The organic thin film transistor has a configuration including a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path. The organic semiconductor layer is composed of an organic thin film containing the composition of the present invention. Examples of such an organic thin film transistor include a field effect type and an electrostatic induction type.

  A field-effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer (active layer) that becomes a current path between these electrodes, a gate electrode that controls the amount of current passing through the current path, and an organic semiconductor layer and a gate. It is preferable to provide an insulating layer disposed between the electrodes. In particular, the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer (active layer), and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween. In the field effect organic thin film transistor, the organic semiconductor layer is constituted by an organic thin film containing the composition of the present invention.

  The static induction organic thin film transistor has a source electrode and a drain electrode, an organic semiconductor layer (active layer) that becomes a current path between these electrodes, and a gate electrode that controls the amount of current passing through the current path. Is preferably provided in the organic semiconductor layer. In particular, the source electrode, the drain electrode, and the gate electrode provided in the organic semiconductor layer are preferably provided in contact with the organic semiconductor layer. Here, the structure of the gate electrode may be a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. An electrode is mentioned. Also in the static induction organic thin film transistor, the organic semiconductor layer is constituted by an organic thin film containing the composition of the present invention.

<Organic electroluminescence device>
The composition of the present invention can also be used for an organic electroluminescence device (hereinafter sometimes referred to as “organic EL device”). An organic EL element has a light emitting layer between a pair of electrodes, at least one of which is transparent or translucent. The organic EL element may include a hole transport layer and an electron transport layer in addition to the light emitting layer. The composition of the present invention is contained in any one of the light emitting layer, the hole transport layer, and the electron transport layer. In addition to the composition of the present invention, the light emitting layer may contain a charge transport material (which means a generic term for an electron transport material and a hole transport material). Examples of the organic EL element include i) an element having an anode, a light emitting layer, and a cathode; ii) an anode having an electron transport layer containing an electron transport material adjacent to the light emitting layer between the cathode and the light emitting layer; An element having a light-emitting layer, an electron transport layer, and a cathode, iii) an anode and a hole transport layer having a hole transport layer containing a hole transport material adjacent to the light-emitting layer between the anode and the light-emitting layer; Examples include an element having a light emitting layer and a cathode, and iv) an element having an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.

<Application of device>
The photoelectric conversion element using the composition of the present invention can be operated as an organic thin film solar cell by generating photovoltaic power between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. it can. 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 photoelectric conversion element using the composition of the present invention is a state in which a voltage is applied between the electrodes, or in a non-applied state, by irradiating light from a transparent or translucent electrode, a photocurrent flows, It 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.

  The organic thin film transistor described above is used as a pixel driving element used for controlling the pixels of a display such as an electrophoretic display, a liquid crystal display, an organic electroluminescence display, etc., and controlling the uniformity of screen luminance and the screen rewriting speed. Can do.

<Solar cell module>
The organic thin film solar cell can basically have the same module structure as a conventional solar cell module. The solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known. The organic thin-film solar cell produced using the composition of the present invention can also be appropriately selected from these module structures depending on the purpose of use, the place of use and the environment.

In a typical super straight type or substrate type module, cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are connected by metal leads or flexible wiring. The current collector electrode is connected to the outer edge portion, and the generated power is taken out to the outside. Various types of plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filling resin depending on the purpose in order to protect the cell and improve the current collection efficiency. In addition, when used in a place where it is not necessary to cover the surface with a hard material such as a place where there is little impact from the outside, the surface protection layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin. It is possible to eliminate the supporting substrate on one side.
The periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material. In addition, if a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.

  In the case of a solar cell using a flexible support such as a polymer film, cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material. Thus, the battery body can be produced. Further, a module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 may be used. Furthermore, a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.

<Electronic element>
The electronic device of this invention contains the electron-accepting compound represented by Formula (1). Examples of the electronic element include a photoelectric conversion element, an organic thin film transistor, and an organic EL element. The configuration of each electronic element is as described above.

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

Synthesis example 1
(Synthesis of electron accepting compound 1)

  Dichlorobis (diphenylphosphinoethane) cobalt 36.7 mg (0.069 mmol) synthesized in the manner described in Inorganic Chemistry, Vol. 21, page 2051 (1982), powdered manganese 114 mg (2.07 mmol) in an argon-substituted flask , 90 mL of o-dichlorobenzene was added to form a suspension and stirred at 25 ° C. for 1 hour. Thereafter, 500 mg (0.69 mmol) of C60 fullerene, 536 mg (2.07 mmol) of methyl 4-bromomethyl-3-methoxybenzoate, and 124 mg (6.9 mmol) of water were added and stirred at 25 ° C. for 48 hours. After stirring, the mixture was filtered using Florisil (registered trademark of Floridin) as a filter aid, and the solvent was removed with an evaporator. The obtained crude product was purified by silica gel column chromatography using toluene as an elution solvent. After removing the solvent with an evaporator, the product was washed with an acetone solvent, and the remaining toluene solvent was removed. Thus, 373 mg (0.414 mmol) of the target electron-accepting compound 1 was obtained.

Example 1 (Production and Evaluation of Organic Thin Film Solar Cell)
Regioregular poly (3-hexylthiophene) (Lumtec LT-S909) was dissolved in o-dichlorobenzene at a concentration of 20 mg / mL. An ink was prepared by adding the electron-accepting compound 1 to the obtained liquid at an equal weight with respect to the weight of regioregular poly (3-hexylthiophene). Regioregular poly-3-hexylthiophene acts as an electron donating compound.
An ITO film was formed on the glass substrate by sputtering. The sheet resistance of the ITO film was 10Ω / sq. The glass substrate on which the ITO film was formed was immersed in an acetone bath for ultrasonic cleaning, and then immersed in an ethanol bath for ultrasonic cleaning. Next, a PEDOT: PSS solution (CLEVOS P VP AI 4083, manufactured by HC Starck Co., Ltd.) was applied onto the ITO film by spin coating, and heated in the atmosphere at 110 ° C. for 10 minutes to obtain a positive film thickness of 40 nm. A hole injection layer was prepared. Next, the said ink was apply | coated to the board | substrate with which the PEDOT: PSS film | membrane was formed with the spin coat method, and the active layer of the organic thin film solar cell was obtained. The thickness of the active layer was about 210 nm. Then, it baked for 10 minutes on 110 degreeC conditions in nitrogen atmosphere. Thereafter, lithium fluoride (thickness 1 nm) and aluminum (thickness 80 nm) were sequentially deposited by a vacuum vapor deposition machine to obtain an organic thin film solar cell. The degree of vacuum at the time of vapor deposition was 5 × 10 ⁻⁴ Pa. Moreover, the shape of the obtained organic thin film solar cell was a square of 2 mm × 2 mm. The characteristics of the obtained organic thin film solar cell were irradiated with constant light using a solar simulator (Bunkoh-Keiki Co., trade name OTENTO-SUN III: AM1.5G filter, irradiance 100 mW / cm ² ). It was determined by measuring the generated current and voltage. As a result, the open end voltage was 0.63V.

Comparative Example 1 (Production and Evaluation of Organic Thin Film Solar Cell)
In Example 1, an organic thin film solar cell was prepared in the same manner except that [6,6] -phenyl C ₆₁ -butyric acid methyl ester ([60] -PCBM) was used instead of the electron accepting compound 1. The characteristic of the obtained organic thin film solar cell was calculated | required. As a result, the open end voltage was 0.60V.

Claims (8)

A composition comprising an electron-accepting compound represented by formula (1) and an electron-donating compound.

(In the formula, F represents a fullerene ring. R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, An aryl group which may have a substituent, an aryloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, or .n representing the good acyloxy group which may have a substituent if .R ¹ represents an integer of 1 to 10 there are a plurality, they are good .R ² be different be the same as each other When there are a plurality of them, they may be the same or different from each other Ar ¹ is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a substituent; An alkenyl group which may have .R ⁸ representing the alkynyl which may have a group is a hydrogen atom, an R ^8, and the group containing R ^1, R ² and Ar ^1, respectively, one constituting the fullerene skeleton six ( It is bonded to two adjacent carbon atoms in the member ring .) Ar ¹ is group represented by a following formula (1-1), The composition of Claim 1 characterized by the above-mentioned.

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may each independently have a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, or a substituent. A good alkoxy group, an aryl group which may have a substituent, an aryloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, or a substituent Represents a good acyl group, an acyloxy group which may have a substituent, or a heterocyclic group which may have a substituent.)   The composition according to claim 1 or 2, wherein F is C60 fullerene or C70 fullerene.   The composition according to any one of claims 1 to 3, wherein the electron donating compound is a conjugated polymer.   The composition according to claim 4, wherein the conjugated polymer contains a thiophene ring.   An ink comprising the composition according to any one of claims 1 to 5 and a solvent.   A first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, the active layer according to any one of claims 1 to 5. The photoelectric conversion element containing the composition of description. An electronic device comprising an electron-accepting compound represented by formula (1).

(In the formula, F represents a fullerene ring. R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, An aryl group which may have a substituent, an aryloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, or .n representing the good acyloxy group which may have a substituent if .R ¹ represents an integer of 1 to 10 there are a plurality, they are good .R ² be different be the same as each other When there are a plurality of them, they may be the same or different from each other Ar ¹ is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a substituent; An alkenyl group which may have .R ⁸ representing the alkynyl which may have a group is a hydrogen atom, an R ^8, and the group containing R ^1, R ² and Ar ^1, respectively, one constituting the fullerene skeleton six (It is bonded to two adjacent carbon atoms in the member ring.)