JP5673333B2 - 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、Ｔは、ｎ価の芳香族基を表す。ｎは、２〜４の整数を表す。Ｒ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、アルコキシアルキル基、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、アシル基、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。複数個あるＲは、同一であっても相異なってもよい。） 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, T represents an n-valent aromatic group. N represents an integer of 2 to 4. R represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a fluorine-substituted group. An optionally substituted alkoxy group, an optionally substituted fluorine-substituted alkylthio group, an alkoxyalkyl group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an acyl group Represents an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or an optionally substituted arylalkylthio group, and a plurality of R may be the same or different. )

  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、Ｔは、ｎ価の芳香族基を表す。ｎは、２〜４の整数を表す。Ｒ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、アルコキシアルキル基、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、アシル基、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。複数個あるＲは、同一であっても相異なってもよい。） The organic photoelectric conversion element of this invention has an organic layer containing the compound represented by Formula (1) and a conjugated polymer compound.

(1)
(In the formula, T represents an n-valent aromatic group. N represents an integer of 2 to 4. R represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a fluorine-substituted group. An optionally substituted alkoxy group, an optionally substituted fluorine-substituted alkylthio group, an alkoxyalkyl group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an acyl group Represents an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or an optionally substituted arylalkylthio group, and a plurality of R may be the same or different. )

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

  In formula (1), the alkyl group represented by R 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 the formula (1), the alkoxy group represented by R usually has 1 to 20 carbon atoms, and the alkyl portion 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), the alkylthio group represented by R usually has 1 to 20 carbon atoms, and the alkyl portion may be linear or branched, or may be 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.

（９）
（式中、ｐは、１〜１０の整数を表す。ｑは、０〜９の整数を表す。） In the formula (1), the alkoxyalkyl group represented by R usually has 2 to 20 carbon atoms, and specific examples thereof include a group represented by the formula (9).

(9)
(In the formula, p represents an integer of 1 to 10. q represents an integer of 0 to 9.)

（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 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, independent And those obtained by bonding two or more benzene rings or condensed rings 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. The aryl group may have a substituent. Examples of the substituent include a linear or branched alkyl group having 1 to 20 carbon atoms or an alkoxy group having a cycloalkyl group having 3 to 20 carbon atoms in its structure, a group represented by formula (6), and A fluorine atom. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, and a linear or branched alkyl having 1 to 20 carbon atoms. Group or a phenyl group substituted with a cycloalkyl group having 3 to 20 carbon atoms. Specific examples of the substituted aryl group include a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ represents ₁ to ₁₂ carbon atoms. The same shall apply hereinafter) and a pentafluorophenyl group. Etc. Aryl group which may be preferred substitution _is C 1 _{-C 12} alkoxyphenyl groups and _C 1 _{-C 12} alkylphenyl group. Specific examples of C ₁ -C ₁₂ alkoxyphenyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, butoxyphenyl group, isobutoxyphenyl group, sec- butoxyphenyl, tert- butoxyphenyl Pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctyloxy A phenyl group and a lauryloxyphenyl group; Specific examples of the C _{1 to} C ₁₂ alkylphenyl group include methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, 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 usually has 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms. The aryloxy group may have a substituent. Specific examples of the substituent are the same as those described above as the substituent of the aryl group represented by R. 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 formula (1), the arylthio group represented by R usually has 6 to 60 carbon atoms. The arylthio group may have a substituent. Specific examples of the substituent are the same as those described above as the substituent of the aryl group represented by R. Specific examples of the optionally substituted arylthio group, phenylthio _group, C 1 _{-C 12} alkoxyphenyl-thio _group, C 1 _{-C 12} alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group and pentafluorophenyl A thio group is mentioned.

（式中、Ｒ’は、フッ素置換されていてもよいアルキル基又は置換されていてもよいアリール基を表す。） In formula (1), the acyl group represented by R is, for example, a group represented by the following formula.

(In the formula, R ′ represents an alkyl group which may be substituted with fluorine or an aryl group which may be substituted.)

  Specific examples of the optionally substituted alkyl group represented by R ′ and the optionally substituted aryl group include the optionally substituted fluorine group represented by R and the optionally substituted aryl group. Same as aryl group.

In formula (1), the arylalkyl group represented by R usually has 7 to 60 carbon atoms. The arylalkyl group may have a substituent. Specific examples of the substituent are the same as those described above as the substituent of the aryl group represented by R. Specific examples of the optionally substituted arylalkyl group, a 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 2-naphthyl _-C 1 _{-C 12} alkyl group.

In formula (1), the arylalkoxy group represented by R usually has 7 to 60 carbon atoms. The arylalkoxy group may have a substituent. Specific examples of the substituent are the same as those described above as the substituent of the aryl group represented by R. Substituted Specific examples of which may arylalkoxy group, a phenyl _-C 1 _{-C 12} alkoxy _group, 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 formula (1), the arylalkylthio group represented by R usually has 7 to 60 carbon atoms. The arylalkylthio group may have a substituent. Specific examples of the substituent are the same as those described above as the substituent of the aryl group represented by R. Substituted Specific examples of which may arylalkylthio group, phenyl _-C 1 _{-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.

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

  N in Formula (1) represents the integer of 2-4.

T in Formula (1) is an n-valent aromatic group, and represents an n-valent aromatic carbocyclic group or an n-valent aromatic heterocyclic group. An n-valent aromatic ring group is an n-valent organic group obtained by removing n hydrogen atoms on an aromatic ring from an aromatic carbocyclic compound, and an n-valent aromatic heterocyclic group is an aromatic heterocyclic ring. An n-valent organic group obtained by removing n hydrogen atoms on an aromatic ring from a formula compound.
Examples of the aromatic hydrocarbon compound include benzene, naphthalene, anthracene, pyrene, perylene, fluorene, benzofluorene, biphenyl, terphenyl, and these compounds having a substituent.
Examples of the aromatic heterocyclic compound include pyrrole, pyridine, indole, imidazole, quinoline, isoquinoline, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran and these compounds having a substituent.

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

  In Formula (1), a preferred embodiment of n is 2.

（２）
（式中、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、アルコキシアルキル基、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。４個あるＲ^１は、同一であっても相異なってもよい。） One preferable embodiment of the organic group represented by T is the organic group represented by the formula (2).

(2)
(In the formula, 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, an alkoxyalkyl group, or a substituted group. An optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or a substituted And four R ^{1 s} may be the same or different.)

R ¹ halogen atom, optionally substituted fluorine group alkyl group, optionally substituted fluorine group alkoxy group, optionally substituted fluorine atom substituted alkylthio group, alkoxyalkyl group, optionally substituted aryl group Group, 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 Definitions and specific examples are as follows: a halogen atom represented by R, 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, an alkoxyalkyl group, a substituted group Aryl group which may be substituted, aryloxy group which may be substituted, substituted The definitions and specific examples of the arylthio group which may be substituted, the arylalkyl group which may be substituted, the arylalkoxy group which may be substituted and the arylalkylthio group which may be substituted are the same.

R ¹ is preferably a hydrogen atom or an alkyl group.

（３）
（式中、Ｒ^２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、アルコキシアルキル基、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。８個あるＲ^２は、同一であっても相異なってもよい。） Another preferred embodiment of the organic group represented by T is the organic group represented by the formula (3).

(3)
(In the formula, R ² is 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 an optionally substituted group. An aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an alkoxyalkyl group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or a substituted The eight R ² groups may be the same or different.

A halogen atom represented by R ² , 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, an aryl group which may be substituted; An optionally substituted aryloxy group, an optionally substituted arylthio group, an alkoxyalkyl group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group, and an optionally substituted arylalkylthio group The definitions and specific examples of R 1 include a halogen atom represented by R, an alkyl group that may be substituted with fluorine, an alkoxy group that may be substituted with fluorine, an alkylthio group that may be substituted with fluorine, and an optionally substituted group. Good aryl group, optionally substituted aryloxy group, optionally substituted aryl The definitions and specific examples of the thio group, alkoxyalkyl group, arylalkyl group which may be substituted, arylalkoxy group which may be substituted and arylalkylthio group which may be substituted are the same.

R ² is preferably a hydrogen atom or an alkyl group.

（４）
（式中、Ａ環及びＢ環は、同一又は相異なり、芳香族炭素環又は芳香族複素環を表す。Ａ²は、−Ｓ−、−Ｏ−又は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価の基を表す。） Another preferred embodiment of the organic group represented by T is the organic group represented by the formula (4).

(4)
(In the formula, A ring and B ring are the same or different and represent an aromatic carbocyclic ring or an aromatic heterocyclic ring. A ² is bonded to -S-, -O- or A ring and B ring to form 5; Represents a divalent group forming a membered ring or a six-membered ring.)

  In Formula (4), A ring and B ring are the same or different, and represent an aromatic carbocyclic ring or an aromatic heterocyclic ring. 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 A ring and the B ring are preferably a benzene ring and a naphthalene ring, and more preferably a benzene ring.

In Formula (4), A ² represents -S-, -O-, or a divalent group that forms a 5-membered ring or a 6-membered ring by combining with the A ring and the B ring. Examples of the divalent group that forms a 5-membered or 6-membered ring include —C (R ⁴ ) ₂ —, —O—C (R ⁵ ) ₂ —, —N (R ⁶ ) —, —Si (R ⁷ ) ₂ —, —B (R ⁸ ) —, —C (R ⁹ ) ₂ —C (R ⁹ ) ₂ — and the like. R ^{4 to} R ⁹ are the same or different and each represents a hydrogen atom, an alkyl group that may be substituted with fluorine, an aryl group that may be substituted, an arylalkyl group that may be substituted, or a heterocyclic group. Two R ⁴ may be the same or different. Two R ⁴ may be bonded to each other to form a cyclic structure. Two R ⁵ may be the same or different. Two R ⁷ may be the same or different. Four R ⁹ may be the same or different.

Definitions and specific examples of the optionally substituted alkyl group represented by R ^{4 to} R ⁹ , the optionally substituted aryl group and the optionally substituted arylalkyl group are fluorine represented by R The definition and specific examples of the alkyl group which may be substituted, the aryl group which may be substituted, and the arylalkyl group which may be substituted are the same.

The heterocyclic group represented by R ^{4 to} R ⁹ usually has 2 to 60 carbon atoms and is preferably an aromatic heterocyclic group. Specific examples thereof include an optionally substituted pyridyl group, furyl group, Examples include piperidyl group, quinolyl group, isoquinolyl group and pyrrolyl group.

A ² is preferably —C (R ⁴ ) ₂ — or —N (R ⁶ ) —.
R ⁴ is preferably an alkyl group or an aryl group. R ⁶ is preferably an alkyl group or an aryl group.

（２０）
（式中、Ｒ^２０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、アルコキシアルキル基、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。８個あるＲ^２０は、同一であっても相異なってもよい。） Another preferred embodiment of the organic group represented by T is the organic group represented by the formula (20).

(20)
(In the formula, R ²⁰ 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, an alkoxyalkyl group, or a substituted group. An optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or a substituted The eight R ²⁰ groups may be the same or different.

The halogen atom represented by R ²⁰ , an optionally substituted fluorine-substituted alkyl group, an optionally substituted fluorine-substituted alkoxy group, an optionally substituted fluorine-substituted alkylthio group, an alkoxyalkyl group, and an optionally substituted aryl Group, 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 Definitions and specific examples are as follows: a halogen atom represented by R, 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, an alkoxyalkyl group, a substituted group Optionally substituted aryl group, optionally substituted aryloxy group, substituted The definitions and specific examples of the arylthio group which may be substituted, the arylalkyl group which may be substituted, the arylalkoxy group which may be substituted and the arylalkylthio group which may be substituted are the same.

R ²⁰ is preferably a hydrogen atom or an alkyl group.

（２１）
（式中、Ｒ^２１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、アルコキシアルキル基、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。１２個あるＲ^２１は、同一であっても相異なってもよい。） Another preferred embodiment of the organic group represented by T is the organic group represented by the formula (21).

(21)
(In the formula, R ²¹ 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, an alkoxyalkyl group, or a substituted group. An optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or a substituted The 12 R ^{21 s} may be the same or different.

Halogen atom represented by R ²¹ , optionally substituted fluorine-substituted alkyl group, optionally substituted fluorine-substituted alkoxy group, optionally substituted fluorine-substituted alkylthio group, alkoxyalkyl group, optionally substituted aryl Group, 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 Definitions and specific examples are as follows: a halogen atom represented by R, 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, an alkoxyalkyl group, a substituted group Optionally substituted aryl group, optionally substituted aryloxy group, substituted The definition and specific examples of the arylthio group which may be substituted, the arylalkyl group which may be substituted, the arylalkoxy group which may be substituted or the arylalkylthio group which may be substituted are the same.

R ²¹ is preferably a hydrogen atom or an alkyl group.

  In Formula (1), another preferred embodiment of n is 4.

（５）
（式中、Ｒ^３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、アルコキシアルキル基、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。１２個あるＲ^３は、同一であっても相異なってもよい。） Another preferred embodiment of the organic group represented by T is the organic group represented by the formula (5).

(5)
(In the formula, R ³ 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, an alkoxyalkyl group, substituted An optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or a substituted The 12 R ³ groups may be the same or different.

R ³ halogen atom, fluorine-substituted alkyl group, fluorine-substituted alkoxy group, fluorine-substituted alkylthio group, alkoxyalkyl group, and optionally substituted aryl Group, 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 Definitions and specific examples are as follows: a halogen atom represented by R, 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, an alkoxyalkyl group, a substituted group Aryl group which may be substituted, aryloxy group which may be substituted, substituted The definitions and specific examples of the arylthio group which may be substituted, the arylalkyl group which may be substituted, the arylalkoxy group which may be substituted and the arylalkylthio group which may be substituted are the same.

R ³ is preferably a hydrogen atom or an alkyl group.

  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.

からなる群から選ばれる一種又は二種以上を繰り返し単位とし、該繰り返し単位同士が直接又は連結基を介して結合した高分子化合物である。 <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 In the present specification, specifically, a fluorenediyl group which may be substituted, a benzofluorenediyl group which may be substituted, Dibenzofurandiyl group which may be substituted, dibenzothiophenediyl group which may be substituted, carbazolediyl group which may be substituted, thiophenediyl group which may be substituted, furandyl group which may be substituted, substituted Been Which may be pyrrolediyl group, optionally substituted benzothiadiazole-diyl group, optionally substituted triphenylamine-diyl group, and a divalent group represented by the following structural formula

A polymer compound in which one or two or more selected from the group consisting of is used as a repeating unit and the repeating units are bonded directly or via a linking group.

  In the conjugated polymer compound, when the repeating units are bonded via a linking group, examples of the linking group include phenylene, biphenylene, naphthalenediyl, anthracenediyl and the like.

（７） （８）
〔式中、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８及びＲ^１９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、アルコキシアルキル基、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 ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are the same or different and may be substituted with a hydrogen atom or fluorine. An alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an alkoxyalkyl group, an optionally substituted aryl group, an optionally substituted aryloxy group, a substituted An arylthio group which may be substituted, an arylalkyl group which may be substituted, an arylalkoxy group which may be substituted or an arylalkylthio group which may be substituted. ]

R ^{10 to} R ¹⁹ may be a fluorine-substituted alkyl group, a fluorine-substituted alkoxy group, a fluorine-substituted alkylthio group, an alkoxyalkyl group, or a substituted aryl. Group, 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 Definitions and specific examples of the alkyl group may be a fluorine-substituted alkyl group, a fluorine-substituted alkoxy group, a fluorine-substituted alkylthio group, an alkoxyalkyl group, Aryl group which may be substituted, aryloxy group which may be substituted, There arylthio group, an optionally substituted arylalkyl group, the same definition and specific examples of the optionally substituted arylalkoxy group and an optionally substituted arylalkylthio group.

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 ×. 10 ⁶ is more preferable, and 1 × 10 ⁴ to 1 × 10 ⁶ is even more preferable.

  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 compound in which at least a part of fullerene is modified.

（１１） （１２） （１３） （１４）

（式（１１）〜（１４）中、Ｒ^ａは、フッ素置換されていてもよいアルキル基、置換されていてもよいアリール基、芳香族複素環基又はエステル構造を有する基である。複数個あるＲ^ａは、同一であっても相異なってもよい。Ｒ^ｂはフッ素置換されていてもよいアルキル基又は置換されていてもよいアリール基を表す。複数個あるＲ^ｂは、同一であっても相異なってもよい。） Examples of the fullerene derivative include a compound represented by the formula (11), a compound represented by the formula (12), a compound represented by the formula (13), and a compound represented by the formula (14).

(11) (12) (13) (14)

(In the formulas (11) to (14), R ^a is an alkyl group which may be fluorine-substituted, an aryl group which may be substituted, an aromatic heterocyclic group or a group having an ester structure. R ^a may be the same or different, R ^b represents an alkyl group which may be fluorine-substituted or an aryl group which may be substituted, and a plurality of R ^b are the same Or different.)

Definitions and specific examples of the optionally substituted fluorine group and optionally substituted aryl group represented by R ^a and R ^b are as follows. The definition and specific examples of the aryl group which may be used are the same.

The aromatic heterocyclic group represented by ^Ra usually has 3 to 60 carbon atoms, and examples thereof include a chenyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group.

（１５）
（式中、ｕ１は、１〜６の整数を表す、ｕ２は、０〜６の整数を表す、Ｒ^ｃは、フッ素置換されていてもよいアルキル基、置換されていてもよいアリール基又は芳香族複素環基を表す。） Examples of the group having an ester structure represented by ^Ra include a group represented by the formula (15).

(15)
(In the formula, u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, R ^c represents an alkyl group which may be substituted with fluorine, an aryl group which may be substituted, or an aromatic group. Represents a heterocyclic group.)

The definition and specific examples of the optionally substituted fluorine group represented by R ^c , the optionally substituted aryl group and the aromatic heterocyclic group may be the fluorine substituted group represented by R ^a The definitions and specific examples of the alkyl group, the optionally substituted aryl group and the aromatic heterocyclic group are the same.

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 provided adjacent to the first organic layer An organic photoelectric conversion element having a second organic layer containing a compound;
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。重合体をろ過して回収し、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 and stirred 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 with respect 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.

（Ｆ） 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 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 3
(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 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 (H) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(H)

（Ｉ） 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 (I) produced by the method of Synthesis Example 14 of JP-A-2006-97008 was used instead of the compound (E), and Voc Was measured. The measurement results are shown in Table 1.

(I)

（Ｊ） 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 (J) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(J)

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 5 except that the amount of compound (J) added was 0.5 times the weight of the conjugated polymer compound 1, and Voc was measured. The measurement results are shown in Table 1.

（K） 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 (K) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(K)

（L） 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 (L) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(L)

（Ｍ） 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 (M) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(M)

（Ｎ） Example 11
(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 (N) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(N)

（Ｏ） 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 1 except that the compound (O) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(O)

（Ｐ） Example 13
(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 (P) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(P)

化合物（Ｑ−１）

アルゴン雰囲気下、１０００ｍｌの三つ口フラスコに、１，４−ジヨードベンゼンを１２５．０ｇ（０．３７９ｍｏｌ）、カルバゾ−ルを１５．８４ｇ（０．０９５ｍｏｌ）、炭酸カリウムを３９．３ｇ（０．２８４ｍｏｌ）、酢酸パラジウムを０．４３ｇ（１．８９ｍｍｏｌ）、トルエンを６２５．０ｇ入れた。フラスコ内を５０ｍｍＨｇまで減圧し、その後、フラスコ内にアルゴンを導入して常圧に戻す操作を行った。減圧及び常圧に戻す操作は５回行った。その後、フラスコ内の気体をアルゴンで置換した。７０℃まで昇温し、トリ−ｔｅｒｔ−ブチルホスフィンを５０重量％含むトルエン溶液２．３ｍｌ（４．７ｍｍｏｌ）を加え、さらに昇温し、還流下で５８時間撹拌した。その後、５０℃まで冷却し、反応生成物を濾過し、フィルター上の固形分をクロロホルム１００ｍｌで洗浄した。７０〜７５℃の条件で、エバポレ−タで濾洗液を減圧濃縮し、淡褐色の樹脂状生成物１３２．３ｇを得た。展開溶媒としてクロロホルムとへキサンとを混合した溶媒を用い、シリカゲルクロマトグラフィーで樹脂状生成物を精製することにより、白色結晶１９．７ｇを得た。展開溶媒において、クロロホルムに対するへキサンの容積比は１０であった。この結晶にヘキサン２００ｍｌを加え、還流下１時間撹拌し、その後、室温（２５℃）まで冷却した。生成物を濾過し、濾物をｎ−ヘキサン３０ｍｌで洗浄後、７０〜７５℃の条件で濾物を減圧乾燥し、化合物(Ｑ−１)を１７．５ｇ（収率６３．１％）得た。 Synthesis example 2
(Synthesis of Compound (Q-1))

Compound (Q-1)

Under an argon atmosphere, in a 1000 ml three-necked flask, 125.0 g (0.379 mol) of 1,4-diiodobenzene, 15.84 g (0.095 mol) of carbazole, 39.3 g (0 .284 mol), 0.43 g (1.89 mmol) of palladium acetate, and 625.0 g of toluene were added. The inside of the flask was decompressed to 50 mmHg, and then argon was introduced into the flask to return to normal pressure. The operation of reducing the pressure and returning to normal pressure was performed 5 times. Thereafter, the gas in the flask was replaced with argon. The temperature was raised to 70 ° C., 2.3 ml (4.7 mmol) of a toluene solution containing 50% by weight of tri-tert-butylphosphine was added, the temperature was further raised, and the mixture was stirred under reflux for 58 hours. Then, it cooled to 50 degreeC, the reaction product was filtered, and solid content on a filter was wash | cleaned with 100 ml of chloroform. The filtrate was concentrated under reduced pressure with an evaporator at 70 to 75 ° C. to obtain 132.3 g of a light brown resinous product. Using a mixed solvent of chloroform and hexane as a developing solvent, the resinous product was purified by silica gel chromatography to obtain 19.7 g of white crystals. In the developing solvent, the volume ratio of hexane to chloroform was 10. To this crystal, 200 ml of hexane was added, stirred under reflux for 1 hour, and then cooled to room temperature (25 ° C.). The product was filtered, and the residue was washed with 30 ml of n-hexane and then dried under reduced pressure at 70 to 75 ° C. to obtain 17.5 g of Compound (Q-1) (yield 63.1%). It was.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.26 to 7.44 (m, 8H), 7.90 to 7.94 (d, 2H), 8.12 to 8.15 (d, 2H)

化合物（Ｑ−２）

アルゴン雰囲気下、１００ｍｌの三つ口フラスコに、化合物（Ｑ−１）を３．６９ｇ（１０．０ｍｍｏｌ）、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリドを０．３５ｇ（０．５ｍｍｏｌ）、トリフェニルホスフィンを０．２６ｇ（１．０ｍｍｏｌ）、ヨウ化銅（Ｉ）を０．１９ｇ（１．０ｍｍｏｌ）、トリエチルアミンを２０．２ｇ（０．２ｍｏｌ）、酢酸エチルを２２．１ｇ入れ、７０℃まで昇温した。次に、７０〜７５℃で、トリメチルシリルアセチレン１．８９ｇ（１５．０ｍｍｏｌ）を３５分かけてフラスコ内に滴下した。７０〜７５℃で２．５時間撹拌し、その後、室温（２５℃）まで冷却した。エバポレータを用い、７５℃で反応生成物を減圧濃縮し、濃縮物５．６５ｇを得た。展開溶媒としてクロロホルムとへキサンとトリエチルアミンとを混合した溶媒を用い、シリカゲルクロマトグラフィーで濃縮物を精製し、白色の化合物（Ｑ−２）を３．２９ｇ（収率９６．７％）得た。展開溶媒において、クロロホルムに対するへキサンの容積比は１０であり、トリエチルアミンに対するクロロホルムの容積比は１０００であった。 (Synthesis of Compound (Q-2))

Compound (Q-2)

In a 100 ml three-necked flask under an argon atmosphere, 3.69 g (10.0 mmol) of compound (Q-1), 0.35 g (0.5 mmol) of bis (triphenylphosphine) palladium (II) dichloride, 0.26 g (1.0 mmol) of phenylphosphine, 0.19 g (1.0 mmol) of copper (I) iodide, 20.2 g (0.2 mol) of triethylamine, 22.1 g of ethyl acetate, and up to 70 ° C. The temperature rose. Next, 1.89 g (15.0 mmol) of trimethylsilylacetylene was dropped into the flask over 35 minutes at 70 to 75 ° C. The mixture was stirred at 70 to 75 ° C for 2.5 hours, and then cooled to room temperature (25 ° C). The reaction product was concentrated under reduced pressure at 75 ° C. using an evaporator to obtain 5.65 g of a concentrate. Using a mixed solvent of chloroform, hexane and triethylamine as a developing solvent, the concentrate was purified by silica gel chromatography to obtain 3.29 g (yield 96.7%) of white compound (Q-2). In the developing solvent, the volume ratio of hexane to chloroform was 10, and the volume ratio of chloroform to triethylamine was 1000.

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.30 (s, 9H), 7.26 to 7.31 (m, 2H), 7.40 to 7.42 (m, 4H), 7.50 to 7.53 (d, 2H), 7. 68-7.71 (d, 2H), 8.12-8.15 (d, 2H)

化合物（Ｑ−３）

窒素雰囲気下、１００ｍｌの三つ口フラスコに、化合物（Ｑ−２）を３．２９ｇ（９．７ｍｍｏｌ）、クロロホルムを２０．０ｇ入れ、化合物（Ｑ−２）が溶解した後、エタノールを４０．０ｇ加えた。次に、炭酸ナトリウムを０．５ｇ（９．７ｍｍｏｌ）加え、２０〜２３℃で１８時間撹拌した。エバポレータを用いて、７５℃で反応生成物を減圧濃縮し、濃縮物４．２４ｇを得た。展開溶媒としてクロロホルムとｎ−へキサンとトリエチルアミンとを混合した溶媒を用い、シリカゲルクロマトグラフィーで濃縮物を精製し、白色の化合物（Ｑ−３）を２．５９ｇ（収率１００％）得た。展開溶媒において、クロロホルムに対するｎ−へキサンの容積比は５であり、トリエチルアミンに対するクロロホルムの容積比は１０００であった。 (Synthesis of Compound (Q-3))

Compound (Q-3)

Under a nitrogen atmosphere, 3.29 g (9.7 mmol) of compound (Q-2) and 20.0 g of chloroform were placed in a 100 ml three-necked flask, and after dissolving compound (Q-2), 40. 0 g was added. Next, 0.5 g (9.7 mmol) of sodium carbonate was added and stirred at 20-23 ° C. for 18 hours. The reaction product was concentrated under reduced pressure using an evaporator at 75 ° C. to obtain 4.24 g of a concentrate. Using a mixed solvent of chloroform, n-hexane and triethylamine as a developing solvent, the concentrate was purified by silica gel chromatography to obtain 2.59 g (yield 100%) of white compound (Q-3). In the developing solvent, the volume ratio of n-hexane to chloroform was 5, and the volume ratio of chloroform to triethylamine was 1000.

¹ H-NMR (270 MHz / CDCl ₃ ):
δ 3.18 (s, 1H), 7.26 to 7.34 (m, 2H), 7.40 to 7.42 (m, 4H), 7.53 to 7.56 (m, 2H), 7. 71 to 7.75 (d, 2H), 8.12 to 8.15 (d, 2H)

化合物（Ｑ）

アルゴン雰囲気下、１００ｍｌの三つ口フラスコに、化合物（Ｑ−１）を５．１８ｇ（１４．０ｍｍｏｌ）、化合物（Ｑ−３）を２．５０ｇ（９．４ｍｏｌ）、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリドを０．３３ｇ（０．６８ｍｍｏｌ）、トリフェニルホスフィンを０．２５ｇ（０．９４ｍｍｏｌ）、ヨウ化銅（Ｉ）を０．１８ｇ（１．０ｍｍｏｌ）、トリエチルアミンを１８．９ｇ（０．１８７ｍｏｌ）、酢酸エチル３１．１ｇを入れ、７０〜７５℃で２時間撹拌し、その後、室温（２５℃）まで冷却した。エバポレータを用いて、７５℃で反応生成物を減圧濃縮し、濃縮物１１．０ｇを得た。展開溶媒としてクロロホルムとへキサンとを混合した溶液を用い、シリカゲルクロマトグラフィーで濃縮物を精製し、褐色の固体４．０６ｇを得た。展開溶媒において、クロロホルムに対するへキサンの容積比は２であった。この固体をトルエン１００ｇに分散させ、８０〜８５℃で１時間撹拌し、その後、室温（２５℃）まで冷却した。生成物を濾過し、濾物をトルエン２０ｍｌで洗浄し、その後、７０〜７５℃で濾物を減圧乾燥し、肌色の固体３．６０ｇを得た。この固体を、５０〜５５℃の条件で、テトラヒドロフラン５００ｍｌに溶解し、その後、活性炭４．０ｇを加え、５０〜５５℃で１時間撹拌した。その後、活性炭を濾別し、テトラヒドロフラン３０ｍｌで活性炭を洗浄した。エバポレータを用い、７５℃で濾洗液を減圧濃縮し、白色固体３．４０ｇを得た。この固体をトルエン６８ｇに分散させ、８０〜８５℃で１時間撹拌し、その後、室温（２５℃）まで冷却した。生成物を濾過し、濾物をトルエン２０ｍｌで洗浄後、７０〜７５℃で濾物を減圧乾燥し、無色の固体として化合物（Ｑ）２．５５ｇ（収率５３．６％）を得た。 (Synthesis of Compound (Q))

Compound (Q)

In a 100 ml three-necked flask under an argon atmosphere, 5.18 g (14.0 mmol) of compound (Q-1), 2.50 g (9.4 mol) of compound (Q-3), bis (triphenylphosphine) 0.33 g (0.68 mmol) of palladium (II) dichloride, 0.25 g (0.94 mmol) of triphenylphosphine, 0.18 g (1.0 mmol) of copper (I) iodide, and 18.9 g of triethylamine ( 0.187 mol) and 31.1 g of ethyl acetate were added, stirred at 70 to 75 ° C. for 2 hours, and then cooled to room temperature (25 ° C.). The reaction product was concentrated under reduced pressure at 75 ° C. using an evaporator to obtain 11.0 g of a concentrate. Using a mixed solution of chloroform and hexane as a developing solvent, the concentrate was purified by silica gel chromatography to obtain 4.06 g of a brown solid. In the developing solvent, the volume ratio of hexane to chloroform was 2. This solid was dispersed in 100 g of toluene, stirred at 80 to 85 ° C. for 1 hour, and then cooled to room temperature (25 ° C.). The product was filtered, and the residue was washed with 20 ml of toluene, and then the residue was dried under reduced pressure at 70 to 75 ° C. to obtain 3.60 g of a flesh-colored solid. This solid was dissolved in 500 ml of tetrahydrofuran under the conditions of 50 to 55 ° C., 4.0 g of activated carbon was added, and the mixture was stirred at 50 to 55 ° C. for 1 hour. Thereafter, the activated carbon was filtered off, and the activated carbon was washed with 30 ml of tetrahydrofuran. Using an evaporator, the filtrate was concentrated under reduced pressure at 75 ° C. to obtain 3.40 g of a white solid. This solid was dispersed in 68 g of toluene, stirred at 80 to 85 ° C. for 1 hour, and then cooled to room temperature (25 ° C.). The product was filtered, and the residue was washed with 20 ml of toluene, and then the residue was dried under reduced pressure at 70 to 75 ° C. to obtain 2.55 g of Compound (Q) as a colorless solid (yield 53.6%).

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.29-7.34 (m, 4H), 7.41-7.49 (m, 8H), 7.60-7.63 (d, 4H), 7.80-7.83 (d, 4H) ), 8.15-8.17 (d, 4H)

化合物(Ｒ−１)

アルゴン雰囲気下、１００ｍｌの三つ口フラスコに、ジヨードベンゼンを９．９０ｇ（３０．０ｍｍｏｌ）、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリドを０．４２ｇ（０．６ｍｍｏｌ）、ヨウ化銅（Ｉ）を０．３９ｇ（１．５ｍｍｏｌ）、トリエチルアミンを３０．４ｇ（０．３ｍｏｌ）、酢酸エチルを３０．４ｇ入れ、６０℃まで昇温した。次に、６５〜７０℃でトリメチルシリルアセチレン７．３７ｇ（７５．０ｍｍｏｌ）を１時間かけてフラスコ内に滴下した。６５〜７０℃で２．５時間撹拌した後、室温（２５℃）まで冷却した。エバポレータを用い、７０℃で反応生成物を減圧濃縮し、濃縮物９．０８ｇを得た。展開溶媒としてクロロホルムとへキサンとトリエチルアミンとを混合した溶媒を用い、シリカゲルクロマトグラフィーで濃縮物を精製し、白色の化合物(Ｒ−１)を７．３０ｇ（収率８８．９％）得た。展開溶媒において、クロロホルムに対するｎ−へキサンの容積比は５であり、トリエチルアミンに対するクロロホルムの容積比は１０であった。 Synthesis example 3
(Synthesis of Compound (R-1))

Compound (R-1)

In an argon atmosphere, in a 100 ml three-necked flask, 9.90 g (30.0 mmol) of diiodobenzene, 0.42 g (0.6 mmol) of bis (triphenylphosphine) palladium (II) dichloride, copper iodide ( 0.39 g (1.5 mmol) of I), 30.4 g (0.3 mol) of triethylamine, and 30.4 g of ethyl acetate were added, and the temperature was raised to 60 ° C. Next, 7.37 g (75.0 mmol) of trimethylsilylacetylene was dropped into the flask at 65 to 70 ° C. over 1 hour. After stirring at 65-70 ° C for 2.5 hours, the mixture was cooled to room temperature (25 ° C). Using an evaporator, the reaction product was concentrated under reduced pressure at 70 ° C. to obtain 9.08 g of a concentrate. Using a mixed solvent of chloroform, hexane and triethylamine as a developing solvent, the concentrate was purified by silica gel chromatography to obtain 7.30 g (yield: 88.9%) of white compound (R-1). In the developing solvent, the volume ratio of n-hexane to chloroform was 5, and the volume ratio of chloroform to triethylamine was 10.

化合物（Ｒ−２）

窒素雰囲気下、１００ｍｌの三つ口フラスコに、化合物（Ｒ−１）を７．３ｇ（２７ｍｍｏｌ）、エタノールを７３．０ｇ入れ、化合物（Ｒ−１）を溶解させた。次に、炭酸カリウムを０．７５ｇ（５．４ｍｍｏｌ）加え、２０〜２３℃で２１時間撹拌した。ろ過した生成物を、クロロホルムと水で洗浄後、エバポレータを用いて７０℃で減圧濃縮し、化合物（Ｒ−２）を３．１０ｇ（収率９１．１％）得た。 (Synthesis of Compound (R-2))

Compound (R-2)

Under a nitrogen atmosphere, 7.3 g (27 mmol) of compound (R-1) and 73.0 g of ethanol were placed in a 100 ml three-necked flask to dissolve compound (R-1). Next, 0.75 g (5.4 mmol) of potassium carbonate was added and stirred at 20-23 ° C. for 21 hours. The filtered product was washed with chloroform and water, and then concentrated under reduced pressure at 70 ° C. using an evaporator to obtain 3.10 g (yield 91.1%) of compound (R-2).

化合物（Ｒ）

アルゴン雰囲気下、１００ｍｌの三つ口フラスコに、化合物（Ｑ−１）を５．５４ｇ（１５．０ｍｍｏｌ）、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリドを０．４２ｇ（０．６ｍｍｏｌ）、トリフェニルホスフィンを０．１６ｇ（０．６ｍｍｏｌ）、ヨウ化銅（Ｉ）を０．１１ｇ（０．６ｍｍｏｌ）、トリエチルアミンを１８．２ｇ（０．１８ｍｏｌ）、酢酸エチルを２２．２ｇ入れ、７０℃に昇温した。その後、７０〜７５℃で攪拌しながら、化合物(Ｒ−２)０．７６ｇ（９．４ｍｏｌ）を３ｇの酢酸エチルに溶かした溶液を４．５時間かけて滴下し、５．５時間攪拌した。得られた反応液をエバポレータで濃縮し、得られた残渣をカラムクロマトグラフィーで精製し、目的物である化合物（Ｒ）が含まれる分画の溶液を回収した。カラムクロマトグラフィーにはシリカゲル２００ｇを使用し、溶媒としてヘキサンとクロロホルムとを混合した溶媒を用いた。クロロホルムに対するヘキサンの容積比が３の条件で精製を開始し、グラジエントをかけ、クロロホルムに対するヘキサンの容積比を１とした。回収した溶液を濃縮し、得られた粗精製物を粗生成物に対して２０重量倍の重量のトルエンでリパルプ洗浄を行い、再度カラムクロマトグラフィーで精製し、精製物を２．５３ｇ得た。カラムクロマトグラフィーにはシリカゲル５００ｇを使用し、溶媒としてヘキサンとクロロホルムとを混合した溶媒を用いた。クロロホルムに対するヘキサンの容積比は１であった。精製物を、５０℃で加熱しながらテトラヒドロフラン５００ｍｌに溶解し、活性炭２．３ｇを入れ、さらに５０℃で３０分加熱攪拌した。反応液をセライトろ過した後、濾液をエバポレータで濃縮し、残渣をトルエン５０ｍｌでリパルプ洗浄し、さらにトルエン５０ｍｌで洗浄し、７５℃、４００Ｐａで減圧乾燥することで化合物（Ｒ）を１．９５ｇ（収率５３．４％）得た。 (Synthesis of Compound (R))

Compound (R)

In a 100 ml three-necked flask under an argon atmosphere, 5.54 g (15.0 mmol) of compound (Q-1), 0.42 g (0.6 mmol) of bis (triphenylphosphine) palladium (II) dichloride, Add 0.16 g (0.6 mmol) of phenylphosphine, 0.11 g (0.6 mmol) of copper (I) iodide, 18.2 g (0.18 mol) of triethylamine, and 22.2 g of ethyl acetate. The temperature rose. Then, stirring at 70-75 degreeC, the solution which melt | dissolved 0.76 g (9.4 mol) of compounds (R-2) in 3 g of ethyl acetate was dripped over 4.5 hours, and it stirred for 5.5 hours. . The obtained reaction solution was concentrated by an evaporator, and the obtained residue was purified by column chromatography to collect a fraction solution containing the target compound (R). For column chromatography, 200 g of silica gel was used, and a solvent in which hexane and chloroform were mixed was used as a solvent. Purification was started under the condition that the volume ratio of hexane to chloroform was 3, and a gradient was applied. The volume ratio of hexane to chloroform was set to 1. The collected solution was concentrated, and the resulting crude product was repulped with 20 times the weight of toluene with respect to the crude product, and purified again by column chromatography to obtain 2.53 g of the purified product. For column chromatography, 500 g of silica gel was used, and a solvent in which hexane and chloroform were mixed was used as a solvent. The volume ratio of hexane to chloroform was 1. The purified product was dissolved in 500 ml of tetrahydrofuran while heating at 50 ° C., 2.3 g of activated carbon was added, and the mixture was further heated and stirred at 50 ° C. for 30 minutes. After the reaction solution was filtered through Celite, the filtrate was concentrated with an evaporator, and the residue was repulped with 50 ml of toluene, further washed with 50 ml of toluene, and dried under reduced pressure at 75 ° C. and 400 Pa to obtain 1.95 g of Compound (R) ( Yield 53.4%).

¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.25 to 7.39 (m, 4H), 7.40 to 7.50 (m, 8H), 7.55 to 7.65 (d, 8H), 7.77 to 7.80 (d, 4H) ), 8.14-8.17 (d, 4H)

（Q） 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 1 except that the compound (Q) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(Q)

（Ｒ） Example 15
(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 (R) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(R)

（Ｔ） Example 16
(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 (T) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(T)

（Ｕ） Example 17
(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 (U) was used instead of the compound (E), and Voc was measured. The measurement results are shown in Table 1.

(U)

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.

Claims (6)

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, and serves as a triplet light emitter or structural unit. An organic photoelectric conversion element that does not include a polymer compound having a triplet light emitter.
(Here, the triplet light emitter refers to a compound that emits light from a triplet state in electroluminescence and exhibits phosphorescence instead of fluorescence. A polymer compound having a triplet light emitter as a structural unit is a main chain. And / or a polymer compound in which a structural unit corresponding to a triplet light emitter is incorporated in the side chain.)

(1)
(In the formula, T represents an organic group represented by the following formula (2), formula (3), formula (4) or formula (20). N represents 2. R represents a hydrogen atom or fluorine. Represents an optionally substituted alkyl group, and a plurality of R may be the same or different.)

(2)
(In the formula, 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, an alkoxyalkyl group, or a substituted group. An optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or a substituted And four R ^{1 s} may be the same or different.)

(3)
(In the formula, R ² is 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 an optionally substituted group. An aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an alkoxyalkyl group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or a substituted The eight R ² groups may be the same or different.

(4)
(In the formula, A ring and B ring are the same or different and represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring. A ² is bonded to A ring and B ring to form a 5-membered ring or 6-membered ring. Represents a divalent group to be formed, -S- or -O-.)

(20)
(In the formula, R ²⁰ 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, an alkoxyalkyl group, or a substituted group. An optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or a substituted The eight R ²⁰ groups may be the same or different.
The organic photoelectric conversion element according to claim 1, wherein the conjugated polymer compound is a conjugated polymer compound having one or more repeating units selected from the group consisting of formula (7) and formula (8).

(7) (8)
(Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are the same or different and may be substituted with a hydrogen atom or fluorine. An alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an alkoxyalkyl group, an optionally substituted aryl group, an optionally substituted aryloxy group, a substituted And represents an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group or an optionally substituted arylalkylthio group.   The organic photoelectric conversion element according to claim 1 or 2, 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 any one of claims 1 to 3 which further contains an electron accepting compound. The organic photoelectric conversion element according to claim 4 , wherein the electron-accepting compound is a fullerene derivative. The organic photoelectric conversion element according to any one of claims 1 to 5 , wherein an electron-donating compound is further contained in the organic layer.