JP5601276B2 - Organic photoelectric conversion element - Google Patents

Description

  The present invention relates to an organic photoelectric conversion element.

  In recent years, studies using an organic semiconductor material for an active layer of an organic photoelectric conversion element (such as an organic solar cell or an optical sensor) have been actively conducted. In particular, if a composition containing a polymer compound is used as an organic semiconductor material, an active layer can be produced by an inexpensive coating method. Therefore, an organic photoelectric conversion element including a composition containing various polymer compounds has been studied. Has been. For example, an organic solar cell having an organic layer containing poly-3-hexylthiophene that is a conjugated polymer compound and C60PCBM that is a fullerene derivative is described (Non-Patent Document 1).

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

  However, the organic photoelectric conversion element has a problem that an open circuit voltage (Voc) is not always sufficient.

  Then, an object of this invention is to provide the organic photoelectric conversion element which can provide a high open end voltage.

（１）
（式中、Ａ環及びＢ環は、同一又は相異なり、芳香環を表す。Ａ²は、Ａ環及びＢ環と結合して５員環若しくは６員環を形成する２価の基、−Ｓ−又は−Ｏ−を表す。Ｒ^１は、水素原子、ハロゲン原子、フッ素置換されていてもよいアルキル基、フッ素置換されていてもよいアルコキシ基、フッ素置換されていてもよいアルキルチオ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルコキシ基、置換されていてもよいアリールアルキルチオ基、ジヒドロキシボリル基、ホウ酸エステル残基、ハロマグネシウム基、置換されていてもよいスタンニル基、又は、スルホン酸残基を表す。２個あるＲ^１は、同一であっても相異なっていてもよい。） That is, the present invention first includes an organic layer having a pair of electrodes and an organic layer provided between the electrodes, wherein the organic layer includes a compound represented by the formula (1) and a conjugated polymer compound. A photoelectric conversion element is provided.

(1)
(In the formula, A ring and B ring are the same or different and each represents an aromatic ring. A ² is a divalent group that forms a 5-membered or 6-membered ring by combining with A ring and B ring; R ¹ represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted with fluorine, an alkoxy group which may be substituted with fluorine, an alkylthio group which may be substituted with fluorine, or substituted. Aryl group which may be substituted, aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted, substituted An arylalkylthio group, a dihydroxyboryl group, a boric acid ester residue, a halomagnesium group, an optionally substituted stannyl group, or a sulfonic acid residue. ¹ may be different and the same.)

  Secondly, the present invention provides the organic photoelectric conversion element in which the weight of the compound represented by the formula (1) in the organic layer is 0.1 to 10,000 parts by weight with respect to 100 parts by weight of the conjugated polymer compound. provide.

  Thirdly, the present invention provides the organic photoelectric conversion device, wherein the organic layer further contains an electron accepting compound.

  Fourthly, the present invention provides the organic photoelectric conversion element, wherein the electron accepting compound is a fullerene derivative.

  Fifth, the present invention provides the organic photoelectric conversion device, wherein the organic layer further contains an electron donating compound.

  Since the organic photoelectric conversion device of the present invention exhibits a high open-circuit voltage, the present invention is extremely useful.

  Hereinafter, the present invention will be described in detail.

（１）
（式中、Ａ環及びＢ環は、同一又は相異なり、芳香環を表す。Ａ²は、Ａ環及びＢ環と結合して５員環若しくは６員環を形成する２価の基、−Ｓ−又は−Ｏ−を表す。Ｒ^１は、水素原子、ハロゲン原子、フッ素置換されていてもよいアルキル基、フッ素置換されていてもよいアルコキシ基、フッ素置換されていてもよいアルキルチオ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルコキシ基、置換されていてもよいアリールアルキルチオ基、ジヒドロキシボリル基、ホウ酸エステル残基、ハロマグネシウム基、置換されていてもよいスタンニル基、又は、スルホン酸残基を表す。２個あるＲ^１は、同一であっても相異なっていてもよい。） The organic photoelectric conversion element of the present invention has an organic layer containing a compound represented by the formula (1) and a conjugated polymer compound.

(1)
(In the formula, A ring and B ring are the same or different and each represents an aromatic ring. A ² is a divalent group that forms a 5-membered or 6-membered ring by combining with A ring and B ring; R ¹ represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted with fluorine, an alkoxy group which may be substituted with fluorine, an alkylthio group which may be substituted with fluorine, or substituted. Aryl group which may be substituted, aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted, substituted An arylalkylthio group, a dihydroxyboryl group, a boric acid ester residue, a halomagnesium group, an optionally substituted stannyl group, or a sulfonic acid residue. ¹ may be different and the same.)

In formula (1), examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In formula (1), the alkyl group represented by R ¹ usually has 1 to 20 carbon atoms, and may be linear or branched, or may be 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, 3,7-dimethyloctyl group and lauryl group. A hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

In formula (1), in the alkoxy group represented by R ¹ , the alkyl moiety usually has 1 to 20 carbon atoms, and may be linear or branched, or may be cyclic. 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, heptyl Examples thereof include an oxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, and a lauryloxy group. A hydrogen atom in the alkoxy group may be substituted with a fluorine atom. Examples of the alkoxy group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.

In formula (1), in the alkylthio group represented by R ¹ , the alkyl moiety usually has about 1 to 20 carbon atoms, and may be linear or branched, or cyclic. Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group. Octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group and laurylthio group. A hydrogen atom in the alkylthio group may be substituted with a fluorine atom. Examples of the alkylthio group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethylthio group.

（６）
（式（６）中、ｇは１〜６の整数を表し、ｈは０〜５の整数を表す。） In formula (1), the aryl group represented by R ¹ is an atomic group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, having a benzene ring, having a condensed ring, Those in which two or more independent benzene rings or condensed rings are bonded directly or via a group such as vinylene are also included. The aryl group usually has 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms. Specific examples of the aryl group include a phenyl group, a C _{1 to} C ₁₂ alkylphenyl group (C _{1 to} C ₁₂ represents ₁ to ₁₂ carbon atoms, the same shall apply hereinafter), and a 1-naphthyl group. , 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group and 9-anthracenyl group. The aryl group may have a substituent. Examples of the substituent include a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms, or a carbon number. Specific examples of the substituted aryl group include an alkoxy group having 3 to 20 cycloalkyl groups in its structure, an alkoxyalkoxy group represented by the formula (6), and a fluorine atom, and C _{1 to} C _12. Examples thereof include an alkoxyphenyl group and a pentafluorophenyl group. Preferred examples of optionally substituted aryl groups _include C 1 _{-C 12} alkoxyphenyl groups and _C 1 _{-C 12} alkylphenyl group. Specific examples of the C _{1 to} C ₁₂ alkoxyphenyl group include a methoxyphenyl group, an ethoxyphenyl group, a propoxyphenyl group, an isopropoxyphenyl group, a butoxyphenyl group, an isobutoxyphenyl group, a sec-butoxyphenyl group, and a tert-butoxyphenyl group. Group, pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctyl An oxyphenyl group and a lauryloxyphenyl group are mentioned. Specific examples of C ₁ -C ₁₂ alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, Examples include sec-butylphenyl group, tert-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group and dodecylphenyl group.

(6)
(In formula (6), g represents an integer of 1-6, and h represents an integer of 0-5.)

In formula (1), the aryloxy group represented by R ¹ usually has 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms. Specific examples of the aryloxy group which may be substituted, phenoxy _group, C 1 _{-C 12} alkoxy phenoxy _group, C 1 _{-C 12} alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group and pentafluoro include phenyl _group, C 1 _{-C 12} alkoxy phenoxy group, and a _C 1 _{-C 12} alkylphenoxy group are preferable. Specific examples of C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2- Examples include ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy and lauryloxy. Specific examples of the C _{1 to} C ₁₂ alkylphenoxy group include methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, butyl Phenoxy group, isobutylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group and dodecylphenoxy group Is mentioned.

In the formula (1), the arylthio group represented by R ¹ usually has 6 to 60 carbon atoms, and specific examples of the optionally substituted arylthio group include a phenylthio group and a C _{1 to} C ₁₂ alkoxy group. phenylthio _group, C 1 _{-C 12} alkyl phenylthio group, 1-naphthylthio group, and a 2-naphthylthio group and a pentafluorophenylthio group.

In the formula (1), the arylalkyl group represented by R ¹ usually has about 7 to 60 carbon atoms. Specific examples of the optionally substituted arylalkyl group include phenyl-C ₁ -C ₁₂ alkyl _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkyl group, 1-naphthyl _-C 1 _{-C 12} alkyl group, and a 2 naphthyl _-C 1 _{-C 12} alkyl group.

In formula (1), the arylalkoxy group represented by R ¹ usually has 7 to 60 carbon atoms. Specific examples of the optionally substituted arylalkoxy group include phenyl-C _{1 to} C _12. alkoxy _groups, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkoxy _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkoxy groups, 1-naphthyl _-C 1 _{-C 12} alkoxy group and 2-naphthyl -C ₁ -C ₁₂ alkoxy group.

In the formula (1), the arylalkylthio group represented by R ¹ usually has 7 to 60 carbon atoms. Specific examples of the optionally substituted arylalkylthio group include phenyl-C _{1 to} C _12. alkylthio _group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkylthio _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkylthio group, 1-naphthyl _-C 1 _{-C 12} alkylthio group and a 2-naphthyl -C ₁ -C ₁₂ alkylthio group.

In the formula (1), the boric acid ester residue represented by R ¹ means a group obtained by removing a hydroxyl group from a boric acid diester, and a dialkyl ester residue, a diaryl ester residue, a diarylalkyl ester residue, etc. Can be mentioned. Specific examples of the boric acid ester residue include groups represented by the following formulas.

In the formula (1), as an optionally substituted stannyl group represented by R ¹ , a stannyl group, a trichlorostannyl group, a trimethylstannyl group, a triethylstannyl group, a tri-n-butylstannyl group, Examples thereof include a triphenylstannyl group and a tribenzylstannyl group.

In formula (1), the sulfonic acid residue represented by R ¹ means a group obtained by removing an acidic hydrogen atom (H of the —SO ₃ H moiety) from sulfonic acid, and specific examples of the sulfonic acid include , Alkanesulfonic acids (eg methanesulfonic acid, ethanesulfonic acid), arenesulfonic acids (eg benzenesulfonic acid, p-toluenesulfonic acid), arylalkanesulfonic acids (eg phenylmethanesulfonic acid) and trifluoromethanesulfonic acid Is mentioned.

R ¹ is preferably a hydrogen atom, an alkyl group, or a halogen atom from the viewpoint of charge transportability.

  In the formula (1), the A ring and B ring aromatic rings are aromatic carbocyclic rings or aromatic heterocyclic rings. Examples of the aromatic carbocycle include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the aromatic heterocycle include a thiophene ring, a pyridine ring, and a furan ring. The aromatic ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

In formula (1), A ² represents a divalent group, —S— or —O—, which is bonded to the A ring and the B ring to form a 5-membered ring or a 6-membered ring. Examples of the divalent group that forms a 5-membered or 6-membered ring include —C (R ² ) ₂ —, —O—C (R ³ ) ₂ —, —N (R ⁴ ) —, —Si (R ⁵ ) ₂ —, —B (R ⁶ ) —, —C (R ⁷ ) ₂ —C (R ⁷ ) ₂ — and the like. R ^{2 to} R ⁷ are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or optionally substituted. Represents an arylalkyl group or a heterocyclic group. Two R ² may be the same or different. Two R ² may be bonded to each other to form a cyclic structure. Two R ³ may be the same or different. Two R ⁵ may be the same or different. The four R ⁷ may be the same or different.

Definitions of an optionally substituted fluorine-substituted alkyl group, an optionally substituted fluorine group, an optionally substituted aryl group, and an optionally substituted arylalkyl group represented by R ^{2 to} R ⁷ , and Specific examples are the definition of an optionally substituted fluorine group, an optionally substituted alkoxy group, an optionally substituted aryl group and an optionally substituted arylalkyl group represented by R ^1. And the same as the specific example.

The heterocyclic group represented by R ^{2 to} R ⁷ usually has 2 to 60 carbon atoms, and is preferably an aromatic heterocyclic group. Specific examples include an optionally substituted pyridyl group, an optionally substituted furyl group, an optionally substituted piperidyl group, an optionally substituted quinolyl group, an optionally substituted isoquinolyl group, and An pyrrolyl group which may be substituted is exemplified.

  Examples of the compound represented by the formula (1) include the following compounds.

（２−１）
（式中、Ａ環、Ｂ環、Ｒ^１及びＲ^２は、前述と同じ意味を表す。） One preferable aspect of the compound represented by Formula (1) is a compound represented by Formula (2-1).

(2-1)
(In the formula, A ring, B ring, R ¹ and R ² have the same meaning as described above.)

（２−２）
（式中、Ｒ^１及びＲ^２は、前述と同じ意味を表す。） In Formula (2-1), the A ring and the B ring are preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
As the compound represented by the formula (2-1), a compound represented by the formula (2-2) is preferable.

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

（３）
（式中、Ｒ^１及びＲ^３は、前述と同じ意味を表す。） Another preferred embodiment of the compound represented by the formula (1) is a compound represented by the formula (3).

(3)
(In the formula, R ¹ and R ³ represent the same meaning as described above.)

（４）
（式中、Ｒ^８は、水素原子、フッ素置換されていてもよいアルキル基、フッ素置換されていてもよいアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールアルキル基又は複素環基を表す。２個あるＲ^８は、同一であっても相異なっていてもよい。Ｒ^１は前述と同じ意味を表す。） Another preferred embodiment of the compound represented by the formula (1) is a compound represented by the formula (4).

(4)
(In the formula, R ⁸ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted arylalkyl group, or Represents a heterocyclic group, and two R ^{8 s} may be the same or different, and R ¹ represents the same meaning as described above.

Definition of an optionally substituted fluorine-substituted alkyl group represented by R ⁸ , an optionally substituted fluorine-substituted alkoxy group, an optionally substituted aryl group, an optionally substituted arylalkyl group, and a heterocyclic group And specific examples include an optionally substituted fluorine-substituted alkyl group represented by R ² , an optionally substituted fluorine-substituted alkoxy group, an optionally substituted aryl group, an optionally substituted arylalkyl group, and The definition and specific examples of the heterocyclic group are the same. R ⁸ is preferably an alkoxy group.

（５）
（式中、Ｒ^１及びＲ^４は、前述と同じ意味を表す。） The preferable aspect of the compound represented by Formula (1) is a compound represented by Formula (5).

(5)
(In the formula, R ¹ and R ⁴ have the same meaning as described above.)

In formula (5), R ⁴ is preferably a phenyl group, a phenyl group substituted with one or more alkyl groups, and a phenyl group substituted with one or more alkoxy groups.

  The compound represented by the formula (1) contained in the organic layer of the organic photoelectric conversion element of the present invention may be one type or two or more types.

<Conjugated polymer compound>
The conjugated polymer compound used in the organic photoelectric conversion device of the present invention includes (1) a polymer compound substantially composed of a structure in which double bonds and single bonds are alternately arranged, and (2) double bonds and single bonds. Compound consisting essentially of a structure in which nitrogen atoms are arranged through nitrogen atoms, (3) a structure in which double bonds and single bonds are arranged alternately, and double bonds and single bonds are arranged through nitrogen atoms Examples thereof include a polymer compound substantially having a structure. Specific examples of the conjugated polymer compound include an optionally substituted fluorenediyl group, an optionally substituted benzofluorenediyl group, an optionally substituted dibenzofurandiyl group, and an optionally substituted dibenzo. A thiophenediyl group, an optionally substituted carbazolediyl group, an optionally substituted thiophenediyl group, an optionally substituted furandyl group, an optionally substituted pyrroldiyl group, and an optionally substituted benzo One or more selected from the group consisting of a thiadiazolediyl group, an optionally substituted phenylene vinylene group, an optionally substituted thienylene vinylene group, and an optionally substituted triphenylamine diyl group as a repeating unit , Polymer compounds in which the repeating units are bonded directly or via a linking group A.

  Here, examples of the linking group include phenylene, biphenylene, naphthalenediyl, and anthracenediyl.

（７） （８）
〔式中、Ｒ⁹、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８は、同一又は相異なり、水素原子、フッ素置換されていてもよいアルキル基、フッ素置換されていてもよいアルコキシ基、フッ素置換されていてもよいアルキルチオ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアリールチオ基、置換されていてもよいアリールアルキル基、置換されていてもよいアリールアルコキシ基又は置換されていてもよいアリールアルキルチオ基を表す。〕 The conjugated polymer compound used in the present invention preferably has one or more repeating units selected from the group consisting of formula (7) and formula (8) from the viewpoint of charge transportability.

(7) (8)
[Wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different and may be substituted with a hydrogen atom or fluorine. Alkyl group, optionally substituted fluorine group alkoxy group, optionally substituted fluorine atom substituted alkylthio group, optionally substituted aryl group, optionally substituted aryloxy group, optionally substituted arylthio group Represents an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or an optionally substituted arylalkylthio group. ]

Fluorine-substituted alkyl group represented by R ^{9 to} R ¹⁸ , fluorine-substituted alkoxy group, fluorine-substituted alkylthio group, optionally substituted aryl group, substituted Definition and specifics of aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted and arylalkylthio group which may be substituted Examples are the same as the definitions and specific examples regarding R ¹ described above.

The conjugated polymer compound preferably has a polystyrene-equivalent weight average molecular weight of 5 × 10 ² to 1 × 10 ⁷ from the viewpoint of film forming ability and solubility in a solvent, and preferably 1 × 10 ³ to 1 ×. More preferably, it is 10 ⁶ .

  The conjugated polymer compound contained in the organic layer of the organic photoelectric conversion element of the present invention may be one type or two or more types.

  The conjugated polymer compound is prepared by synthesizing a monomer having a functional group suitable for the polymerization reaction used for its production, and then, if necessary, dissolving the monomer in an organic solvent to obtain an alkali or a suitable catalyst. It can be produced by polymerizing the monomer by a known polymerization method such as aryl coupling using a ligand.

<Organic layer>
The organic layer of the organic photoelectric conversion element of the present invention includes a compound represented by the formula (1) and a conjugated polymer compound. The weight of the compound represented by the formula (1) in the organic layer is preferably 0.1 to 10,000 parts by weight, more preferably 1 to 1000 parts by weight with respect to 100 parts by weight of the conjugated polymer compound. .

The organic layer of the organic photoelectric conversion device of the present invention may contain only the compound represented by the formula (1) and the conjugated polymer compound, and may further contain an electron accepting compound. Examples of the electron-accepting compound include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerene and derivatives thereof such as C _60, carbon nanotube, 2,9 Examples include phenanthroline derivatives such as -dimethyl-4,7-diphenyl-1,10-phenanthroline, and fullerene and derivatives thereof are particularly preferable.

  When the electron-accepting compound is contained, the weight of the electron-accepting compound in the organic layer is 1 to 1 when the total weight of the compound represented by formula (1) and the weight of the conjugated polymer compound is 100 parts by weight. The amount is preferably 10,000 parts by weight, and more preferably 10 to 2000 parts by weight.

Fullerenes and derivatives thereof include C ₆₀ , C ₇₀ , C ₈₄ and derivatives thereof. The fullerene derivative represents a fullerene having a substituent.

Specific examples of the C ₆₀ derivative include the following.

Specific examples of the C ₇₀ derivative include the following.

  The organic layer of the organic photoelectric conversion device of the present invention may further contain an electron donating compound. Examples of the electron donating compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and aromatic amines in side chains or main chains. And polysiloxane derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.

  When the electron donating compound is contained, the weight of the electron donating compound in the organic layer is 1 to 1 when the total weight of the compound represented by the formula (1) and the weight of the conjugated polymer compound is 100 parts by weight. The amount is preferably 100,000 parts by weight, and more preferably 10 to 1,000 parts by weight.

  The organic layer of the organic photoelectric conversion device of the present invention has a compound represented by the formula (1), a conjugated polymer compound, an electron donating compound, and an electron accepting property as long as the charge transporting property and the charge injecting property are not impaired. Components other than the compound may be included.

<Organic photoelectric conversion element>
The organic photoelectric conversion element of the present invention has a pair of electrodes and an organic layer containing a compound represented by the formula (1) and a conjugated polymer compound between the electrodes. The composition of the compound represented by the formula (1) and the conjugated polymer compound can be used as an electron accepting compound or an electron donating compound. Further, when one of the compound represented by the formula (1) and the conjugated polymer compound is an electron donating compound and the other is an electron accepting compound, both of the electron donor and the electron acceptor are used. It may have a function. In these embodiments, the composition is preferably used as an electron donating compound. It is preferable that at least one of the pair of electrodes is transparent or translucent.

  Next, the operation mechanism of the organic photoelectric conversion element will be described. Light energy incident from a transparent or translucent electrode is absorbed by the electron-accepting compound and / or the electron-donating compound to generate excitons in which electrons and holes are combined. When the generated excitons move and reach the heterojunction 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 are generated. The generated charges can be taken out as electric energy (current) by moving to the electrodes.

  Voc (open end voltage) is a voltage when the current flowing to the outside is zero, and a high value of Voc is one of the factors that develop high photoelectric conversion efficiency.

Specific examples of the organic photoelectric conversion device of the present invention include the following 1. ~ 5. The organic photoelectric conversion element of this is mentioned.
1. A pair of electrodes, a first organic layer containing a compound represented by formula (1) and a conjugated polymer compound between the electrodes, and an electron donating property provided adjacent to the first organic layer An organic photoelectric conversion element having a second organic layer containing a compound;
2. A pair of electrodes, a first organic layer containing an electron-accepting compound between the electrodes, a compound represented by formula (1) and a conjugated polymer compound provided adjacent to the first organic layer An organic photoelectric conversion element having a second organic layer containing
3. An organic photoelectric conversion element having at least one organic layer containing a pair of electrodes and a compound represented by the formula (1), a conjugated polymer compound, and an electron-donating compound between the electrodes;
4). An organic photoelectric conversion element having a pair of electrodes and an organic layer containing a compound represented by the formula (1), a conjugated polymer compound, and an electron-accepting compound between the electrodes;
5. An organic photoelectric conversion element having a pair of electrodes and at least one organic layer containing a compound represented by the formula (1), a conjugated polymer compound, and an electron-accepting compound between the electrodes, An organic photoelectric conversion element in which the compound is a fullerene derivative;

  In addition, said 5. In the organic photoelectric conversion element, the weight of the fullerene derivative in the organic layer is 10 to 1000 parts by weight when the total of the weight of the compound represented by the formula (1) and the weight of the conjugated polymer compound is 100 parts by weight. It is preferable that it is 50-500 weight part.

  As the organic photoelectric conversion element of the present invention, 3. 4. 5. From the standpoint of including a large number of heterojunction interfaces, the above organic photoelectric conversion element is preferable. The organic photoelectric conversion element is more preferable. In the organic photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the organic layer in the element. Examples of the additional layer include a charge transport layer that transports holes or electrons.

  When the composition of the compound represented by the formula (1) and the conjugated polymer compound is used as an electron donor, the electron acceptor suitably used for the organic photoelectric conversion element has a conjugated polymer in which the HOMO energy of the electron acceptor is The HOMO energy of the compound and the HOMO energy of the compound represented by the formula (1) are higher, and the LUMO energy of the electron acceptor is the LUMO energy of the conjugated polymer compound and the LUMO energy of the compound represented by the formula (1) Is a higher compound. Moreover, when using the high molecular compound of the compound represented by Formula (1) and a conjugated high molecular compound as an electron acceptor, the electron donor used suitably for an organic photoelectric conversion element has the HOMO energy of an electron donor. The HOMO energy of the conjugated polymer compound is lower than the HOMO energy of the compound represented by the formula (1), and the LUMO energy of the electron donor is the LUMO energy of the conjugated polymer compound and the compound represented by the formula (1) This is a compound having a lower LUMO energy.

  The organic 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 is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent.

As a material of the pair of electrodes, a metal, a conductive polymer, or the like can be used, and one of the pair of electrodes is preferably a material having a low work function. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and two of them One or more alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or a graphite intercalation compound are used. It is done. 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, and calcium-aluminum alloy.
Examples of the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA Gold, platinum, silver, and copper are used, and ITO, indium / zinc / oxide, 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. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

As the material used for the charge transport layer as the additional layer, that is, the hole transport layer and the electron transport layer, the aforementioned electron donating compound and electron accepting compound can be used, respectively.
As a material used for the buffer layer as an additional layer, an alkali metal such as lithium fluoride, a halide of an alkaline earth metal, an oxide, or the like can be used. In addition, fine particles of an inorganic semiconductor such as titanium oxide can be used.

  As said organic layer in the organic photoelectric conversion element of this invention, the organic thin film containing the compound and conjugated polymer compound which are represented by Formula (1) can be used, for example.

  The organic thin film has a thickness of 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.

  In order to enhance the hole transport property of the organic thin film, a low molecular compound and / or a conjugated polymer compound other than the compound represented by the formula (1) as an electron donating compound and / or an electron accepting compound in the organic thin film It is also possible to use a mixture of other polymers.

<Method for producing organic thin film>
The organic layer contained in the organic photoelectric conversion element of the present invention can be produced using a composition of a compound represented by the formula (1) and a conjugated polymer compound. When the organic layer further contains an electron-accepting compound, it can be produced using a composition of the compound represented by formula (1), a conjugated polymer compound, and an electron-accepting compound. Further, when the organic layer further contains an electron donating compound, it can be produced by using a composition of a compound represented by the formula (1), a conjugated polymer compound and an electron donating compound.

  The weight of the compound represented by formula (1) in the composition is preferably 0.1 to 10000 parts by weight, more preferably 1 to 1000 parts by weight with respect to 100 parts by weight of the conjugated polymer compound. is there. When an electron-accepting compound is contained in the composition, the weight of the electron-accepting compound in the composition is 100 parts by weight of the sum of the weight of the compound represented by formula (1) and the weight of the conjugated polymer compound. Then, it is preferable that it is 1-10000 weight part, and it is more preferable that it is 10-2000 weight part. When the composition includes an electron donating compound, the weight of the electron donating compound in the composition is 100 parts by weight of the sum of the weight of the compound represented by the formula (1) and the weight of the conjugated polymer compound. Then, it is preferable that it is 1-100000 weight part, and it is more preferable that it is 10-1000 weight part.

  The method for producing the organic thin film is not particularly limited, and examples thereof include a method by film formation from a solution containing the composition and a solvent, but the thin film may be formed by a vacuum deposition method. Examples of the method for producing an organic thin film by film formation from a solution include a method of producing an organic thin film by applying the solution on one electrode and then evaporating the solvent.

  The solvent used for film formation from a solution is not particularly limited as long as it dissolves the compound represented by the formula (1) and the conjugated polymer compound. Examples of the solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbezen, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane. Halogenated saturated hydrocarbon solvents such as chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, tetrahydrofuran, And ether solvents such as tetrahydropyran. The composition of the compound represented by formula (1) and the conjugated polymer compound used in the present invention can be usually dissolved in the solvent in an amount of 0.1% by weight or more.

  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.

<Application of device>
By irradiating light such as sunlight from a transparent or translucent electrode, the organic photoelectric conversion element generates a photovoltaic force between the electrodes and can be operated as an organic thin film solar cell. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.

  In addition, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes, a photocurrent flows and it can be operated as an organic photosensor. It can also be used as an organic image sensor by integrating a plurality of organic photosensors.

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

-Method for measuring molecular weight-
In the following Examples, the molecular weight of the conjugated polymer compound was determined by GPC Laboratories GPC (PL-GPC2000). The conjugated polymer compound was dissolved in o-dichlorobenzene so as to have a concentration of about 1% by weight. As the mobile phase of GPC, o-dichlorobenzene was used and allowed to flow at a measurement temperature of 140 ° C. at a flow rate of 1 mL / min. As the column, three PLGEL 10 μm MIXED-B (manufactured by PL Laboratory) were connected in series.

フラスコ内の気体をアルゴンで置換した２Ｌ四つ口フラスコに、化合物（Ｃ）を７．９２８ｇ（１６．７２ｍｍｏｌ）、化合物（Ｄ）を１３．００ｇ（１７．６０ｍｍｏｌ）、メチルトリオクチルアンモニウムクロライド（商品名：aliquat336（登録商標）、Aldrich製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml，25℃）を４．９７９ｇ、及び、トルエンを４０５ｍｌ入れ、撹拌しながら反応系内を３０分間アルゴンバブリングした。フラスコ内にジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）を０．０２ｇ加え、１０５℃に昇温し、撹拌しながら２ｍｏｌ／Ｌの炭酸ナトリウム水溶液４２．２ｍｌを滴下した。滴下終了後５時間反応させ、反応液にフェニルボロン酸２．６ｇとトルエン１．８ｍｌとを加え、１０５℃で１６時間撹拌した。その後、反応液にトルエン７００ｍｌ及び７．５％ジエチルジチオカルバミン酸ナトリウム三水和物水溶液２００ｍｌを加え、８５℃で３時間撹拌した。反応液の水層を除去後、有機層を６０℃のイオン交換水３００ｍｌで２回、６０℃の３％酢酸３００ｍｌで１回、さらに６０℃のイオン交換水３００ｍｌで３回洗浄した。有機層をセライト、アルミナ及びシリカを充填したカラムに通し、濾液を回収した。その後、熱トルエン８００ｍｌでカラムを洗浄し、洗浄後のトルエン溶液を濾液に加えた。得られた溶液を７００ｍｌまで濃縮した後、濃縮した溶液を２Ｌのメタノールに加え、重合体を再沈殿させた。重合体を濾過して回収し、５００ｍｌのメタノール、５００ｍｌのアセトン、５００ｍｌのメタノールで重合体を洗浄した。重合体を５０℃で一晩真空乾燥することにより、下記式：

で表されるペンタチエニル−フルオレンコポリマー（以下、「共役高分子化合物１」という）を１２．２１ｇ得た。共役高分子化合物１のポリスチレン換算の数平均分子量は５．４×１０⁴、ポリスチレン換算の重量平均分子量は１．１×１０⁵であった。 Synthesis example 1
(Synthesis of Conjugated Polymer Compound 1)

In a 2 L four-necked flask in which the gas in the flask was replaced with argon, 7.928 g (16.72 mmol) of compound (C), 13.00 g (17.60 mmol) of compound (D), methyltrioctylammonium chloride ( Product name: aliquat336 (registered trademark), manufactured by Aldrich, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C.) 4.979 g and toluene 405 ml were added and stirred. Then, argon was bubbled through the reaction system for 30 minutes. 0.02 g of dichlorobis (triphenylphosphine) palladium (II) was added to the flask, the temperature was raised to 105 ° C., and 42.2 ml of a 2 mol / L sodium carbonate aqueous solution was added dropwise with stirring. After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours, and 2.6 g of phenylboronic acid and 1.8 ml of toluene were added to the reaction solution, followed by stirring at 105 ° C. for 16 hours. Thereafter, 700 ml of toluene and 200 ml of 7.5% sodium diethyldithiocarbamate trihydrate aqueous solution were added to the reaction solution, followed by stirring at 85 ° C. for 3 hours. After removing the aqueous layer from the reaction solution, the organic layer was washed twice with 300 ml of ion exchanged water at 60 ° C., once with 300 ml of 3% acetic acid at 60 ° C., and further three times with 300 ml of ion exchanged water at 60 ° C. The organic layer was passed through a column packed with celite, alumina and silica, and the filtrate was collected. Thereafter, the column was washed with 800 ml of hot toluene, and the washed toluene solution was added to the filtrate. After the obtained solution was concentrated to 700 ml, the concentrated solution was added to 2 L of methanol to reprecipitate the polymer. The polymer was recovered by filtration, and the polymer was washed with 500 ml of methanol, 500 ml of acetone, and 500 ml of methanol. By vacuum drying the polymer at 50 ° C. overnight, the following formula:

12.21 g of a pentathienyl-fluorene copolymer represented by the following (hereinafter referred to as “conjugated polymer compound 1”) was obtained. The conjugated polymer compound 1 had a polystyrene-equivalent number average molecular weight of 5.4 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.1 × 10 ⁵ .

Example 1
(Production and evaluation of organic thin-film solar cells)
The conjugated polymer compound 1 was dissolved in o-dichlorobenzene at a concentration of 0.5% (weight%). Thereafter, C60PCBM (Phenyl C61-butyric acid methyl ester, trade name E100, manufactured by Frontier Carbon Co., Ltd.) 3 times the weight of the conjugated polymer compound 1 was mixed into the solution as an electron acceptor. Furthermore, the compound (E) was mixed with the solution in an equal weight relative to the weight of the conjugated polymer compound 1. The solution was filtered through a Teflon (registered trademark) filter having a pore size of 1.0 μm to prepare a coating solution.

（Ｅ）

(E)

A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, the coating solution was applied onto the ITO film by spin coating to obtain an active layer (film thickness of about 100 nm) of the organic thin film solar cell. 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 to 9 × 10 ⁻³ Pa in all cases. Moreover, the shape of the obtained organic thin film solar cell was a square of 2 mm × 2 mm.
Voc (open end voltage) of the obtained organic thin film solar cell was measured with a solar simulator (manufactured by Spectrometer, trade name OTENTO-SUNII: AM1.5G filter, irradiance 100 mW / cm ² ). The measurement results are shown in Table 1.

Example 2
(Production and evaluation of organic thin-film solar cells)
An organic thin-film solar cell was prepared in the same manner as in Example 1 except that the amount of compound (E) added was double the weight of the conjugated polymer compound 1, and Voc was measured. The measurement results are shown in Table 1.

Example 3
(Production and evaluation of organic thin-film solar cells)
An organic thin-film solar cell was prepared in the same manner as in Example 1 except that the amount of compound (E) added was 4 times the weight of the conjugated polymer compound 1, and Voc was measured. The measurement results are shown in Table 1.

（Ｆ） Example 4
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 1 except that the compound (F) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(F)

（Ｇ） Example 5
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 1 except that the compound (G) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(G)

（Ｈ） Example 6
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 1 except that the compound (H) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(H)

（Ｉ） Example 7
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 1 except that the compound (I) produced by the method of Example 1 of JP-A-2004-2703 was used instead of the compound (E), and Voc Was measured. The measurement results are shown in Table 1.

(I)

（Ｊ） Example 8
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 1 except that the compound (J) produced by the method of Example 1 of JP-A-2006-169265 was used instead of the compound (E), and Voc Was measured. The measurement results are shown in Table 1.

(J)

（Ｋ） Example 9
(Production and evaluation of organic thin-film solar cells)
An organic thin-film solar cell was prepared in the same manner as in Example 1 except that the compound (K) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(K)

（Ｌ） Example 10
(Production and evaluation of organic thin-film solar cells)
An organic thin-film solar cell was prepared in the same manner as in Example 1 except that the compound (L) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(L)

（Ｍ） Example 11
(Production and evaluation of organic thin-film solar cells)
An organic thin-film solar cell was prepared in the same manner as in Example 1 except that the compound (M) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(M)

Example 12
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 5 except that the amount of C60PCBM was 10 times the weight of the conjugated polymer compound 1, and Voc was measured. The measurement results are shown in Table 1.

Example 13
(Production and evaluation of organic thin-film solar cells)
An organic thin-film solar cell was produced in the same manner as in Example 12 except that the amount of compound (G) added was 5 times the weight of the conjugated polymer compound 1, and Voc was measured. The measurement results are shown in Table 1.

Example 14
(Production and evaluation of organic thin-film solar cells)
An organic thin-film solar cell was produced in the same manner as in Example 12 except that the amount of compound (G) added was 10 times the weight of the conjugated polymer compound 1, and Voc was measured. The measurement results are shown in Table 1.

Comparative Example 1
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 1 except that the compound represented by the formula (1) was not used, and Voc was measured. The measurement results are shown in Table 1.

Comparative Example 2
(Production and evaluation of organic thin-film solar cells)
An organic thin film solar cell was produced in the same manner as in Example 12 except that the compound represented by the formula (1) was not used, and Voc was measured. The measurement results are shown in Table 1.

Claims (5)

An organic photoelectric conversion element having a pair of electrodes and an organic layer provided between the electrodes, wherein the organic layer includes a compound represented by formula (1) and a conjugated polymer compound ,
The organic photoelectric conversion element whose compound represented by Formula (1) is a compound represented by either of Formula (3)-Formula (5) .

(1)
(In the formula, A ring and B ring are the same or different and each represents an aromatic ring. A ² is a divalent group that forms a 5-membered or 6-membered ring by combining with A ring and B ring; R ¹ represents a hydrogen atom, a halogen atom, an alkyl group which may be substituted with fluorine, an alkoxy group which may be substituted with fluorine, an alkylthio group which may be substituted with fluorine, or substituted. Aryl group which may be substituted, aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted, substituted An arylalkylthio group, a dihydroxyboryl group, a boric acid ester residue, a halomagnesium group, an optionally substituted stannyl group, or a sulfonic acid residue. ¹ may be different and the same.)

(3)
(Wherein R ³ represents a hydrogen atom, an alkyl group which may be substituted with fluorine, an aryl group which may be substituted, an arylalkyl group which may be substituted or a heterocyclic group. ³ may be the same or different, and R ¹ represents the same meaning as described above.

(4)
(In the formula, R ⁸ represents a hydrogen atom, an alkyl group which may be substituted with fluorine, an aryl group which may be substituted, an arylalkyl group which may be substituted or a heterocyclic group. ⁸ may be the same or different, and R ¹ represents the same meaning as described above.

(5)
(.R ¹ wherein, R ⁴ is representing a hydrogen atom, a fluorine optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted arylalkyl group or heterocyclic group, It represents the same meaning as above.)   The organic photoelectric conversion element according to claim 1, wherein the weight of the compound represented by the formula (1) in the organic layer is 0.1 to 10,000 parts by weight with respect to 100 parts by weight of the conjugated polymer compound. In the organic layer, the organic photoelectric conversion element according to claim 1 or 2 include further electron-accepting compound. The organic photoelectric conversion element according to claim 3 , wherein the electron-accepting compound is a fullerene derivative. The organic photoelectric conversion element according to any one of claims 1 to 4 , wherein an electron-donating compound is further contained in the organic layer.