WO2012173030A1

WO2012173030A1 - Photoelectric conversion element

Info

Publication number: WO2012173030A1
Application number: PCT/JP2012/064615
Authority: WO
Inventors: 吉村　研
Original assignee: 住友化学株式会社
Priority date: 2011-06-16
Filing date: 2012-05-31
Publication date: 2012-12-20
Also published as: JP2013004722A

Abstract

A useful photoelectric conversion element that has a high open-circuit voltage. Said photoelectric conversion element has a first electrode, a second electrode, and an active layer between said first and second electrodes. Said active layer contains an organic compound containing a constitutional unit represented by formula (1). (In the formula, R¹ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aryl alkyl group, an aryl alkoxy group, an aryl alkylthio group, an aryl alkenyl group, an aryl alkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a heterocyclic group, an acyl group, an acyloxy group, an amide group, a carboxyl group, a nitro group, or a cyano group; and each of rings D and E independently represent an aromatic ring that may have a substituent.)

Description

Photoelectric conversion element

The present invention relates to a photoelectric conversion element using an organic compound having a specific structure.

In recent years, in order to prevent global warming, reduction of CO ₂ released into the atmosphere has been demanded. For example, it has been proposed to switch to a solar system using a pn-junction type silicon solar cell on the roof of a house. The single crystal, polycrystalline and amorphous silicon used in the silicon solar cell are manufactured in the process of However, there is a problem that high temperature and high vacuum conditions are required.
On the other hand, a photoelectric conversion element having an active layer containing an organic compound can omit the high-temperature and high-vacuum process used in the production process of silicon-based solar cells, and can be manufactured at low cost only by a coating process. It is coming. As a photoelectric conversion element, there is a photoelectric conversion element having an organic layer containing a polymer compound composed of a repeating unit (A) and a repeating unit (B) (WO2007 / 011739).

However, the photoelectric conversion element does not have a sufficiently high open end voltage.

The present invention provides a photoelectric conversion element having a high open-circuit voltage.
That is, the present invention is as follows.
1. A first electrode and a second electrode; an active layer between the first electrode and the second electrode; and a structural unit represented by formula (1) in the active layer: A photoelectric conversion element containing an organic compound.

(In the formula, R ¹ is a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted atom. A good alkylthio 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, arylalkylthio group which may be substituted, arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted Silyloxy group, heterocyclic group, acyl group, acyloxy group, amide group, carboxyl group, nitro group or Represents an ano group, and the D ring and the E ring each independently represent an aromatic ring optionally having a substituent.)
2. The organic compound is further a structural unit represented by the formula (A-1), a structural unit represented by the formula (B-1), a structural unit represented by the formula (C-1), and the formula (D-1). The said photoelectric conversion element containing the at least 1 sort (s) of structural unit chosen from the group 1 which consists of the structural unit represented by and the structural unit represented by Formula (E-1).
(Group 1)

(In formulas (A-1) to (E-1), Q ¹ represents a sulfur atom, an oxygen atom, a selenium atom, —N (R ³⁰ ) — or —CR ³¹ ═CR ³² —. R ³⁰ , R ³¹ and R ³² each independently represents a hydrogen atom or a substituent, R ²⁰ to R ²⁵ each independently represents a hydrogen atom or a substituent, and R ²⁰ and R ²¹ are linked to form a cyclic structure. (G ring to N ring each independently represents an aromatic ring which may have a substituent.)
3. 1 above. Or 2. Solar cell module including a photoelectric conversion element.
4). 1 above. Or 2. Image sensor including a photoelectric conversion element.
5. An organic thin film transistor having a gate electrode, a source electrode, a drain electrode, and an active layer, and containing an organic compound containing a structural unit represented by formula (1) in the active layer.
6). Formula (1-1)

Wherein R ¹ is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, 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, arylalkylthio group which may be substituted, substituted Arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group, Represents an amide group, a carboxyl group, a nitro group or a cyano group, wherein the D ″ ring and the E ″ ring are each independently May have a substituent represents an thiophene ring.)
And a structural unit represented by the above formula (A-1), a structural unit represented by the formula (B-1), and a structure represented by the formula (C-1). A polymer compound comprising at least one structural unit selected from the group consisting of a unit, a structural unit represented by the formula (D-1), and a structural unit represented by the formula (E-1).
7. A compound represented by formula (1-2).

Wherein R ¹ is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, 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, arylalkylthio group which may be substituted, substituted Arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group, An amide group, a carboxyl group, a nitro group or a cyano group, each of the D ′ ring and the E ′ ring independently; .W ¹ and W ² representing an aromatic heterocyclic ring optionally having a substituent are each independently a hydrogen atom, a halogen atom, a sulfonic acid residue, a boric acid ester residue, a monohalogenated methyl group, (Represents a dihydroxyboryl group, a formyl group, a vinyl group or a substituted stannyl group.)

Hereinafter, the present invention will be described in detail.
The photoelectric conversion element of the present invention has a first electrode and a second electrode, and has an active layer between the first electrode and the second electrode, and the active layer has the above formula ( The organic compound containing the structural unit represented by 1) is contained.
In equation (1), R¹The alkyl group represented by may be linear, branched or cyclic. The alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom. The alkyl group usually has 1 to 30 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl. Group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group And chain alkyl groups such as decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.
The alkyl part of the alkoxy group may be linear, branched or cyclic. The alkoxy group usually has 1 to 20 carbon atoms, and the alkoxy group may have a substituent. Examples of the substituent that the alkoxy group may have include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms). Specific examples of the optionally substituted alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, Heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, trifluoromethoxy, pentafluoroethoxy, perfluorobutoxy, perfluoro Examples include a hexyloxy group, a perfluorooctyloxy group, a methoxymethyloxy group, and a 2-methoxyethyloxy group.
The alkyl part of the alkylthio group may be linear, branched or cyclic. The alkylthio group usually has 1 to 20 carbon atoms, and the alkylthio group may have a substituent. Examples of the substituent that the alkylthio group may have include a halogen atom. Specific examples of the optionally substituted alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group. Group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group and trifluoromethylthio group.
An aryl group means a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and usually has 6 to 60 carbon atoms. The aryl group may have a substituent, and examples of the substituent include a halogen atom and an optionally substituted alkoxy group. Specific examples of the optionally substituted alkoxy group include R¹Are the same as the specific examples of the alkoxy group which may be substituted. Specific examples of the optionally substituted aryl group include a phenyl group, a C1-C12 alkoxyphenyl group, a C1-C12 alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a pentafluorophenyl group.
The aryloxy group usually has 6 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an optionally substituted alkoxy group. Specific examples of the optionally substituted alkoxy group include R¹Are the same as the specific examples of the alkoxy group which may be substituted. Specific examples of the optionally substituted aryloxy group include a phenoxy group, a C1-C12 alkoxyphenoxy group, a C1-C12 alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenoxy group. It is done.
The arylthio group usually has 6 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an optionally substituted alkoxy group. Specific examples of the optionally substituted alkoxy group include R¹Are the same as the specific examples of the alkoxy group which may be substituted. Specific examples of the arylthio group which may be substituted include a phenylthio group, a C1-C12 alkoxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group. It is done.
The arylalkyl group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an optionally substituted alkoxy group. Specific examples of the optionally substituted alkoxy group include R¹Are the same as the specific examples of the halogen atom represented by the formula (1) and the optionally substituted alkoxy group. Specific examples of the optionally substituted arylalkyl group include a phenyl-C1 to C12 alkyl group, a C1 to C12 alkoxyphenyl-C1 to C12 alkyl group, a C1 to C12 alkylphenyl-C1 to C12 alkyl group, and 1-naphthyl. -C1-C12 alkyl group and 2-naphthyl-C1-C12 alkyl group are mentioned.
The arylalkoxy group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an optionally substituted alkoxy group. Specific examples of the optionally substituted alkoxy group include R¹Are the same as the specific examples of the alkoxy group which may be substituted. Specific examples of the optionally substituted arylalkoxy group include a phenyl-C1 to C12 alkoxy group, a C1 to C12 alkoxyphenyl-C1 to C12 alkoxy group, a C1 to C12 alkylphenyl-C1 to C12 alkoxy group, and 1-naphthyl. -C1-C12 alkoxy group and 2-naphthyl-C1-C12 alkoxy group are mentioned.
The arylalkylthio group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an optionally substituted alkoxy group. Specific examples of the optionally substituted alkoxy group include R¹Are the same as the specific examples of the alkoxy group which may be substituted. Specific examples of the optionally substituted arylalkylthio group include phenyl-C1-C12 alkylthio group, C1-C12 alkoxyphenyl-C1-C12 alkylthio group, C1-C12 alkylphenyl-C1-C12 alkylthio group, and 1-naphthyl. -C1-C12 alkylthio group and 2-naphthyl-C1-C12 alkylthio group are mentioned.
The arylalkenyl group usually has 8 to 20 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an optionally substituted alkoxy group. Specific examples of the optionally substituted alkoxy group include R¹Are the same as the specific examples of the alkoxy group which may be substituted. Specific examples of the arylalkenyl group include a styryl group.
The arylalkynyl group usually has 8 to 20 carbon atoms, and the aryl moiety may have a substituent. Examples of the substituent include a halogen atom and an optionally substituted alkoxy group. Specific examples of the optionally substituted alkoxy group include R¹Are the same as the specific examples of the alkoxy group which may be substituted. Specific examples of the arylalkynyl group include a phenylacetylenyl group.
The substituted amino group is a group in which one or two hydrogen atoms of the amino group are substituted, and the substituent is, for example, an optionally substituted alkyl group or an optionally substituted aryl group. . Specific examples of the optionally substituted alkyl group and the optionally substituted aryl group include R¹Specific examples of the alkyl group which may be substituted and the aryl group which may be substituted are the same as those described above. The substituted amino group usually has 1 to 40 carbon atoms. Specific examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, tert -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C1-C12 alkoxy Siphenylamino group, di (C1-C12 alkoxyphenyl) amino group, di (C1-C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyrida Dinylamino group, pyrimidylamino group, pyrazylamino group, triazylamino group, phenyl-C1-C12 alkylamino group, C1-C12 alkoxyphenyl-C1-C12 alkylamino group, C1-C12 alkylphenyl-C1-C12 alkylamino group , Di (C1-C12 alkoxyphenyl-C1-C12 alkyl) amino group, di (C1-C12 alkylphenyl-C1-C12 alkyl) amino group, 1-naphthyl-C1-C12 alkylamino group and 2-naphthyl-C1- A C12 alkylamino group is mentioned.
A substituted silyl group is one in which one, two, or three of the hydrogen atoms of the silyl group are substituted, and in general, all three hydrogen atoms in the silyl group are substituted. These are an optionally substituted alkyl group and an optionally substituted aryl group. Specific examples of the optionally substituted alkyl group and the optionally substituted aryl group include R¹Specific examples of the alkyl group which may be substituted and the aryl group which may be substituted are the same as those described above. Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, Examples include a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, and a dimethylphenylsilyl group.
The substituted silyloxy group is a group in which an oxygen atom is bonded to the above substituted silyl group. Specific examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylyl group. Examples thereof include a silyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.
As the heterocyclic group, optionally substituted furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, Triazole, thiadiazole, oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline , Chromene, chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzimidazole, benzothiazole, Such as dazole, naphthyridine, quinoxaline, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridine, acridine, β-carboline, perimidine, phenanthroline, thianthrene, phenoxathiin, phenoxazine, phenothiazine, phenazine And a group obtained by removing one hydrogen atom from a heterocyclic compound. As the heterocyclic group, an aromatic heterocyclic group is preferable.
Acyl group means a group excluding the hydroxyl group in the —COOH part of the carboxylic acid, and usually has 2 to 20 carbon atoms. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a trifluoroacetyl group, an alkylcarbonyl group which may be substituted with a halogen having 2 to 20 carbon atoms, a benzoyl group, Examples thereof include a phenylcarbonyl group which may be substituted with a halogen such as a pentafluorobenzoyl group.
Acyloxy group means a group in which a hydrogen atom in the -COOH part of carboxylic acid is removed, and its carbon number is usually 2-20. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.
An amide group means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an amide, and the carbon number is usually 2 to 20. Specific examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.
The D ring and the E ring each independently represent an aromatic ring which may have a substituent. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a perylene ring, and a tetracene ring. , Aromatic carbon rings such as pentacene ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, acridine ring, phenanthroline ring, thiophene ring, benzothiophene ring, dibenzo Thiophene ring, thiophene oxide ring, benzothiophene oxide ring, dibenzothiophene oxide ring, thiophene dioxide ring, benzothiophene dioxide ring, dibenzothiophene dioxide ring, furan ring, benzofuran ring, dibenzofuran ring, pyrrole ring, indole ring, dibenzo Roll ring, silole ring, Benzoshiroru ring, dibenzosilole ring, Bororu ring, Benzobororu ring, aromatic heterocyclic ring such as dibenzo ball roll ring.
In the formula (1), the D ring and the E ring are preferably an aromatic heterocyclic ring which may have a substituent, and the aromatic heterocyclic ring is preferably an aromatic heterocyclic ring containing a 5-membered ring, and a thiophene ring is More preferred.
Examples of the substituent of the aromatic ring represented by D ring and E ring include a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and a substituted group. 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 Arylalkylthio group which may be substituted, arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic ring Groups, acyl groups, acyloxy groups, amide groups, carboxyl groups, nitro groups and cyano groups.An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted aryloxy group, a substituted An optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group, an optionally substituted arylalkylthio group, an optionally substituted arylalkenyl group, an optionally substituted Definitions and specific examples of a good arylalkynyl group, substituted amino group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group and amide group are the above-mentioned R¹An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio 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, an optionally substituted arylalkylthio group, an optionally substituted arylalkenyl group, a substituted The definition and specific examples of arylalkynyl group, substituted amino group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group and amide group which may be used are the same.
Examples of the structural unit represented by Formula (1) include structural units represented by Formula (601) to Formula (660).

In the formulas (601) to (660), R represents a hydrogen atom or a substituent. A plurality of R may be the same or different, and may be bonded to each other to form a ring. When R is a substituent, examples of the substituent include a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, and a substituted group. An optionally substituted aryloxy group, an optionally substituted aryloxy group, an optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group, an optionally substituted Arylalkylthio group, optionally substituted arylalkenyl group, optionally substituted arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl Groups, acyloxy groups, amide groups, carboxyl groups, nitro groups and cyano groups. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted aryloxy group, a substituted An optionally substituted arylthio group, an optionally substituted arylalkyl group, an optionally substituted arylalkoxy group, an optionally substituted arylalkylthio group, an optionally substituted arylalkenyl group, an optionally substituted Definitions and specific examples of a good arylalkynyl group, substituted amino group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group and amide group are the above-mentioned R¹An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio 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, an optionally substituted arylalkylthio group, an optionally substituted arylalkenyl group, a substituted The definition and specific examples of arylalkynyl group, substituted amino group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group and amide group which may be used are the same.
Among the structural units represented by the formulas (601) to (660), the structural units represented by the formulas (621) to (640) are preferable from the viewpoint of increasing the photoelectric conversion efficiency, and the formula (621) A structural unit represented by Formula (625) is more preferable.
From the viewpoint of increasing the light absorption intensity of the organic compound containing the structural unit represented by the formula (1), the structural unit represented by the formula (1) preferably contains an aromatic heterocyclic ring. By including the aromatic heterocycle, the planarity of the organic compound containing the structural unit represented by the formula (1) is increased, and the light absorption intensity is improved. By improving the light absorption intensity, the light absorption amount of the organic compound is increased, and the short-circuit current density of the photoelectric conversion element of the present invention is improved.
From the viewpoint of lengthening the light absorption terminal wavelength of the organic compound containing the structural unit represented by the formula (1), the structural unit represented by the formula (1) preferably contains a thiophene ring. By having a thiophene ring, charge transfer inside the molecule occurs, and the light absorption terminal wavelength is increased. By increasing the light absorption terminal wavelength, the light absorption amount of the organic compound is increased, and the short-circuit current density is improved.
When the structural unit represented by the formula (1) includes a thiophene ring, the absorption strength of the organic compound and the fill factor of the photoelectric conversion element of the present invention are also improved. Conversion efficiency is increased.
From the viewpoint of enhancing the durability of the photoelectric conversion element, R in the structural unit represented by the formula (1)¹Is preferably a benzene ring having substituents at the 2-position and 5-position. The substituent is preferably an isopropyl group.
The organic compound used in the photoelectric conversion element of the present invention preferably contains a structural unit different from the structural unit represented by the formula (1) in addition to the structural unit represented by the formula (1). In this case, it is preferable that the structural unit represented by Formula (1) and the structural unit different from the structural unit represented by Formula (1) form a conjugate. Conjugation in the present invention means that multiple bonds exist with one single bond in between.
Examples of the structural unit different from the structural unit represented by the formula (1) include an optionally substituted arylene group, an optionally substituted heteroarylene group, an alkenylene group, and an alkynylene group. From the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element of the present invention, an optionally substituted arylene group and an optionally substituted heteroarylene group are preferable.
Here, the arylene group means a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon, and the carbon number is usually 6 to 60. A heteroarylene group means a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic heterocycle. Specific examples of the aromatic ring are the same as the specific examples of the D ring and the E ring described above, and specific examples of the substituent of the arylene group and the heteroarylene group are specific examples of the substituent of the D ring and the E ring described above. Is the same.
Examples of the optionally substituted arylene group and the optionally substituted heteroarylene group include at least one structural unit selected from Group 1 described above.
In Group 1, the aromatic ring represented by ring G to ring N may be a monocyclic aromatic ring or a polycyclic aromatic ring. As the monocyclic aromatic ring, for example, benzene ring, pyrrole ring, furan ring, thiophene ring, oxazole ring, thiazole ring, thiadiazole ring, pyrazole ring, pyridine ring, pyrazine ring, imidazole ring, triazole ring, isoxazole ring, Examples include isothiazole ring, pyrimidine ring, pyridazine ring and triazine ring.
Examples of the polycyclic aromatic ring include an aromatic ring in which an arbitrary ring is condensed to the monocyclic aromatic ring. Examples of the ring condensed with the monocyclic aromatic ring include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, and an imidazoline. Ring, imidazolidine ring, pyrazole ring, pyrazoline ring, prazolidine ring, furazane ring, triazole ring, thiadiazole ring, oxadiazole ring, tetrazole ring, pyran ring, pyridine ring, piperidine ring, thiopyran ring, lidazine ring, pyrimidine ring, Pyrazine ring, piperazine ring, morpholine ring, triazine ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, isoindole ring, indolizine ring, indoline ring, isoindoline ring, chromene ring, chroman ring, isochroma Ring, benzopyran ring, quinoline ring, isoquinoline ring, quinolidine ring, benzimidazole ring, benzothiazole ring, indazole ring, naphthyridine ring, quinoxaline ring, quinazoline ring, quinazolidine ring, cinnoline ring, phthalazine ring, purine ring, pteridine ring, carbazole Ring, xanthene ring, phenanthridine ring, acridine ring, β-carboline ring, perimidine ring, phenanthroline ring, thianthrene ring, phenoxathiin ring, phenoxazine ring, phenothiazine ring and phenazine ring.
R³⁰, R³¹And R³²When is a substituent, examples of the substituent include a halogen atom (for example, a fluorine atom, a bromine atom, a chlorine atom) and a group having 1 to 30 carbon atoms. Examples of the group having 1 to 30 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, and an octyloxy group. , Alkoxy groups such as dodecyloxy group, and aryl groups such as phenyl group and naphthyl group.
In group 1, R²⁰~ R²⁵Represents a hydrogen atom or a substituent. R²⁰~ R²⁵When is a substituent, examples of the substituent include a halogen atom (for example, a fluorine atom, a bromine atom, a chlorine atom) and a group having 1 to 30 carbon atoms. Examples of the group having 1 to 30 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, and an octyloxy group. , Alkoxy groups such as dodecyloxy group, and aryl groups such as phenyl group and naphthyl group.
R²⁰And R²¹May be connected to each other to form a ring structure. Specific examples of the cyclic structure formed by linking include structures of the following formulas (a) to (c).

R in formula (a) to formula (c)⁷⁰And R⁷¹Each independently represents a hydrogen atom or a substituent. R⁷⁰And R⁷¹When is a substituent, examples of the substituent include a halogen atom (for example, a fluorine atom, a bromine atom, a chlorine atom) and a group having 1 to 30 carbon atoms. Examples of the group having 1 to 30 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, and an octyloxy group. , Alkoxy groups such as dodecyloxy group, and aryl groups such as phenyl group and naphthyl group.
X³⁰And X³¹Each independently represents a sulfur atom or a selenium atom. X³⁰And X³¹Is preferably a sulfur atom. Y³⁰~ Y³⁵Each independently represents a nitrogen atom or ═CH—. Y³⁰~ Y³⁵Is preferably a nitrogen atom.
Ring G to Ring N are R²⁰~ R²⁵Examples of the substituent include a halogen atom (for example, a fluorine atom, a bromine atom, a chlorine atom) and a group having 1 to 30 carbon atoms. Examples of the group having 1 to 30 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, and an octyloxy group. , Alkoxy groups such as dodecyloxy group, and aryl groups such as phenyl group and naphthyl group.
Among the structural units included in Group 1, from the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element of the present invention, the structural units represented by Formula (A-2) to Formula (E-2) in Group 2 below are included. preferable.
(Group 2)

Q in formula (A-2) to formula (E-2)²~ Q⁹Each independently represents a sulfur atom, an oxygen atom, a selenium atom, -N (R³⁰)-Or -CR³¹= CR³²-Represents. R³⁰, R³¹, R³²Represents the same meaning as described above. Q²~ Q⁹Is preferably a sulfur atom. Y¹~ Y⁴Each independently represents a nitrogen atom or ═CH—. Y¹~ Y⁴Is preferably a nitrogen atom.
R⁴⁰~ R⁴⁹Each independently represents a hydrogen atom or a substituent. R⁴⁰~ R⁴⁹When is a substituent, examples of the substituent include a halogen atom (for example, a fluorine atom, a bromine atom, a chlorine atom) and a group having 1 to 30 carbon atoms. Examples of the group having 1 to 30 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group and a dodecyl group, a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, and an octyloxy group. , Alkoxy groups such as dodecyloxy group, and aryl groups such as phenyl group and naphthyl group. R⁴⁰And R⁴¹, R⁴²And R⁴³May be connected to each other to form an annular structure.
R⁴⁰And R⁴¹, R⁴²And R⁴³Specific examples of the cyclic structure formed by connecting are cyclic structures represented by the formula (a) and cyclic structures represented by the formula (b).
As the structural unit represented by the formula (A-2) to the formula (E-2), from the viewpoint of increasing the light absorption intensity of the organic compound containing the structural unit represented by the formula (1), the formula (500 ) To groups represented by formula (522) are preferred.

(Wherein R represents the same meaning as described above)
Among the groups represented by formula (500) to formula (522), from the viewpoint of increasing the light absorption terminal wavelength of the organic compound, the group represented by formula (500), represented by formula (506) And a group represented by formula (511) are preferred, and a group represented by formula (511) is more preferred. As the light absorption terminal wavelength becomes longer, the amount of light absorption increases, and the short-circuit current density of the photoelectric conversion efficiency of the present invention improves.
The organic compound used in the photoelectric conversion device of the present invention is preferably a polymer compound from the viewpoint of ease of device production.
The polymer compound in the present invention refers to a polymer having a weight average molecular weight of 1000 or more, and a polymer compound having a weight average molecular weight of 3,000 to 10,000,000 is preferably used. If the weight average molecular weight is lower than 3000, defects may occur in film formation during device fabrication, and if it exceeds 10000000, solubility in a solvent and applicability during device fabrication may be degraded. The weight average molecular weight is more preferably 8,000 to 5,000,000, particularly preferably 10,000 to 1,000,000.
In addition, the weight average molecular weight in this invention points out the weight average molecular weight of polystyrene conversion calculated using the standard sample of polystyrene using gel permeation chromatography (GPC).
When the photoelectric conversion element of this invention contains the high molecular compound containing the structural unit represented by Formula (1), content of the structural unit represented by Formula (1) in this polymeric compound is in a compound. It suffices that at least one is included in. Preferably, the polymer compound contains an average of 2 or more per polymer chain, and more preferably an average of 3 or more per polymer chain.
A preferable compound used in the photoelectric conversion element of the present invention includes a structural unit represented by the formula (1-1) and is a structural unit represented by the formula (A-1), which is represented by the formula (B-1). Selected from the group consisting of a structural unit represented by formula (C-1), a structural unit represented by formula (D-1), and a structural unit represented by formula (E-1). It is a polymer compound containing at least one structural unit.
In the formula (1-1), specific examples of the substituent that the thiophene ring represented by the D ″ ring and the E ″ ring may have are the substituents that the D ring and the E ring may have. The same as the specific example of the group.
The structural unit represented by the formula (1-1), the structural unit represented by the formula (A-1), the structural unit represented by the formula (B-1), and the formula (C-1). And a polymer compound comprising at least one structural unit selected from the group consisting of a structural unit represented by formula (D-1) and a structural unit represented by formula (E-1) When the total number of units is 100, the content of the structural unit represented by the formula (1-1) is preferably 10 to 90, more preferably 20 to 80, and particularly preferably 30 to 70. .
In addition, the polymer compound that can be used in the photoelectric conversion element of the present invention preferably has high solubility in a solvent from the viewpoint of ease of device production. Specifically, it preferably has a solubility capable of producing a solution containing 0.01% by weight (wt)% or more of the polymer compound, and has a solubility capable of producing a solution containing 0.1% by weight or more. More preferably, it has a solubility capable of producing a solution containing 0.4 wt% or more.
From the viewpoint of increasing the photoelectric conversion efficiency of the photoelectric conversion element, the open end voltage of the photoelectric conversion element is preferably high. When using the organic compound containing the structural unit represented by Formula (1) as an electron-donating compound, the higher the ionization potential of the organic compound, the higher the open-circuit voltage of the photoelectric conversion element of the present invention.
The production method of the polymer compound that can be used in the present invention is not particularly limited, but from the viewpoint of the ease of synthesis of the polymer compound, a method using a Suzuki coupling reaction, and a Stille coupling reaction. The method using is preferable.
As a method using the Suzuki coupling reaction, for example, the formula (100):
U¹-E¹-U²(100)
[Where E¹Represents a divalent group containing an aromatic ring. U¹And U²Each independently represents a dihydroxyboryl group (—B (OH)₂) Or a borate ester residue. ]
One or more compounds represented by formula (200):
T¹-E²-T²(200)
[Where E²Represents a divalent group containing an aromatic ring. T¹And T²Each independently represents a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or a sulfonic acid residue. ]
The manufacturing method which has a process with which 1 or more types of compounds represented by these are made to react in presence of a palladium catalyst and a base is mentioned. Where E¹Or E²Is a structural unit represented by the formula (1).
In this case, the total number of moles of the one or more compounds represented by the formula (200) used for the reaction is 0.8 to about the total number of moles of the one or more compounds represented by the formula (100). The amount is preferably 1.2 mol, and more preferably 0.9 to 1.1 mol.
The boric acid ester residue means a group obtained by removing a hydroxyl group from a boric acid diester, and examples thereof include a dialkyl ester residue, a diaryl ester residue, and a di (arylalkyl) ester residue. As the borate ester residue, the following formula:

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)
The group represented by these is illustrated.
Because of the ease of polymer compound synthesis, T¹And T²The halogen atom is preferably a bromine atom or an iodine atom, more preferably a bromine atom.
T in equation (200)¹And T²Is a sulfonic acid (-SO₃H) means an atomic group obtained by removing acidic hydrogen from alkyl sulfonate group (for example, methane sulfonate group, ethane sulfonate group), aryl sulfonate group (for example, benzene sulfonate group, p-toluene sulfonate group). , Arylalkyl sulfonate groups (eg, benzyl sulfonate groups) and trifluoromethane sulfonate groups.
Specifically, the method for carrying out the Suzuki coupling reaction includes a method in which a reaction is carried out in the presence of a base using a palladium catalyst as a catalyst in an arbitrary solvent.
Examples of the palladium catalyst used in the Suzuki coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis ( Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, and bis (dibenzylideneacetone) palladium. From the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate, dichlorobis ( Triphenylphosphine) palladium, palladium acetate, and tris (dibenzylideneacetone) dipalladium are preferred.
The addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 mol to 0.5 mol with respect to 1 mol of the compound represented by the formula (100). The amount is preferably 0.0003 mol to 0.1 mol.
When palladium acetate is used as a palladium catalyst used in the Suzuki coupling reaction, for example, a phosphorus compound such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine is added as a ligand. can do. In this case, the addition amount of the ligand is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol with respect to 1 mol of the palladium catalyst. is there.
Examples of the base used for the Suzuki coupling reaction include inorganic bases, organic bases, inorganic salts and the like. Examples of the inorganic base include potassium carbonate, sodium carbonate, and barium hydroxide. Examples of the organic base include triethylamine and tributylamine. An example of the inorganic salt is cesium fluoride.
The amount of the base added is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the compound represented by the formula (100). is there.
The Suzuki coupling reaction is usually performed in a solvent. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran. From the viewpoint of solubility of the polymer compound used in the present invention, toluene and tetrahydrofuran are preferred. Further, the base may be added as an aqueous solution and reacted in a two-phase system. When an inorganic salt is used as the base, it is usually added as an aqueous solution and reacted from the viewpoint of solubility of the inorganic salt.
In addition, when adding a base as aqueous solution and making it react by a two-phase system, you may add phase transfer catalysts, such as a quaternary ammonium salt, as needed.
The temperature at which the Suzuki coupling reaction is carried out depends on the solvent, but is usually about 50 to 160 ° C., and 60 to 120 ° C. is preferable from the viewpoint of increasing the molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time may be reached when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is preferable from the viewpoint that the reaction proceeds efficiently.
The Suzuki coupling reaction is performed in a reaction system in which the Pd (0) catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed in a system sufficiently deaerated with argon gas or nitrogen gas. Specifically, after the inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the compound represented by the formula (100), the compound represented by the formula (200), Dichlorobis (triphenylphosphine) palladium (II) was charged, the polymerization vessel was sufficiently replaced with nitrogen gas, degassed, and then degassed by adding a degassed solvent such as toluene by bubbling with nitrogen gas in advance. Thereafter, a base degassed by bubbling with nitrogen gas in advance, for example, an aqueous sodium carbonate solution, is dropped into this solution, and then heated and heated, for example, while maintaining an inert atmosphere at the reflux temperature for 8 hours. Polymerize.
As a method using Stille coupling reaction, for example, the formula (300):
U³-E³-U⁴(300)
[Where E³Represents a divalent group containing an aromatic ring. U³And U⁴Each independently represents a substituted stannyl group. ]
And a method of reacting one or more compounds represented by the formula (200) with one or more compounds represented by the formula (200) in the presence of a palladium catalyst. Where E³Or E²Is a structural unit represented by the formula (1).
As substituted stannyl group, -SnR¹⁰⁰ ₃The group etc. which are represented by these are mentioned. Where R¹⁰⁰Represents a monovalent organic group. Examples of the monovalent organic group include an alkyl group and an aryl group.
The carbon number of the alkyl group is usually 1 to 30, and specific examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl Group, 2-methylbutyl group, 1-methylbutyl group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, Examples thereof include chain alkyl groups such as nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group. Examples of the aryl group include a phenyl group and a naphthyl group. The organotin residue is preferably -SnMe₃, -SnEt₃, -SnBu₃, -SnPh₃And more preferably -SnMe₃, -SnEt₃, -SnBu₃It is. In the above preferred examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
Specifically, examples of the catalyst include a method of reacting in an arbitrary solvent under a palladium catalyst.
Examples of the palladium catalyst used in the Stille coupling reaction include Pd (0) catalyst, Pd (II) catalyst, and the like. Specifically, palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium are mentioned. From the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate, palladium [ Tetrakis (triphenylphosphine)] and tris (dibenzylideneacetone) dipalladium are preferred.
The addition amount of the palladium catalyst used for the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 per 1 mol of the compound represented by the formula (100). The amount is from mol to 0.5 mol, preferably from 0.0003 mol to 0.2 mol.
In the Stille coupling reaction, a ligand or a cocatalyst can be used as necessary. Examples of the ligand include phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, tris (2-furyl) phosphine, triphenylarsine, and triphenoxyarsine. Examples include arsenic compounds. Examples of the cocatalyst include copper iodide, copper bromide, copper chloride, and copper (I) 2-thenoylate.
When a ligand or promoter is used, the amount of ligand or promoter added is usually 0.5 to 100 moles, preferably 0.9 to 20 moles per mole of palladium catalyst. More preferably, it is 1 mol to 10 mol.
The Stille coupling reaction is usually performed in a solvent. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, toluene, dimethoxyethane, and tetrahydrofuran. From the viewpoint of solubility of the polymer compound used in the present invention, toluene and tetrahydrofuran are preferable.
The temperature at which the Stille coupling reaction is performed depends on the solvent, but is usually about 50 to 160 ° C., and preferably 60 to 120 ° C. from the viewpoint of increasing the molecular weight of the polymer compound. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
The time for performing the reaction (reaction time) may be the end point when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is preferable from the viewpoint that the reaction proceeds efficiently.
The Stille coupling reaction is performed in a reaction system in which the Pd catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is performed in a system sufficiently deaerated with argon gas or nitrogen gas. Specifically, after the inside of the polymerization vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, the polymerization vessel is charged with a compound represented by the formula (300), a compound represented by the formula (200), A palladium catalyst is charged, and the polymerization vessel is sufficiently replaced with nitrogen gas, degassed, and then bubbled with nitrogen gas in advance to add a degassed solvent, for example, toluene, and then coordinate as necessary. After adding the catalyst and the cocatalyst, the mixture is heated and heated, for example, and polymerized while maintaining an inert atmosphere at the reflux temperature for 8 hours.
If the polymerization active group remains at the end of the polymer compound that can be used in the photoelectric conversion device of the present invention, the properties and life of the device obtained when used in the production of the device may be reduced. It may be protected with a stable group. The stable group is preferably a group having a conjugated bond continuous with the conjugated structure of the main chain. The stable group may have a structure bonded to an aryl group or a heterocyclic group via a vinylene group. Examples of the stable group include a phenyl group having no substituent, a naphthyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, and a pentafluoroethyl group.
The compound used for the photoelectric conversion element of the present invention can be produced, for example, by polymerizing a compound represented by the formula (1-2) as one of raw materials.

(Wherein R¹, D 'ring, E' ring, W¹And W²Has the same meaning as described above. )
Specific examples of the aromatic heterocycle represented by the D ′ ring and the E ′ ring are the same as the specific examples of the aromatic heterocycle represented by the D ring and the E ring described above. Specific examples of the substituent that the aromatic heterocycle represented by the D ′ ring and the E ′ ring may have include the aromatic heterocycle represented by the aforementioned D ring and E ring. It is the same as the specific example of a good substituent. The D ′ ring and the E ′ ring are preferably a thiophene ring, a furan ring and a pyrrole ring, and more preferably a thiophene ring.
In formula (1-2), R¹Is preferably an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aryloxy group and an optionally substituted arylalkyl group. An aryl group which may be substituted, an aryloxy group which may be substituted and an arylalkyl group which may be substituted are more preferable, and an aryl group is particularly preferable.
W in formula (1-2)¹And W²The definition and specific examples of the boric acid ester residue represented by¹And U²The definition and specific examples of the boric acid ester residue represented by W¹And W²The definition and specific examples of the sulfonic acid residue represented by¹And T²Are the same as the definitions and specific examples of the halogen atom and the sulfonic acid residue. W¹And W²The definition and specific examples of the substituted stannyl group represented by³And U⁴The definition and specific example of the substituted stannyl group represented by these are the same. W¹And W²The monohalogenated methyl group represented by the formula represents a group in which one hydrogen atom in the methyl group is substituted with a halogen atom.
From the viewpoint of producing high molecular weight compounds, W¹And W²Are each independently preferably a halogen atom, a sulfonic acid residue, a boric acid ester residue, a dihydroxyboryl group or a substituted stannyl group.
W in formula (1-2)¹And W²When a compound in which is a hydrogen atom is used in the reaction, a polymer compound having a structural unit represented by the formula (1) can be produced by oxidative polymerization. In oxidative polymerization, a catalyst is usually used. As such a catalyst, a known catalyst can be used. Examples of the catalyst include a metal halide and a mixture of a metal halide and an amine complex (metal halide / amine complex). Examples of the metal halide include monovalent halides, divalent halides, and trivalent halides of metals such as copper, iron, vanadium, and chromium. Examples of the amine used for producing the amine complex include pyridine, lutidine, 2-methylimidazole, and N, N, N ′, N′-tetramethylethylenediamine. A metal halide / amine complex can be prepared by mixing a metal halide and an amine in a solvent in the presence of oxygen. 1/0. It is about 1 to 1/200, preferably about 1 / 0.3 to 1/100.
As the catalyst, iron chloride can also be used (Polym. Prep. Japan, Vol. 48, 309 (1999)). Further, by using a copper / amine catalyst system (J. Org. Chem., 64, 2264 (1999), J. Polym. Sci. Part A, Polym. Chem., 37, 3702 (1999)) The molecular weight can be increased.
As the solvent in the oxidative polymerization, any solvent can be used as long as the catalyst is not poisoned. Examples of such solvents include hydrocarbons, ethers, and alcohols. Here, examples of the hydrocarbon include toluene, benzene, xylene, trimethylbenzene, tetramethylbenzene, naphthalene, and tetralin. Examples of the ether include diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, diphenyl ether, and tert-butyl methyl ether. Examples of alcohols include methanol, ethanol, isopropanol, and 2-methoxyethanol.
The reaction temperature in oxidative polymerization is usually −100 ° C. to 100 ° C., preferably −50 to 50 ° C.
Further, in the case of producing a copolymer, a method of polymerizing by mixing two or more types of monomers, a method of adding a second type of monomer after polymerizing one type of monomer, and the like can be mentioned. By using or combining these methods, it is possible to produce block copolymers, random copolymers, alternating copolymers, multiblock copolymers, graft copolymers, and the like.
As a manufacturing method of the compound represented by Formula (1-2), it can manufacture by reaction of the compound represented by Formula (1-3), and a boron compound.

(Where¹, W², D 'ring and E' ring have the same meaning as described above. X⁵⁰And X⁵¹Represents a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom). )
In the compound represented by formula (1-3), when the D ′ ring and the E ′ ring have a halogen atom as a substituent, or W¹And W²X is a halogen atom, X⁵⁰And X⁵¹In terms of increasing the yield of the compound represented by formula (1-2), the halogen atom represented by formula (1-2) is a halogen atom possessed by the D ′ ring and the E ′ ring, or W¹And W²A halogen atom having higher reactivity with a base and a metal than a halogen atom represented by
As a manufacturing method of the compound represented by Formula (1-2), for example, after reacting the compound represented by Formula (1-3) with a base, the boron compound represented by Formula (1-4) The method of making this react is mentioned.

(Wherein R¹Has the same meaning as described above. X⁵²And X⁵³Each independently represents a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or an optionally substituted alkoxy group. X⁵²And X⁵³Are an optionally substituted alkoxy group, these may be linked to each other to form a ring. )
X in formula (1-4)⁵²And X⁵³Specific examples of the optionally substituted alkoxy group represented by:¹Are the same as the specific examples of the alkoxy group which may be substituted.
Examples of the base used in the reaction include lithium hydride, sodium hydride, potassium hydride, methyl lithium, butyl lithium (n-BuLi), tert-butyl lithium (tert-BuLi), phenyl lithium, lithium diisopropylamide, lithium hexa Examples include methyl disilazide, sodium hexamethyl disilazide and potassium hexamethyl disilazide.
Solvents used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane and bromobutane. , Halogenated saturated hydrocarbons such as chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methanol, ethanol, propanol, isopropanol, Alcohols such as butanol and tert-butyl alcohol, carboxylic acids such as formic acid, acetic acid and propionic acid, dimethyl ether, diethyl ether, methyl Ethers such as tert-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, amines such as pyridine, N, N-dimethylformamide, N, N-dimethylacetamide Amides such as N, N-diethylacetamide and N-methylmorpholine oxide are exemplified, and a single solvent or a mixed solvent thereof can be used depending on the reaction.
After the reaction, for example, after stopping the reaction with water, the product can be obtained by usual post-treatment such as extraction of the product with an organic solvent and distillation of the solvent. The product can be isolated and purified by methods such as chromatographic fractionation and recrystallization.
Compound (C) which is one embodiment of the compound represented by Formula (1-2) can be produced, for example, by reacting Compound (B) with 2 equivalents of bromine in dichloromethane.

Compound (B) is obtained by reacting compound (A) with 2 equivalents of butyl lithium (n-BuLi) in tetrahydrofuran (hereinafter sometimes referred to as THF), and then 2,4,6-triisopropylphenyl. It can be produced by reacting 1 equivalent of dimethoxyborane.
Compound (B) is obtained by reacting compound (A) with 2 equivalents of n-BuLi in THF, then reacting compound (A) with 2 equivalents of magnesium bromide, and 2,4,6-tri It can also be produced by reacting 1 equivalent of isopropylphenyldimethoxyborane.
Another method for producing the compound represented by the formula (1-2) includes a method of coupling the compound represented by the formula (1-5) in the molecule.

(Wherein R¹, W¹, W², D ′ ring and E ′ ring have the same meaning as described above. X⁵⁴And X⁵⁵Represents a halogen atom (for example, a chlorine atom, a bromine atom and an iodine atom). )
X⁵⁴And X⁵⁵The halogen atom represented by is preferably a bromine atom or an iodine atom.
Intramolecular coupling is preferably performed in the presence of a metal. Examples of the metal include copper, iron, nickel, zinc, and the like, preferably copper.
Examples of the solvent used for intramolecular coupling include aliphatic hydrocarbons, aromatic hydrocarbons, amides, sulfoxides, and lactams. Examples of the aliphatic hydrocarbon include pentane, hexane, heptane, octane and cyclohexane. Examples of the aromatic hydrocarbon include benzene, toluene, ethylbenzene, and xylene. Examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide and N, N-diethylacetamide. Examples of the sulfoxide include dimethyl sulfoxide. As a lactam, N-methylpyrrolidone is mentioned, for example.
After the reaction, for example, after adding water to the reaction system to stop the reaction, the product can be obtained by usual post-treatment such as extracting the product with an organic solvent and distilling off the solvent. The product can be isolated and purified by methods such as chromatographic fractionation and recrystallization.
The compound represented by the formula (1-5) can be obtained, for example, by halogenating (for example, bromination or iodination) the compound represented by the formula (1-6).

(Wherein R¹, W¹, W², D ′ ring and E ′ ring have the same meaning as described above. )
The compound represented by the formula (1-6) is brominated to form X⁵⁴And X⁵⁵In the method for producing the compound represented by the formula (1-5) in which is a bromine atom, a known method can be used as a bromination method, for example, represented by the formula (1-6) And bromination by bringing the compound into contact with bromine or N-bromosuccinimide (NBS). The conditions for bromination can be arbitrarily set, but the method of reacting with NBS in a solvent is desirable from the viewpoint of high bromination rate and high selectivity of the bromine atom introduction position. Examples of the solvent used in the method include N, N-dimethylformamide, chloroform, methylene chloride, carbon tetrachloride and the like. The reaction time is usually about 1 minute to 10 hours, and the reaction temperature is usually about −50 ° C. to 50 ° C. The amount of bromine used is preferably about 1 mol to 5 mol with respect to 1 mol of the compound represented by the formula (1-6). After the reaction, for example, after adding water to the reaction system to stop the reaction, the product is extracted with an organic solvent and subjected to usual post-treatment such as evaporation of the solvent.⁵²And X⁵³A compound represented by the formula (1-5) in which is a bromine atom can be obtained. The product can be isolated and purified by a method such as chromatographic fractionation or recrystallization.
X is obtained by iodination of the compound represented by formula (1-6)⁵⁴And X⁵⁵In the method for producing the compound represented by the formula (1-5) in which is an iodine atom, the method for iodination is to react the compound represented by the formula (1-6) with a base and then react with iodine. A method is mentioned. The base and solvent used in the method are used in the step of reacting the compound represented by the above formula (1-3) with a base and then reacting with the boron compound represented by the formula (1-4). The same thing as a base and a solvent is mentioned.
The compound represented by the formula (1-6) is represented by the above formula (1-4) after reacting a halide containing an aromatic heterocycle corresponding to the D ′ ring and the E ′ ring with a base. It can be produced by reacting with a compound to be prepared. The base and solvent used in the reaction are used in the step of reacting the compound represented by the above formula (1-3) with a base and then reacting with the boron compound represented by the formula (1-4). The same thing as a base and a solvent is mentioned.
Compound (G) can be produced, for example, by adding 5 equivalents of copper powder to compound (F) in N, N-dimethylformamide and stirring at 100 ° C. with heating.

Compound (F) can be produced by reacting compound (E) with 2 equivalents of n-BuLi in THF and then reacting 2 equivalents of iodine.
Compound (E) can be produced by reacting compound (D) with 2 equivalents of n-BuLi in THF and then reacting 1 equivalent of 2,4,6-triisopropylphenyldimethoxyborane.
W¹And W²As a method for producing a compound represented by the formula (1-2) in which is a bromine atom, W¹And W²Bromine a compound represented by the formula (1-2) in which is hydrogen atom¹And W²And the like, and the like. W¹And W²A known method can be used as a method for converting benzene into a bromine atom.¹And W²And bromine by bringing a compound represented by the formula (1-2) in which is a hydrogen atom into contact with bromine or N-bromosuccinimide (NBS). The conditions for bromination can be arbitrarily set. For example, a method of reacting with NBS in a solvent is desirable because the bromination rate is high and the selectivity of the introduction position of bromine atoms is high. Examples of the solvent used at this time include N, N-dimethylformamide, chloroform, methylene chloride, and carbon tetrachloride. The reaction time is usually about 1 minute to 10 hours, and the reaction temperature is usually about −50 ° C. to 50 ° C. The amount of bromine used is W¹, W²Is preferably about 1 mol to 5 mol with respect to 1 mol of the compound represented by the formula (1-2) in which is a hydrogen atom. After the reaction, for example, after stopping the reaction by adding water, the product is extracted with an organic solvent and subjected to usual post-treatment such as distilling off the solvent.¹And W²A compound represented by the formula (1-2) in which is a bromine atom can be obtained. The product can be isolated and purified by a method such as chromatographic fractionation or recrystallization.
The polymer compound that can be used in the present invention preferably has a long wavelength at the light absorption terminal wavelength. The light absorption terminal wavelength in the present invention means a value obtained by the following method.
For the measurement, a spectrophotometer (for example, JASCO-V670, made by JASCO Corporation) operating in the wavelength region of ultraviolet, visible, and near infrared is used. When JASCO-V670 is used, since the measurable wavelength range is 200 to 1500 nm, the measurement is performed in the wavelength range. First, the absorption spectrum of the substrate used for measurement is measured. As the substrate, a quartz substrate, a glass substrate, or the like is used. Next, a thin film containing the first compound is formed on the substrate from a solution containing the first compound or a melt containing the first compound. In film formation from a solution, drying is performed after film formation. Thereafter, an absorption spectrum of the laminate of the thin film and the substrate is obtained. The difference between the absorption spectrum of the laminate of the thin film and the substrate and the absorption spectrum of the substrate is obtained as the absorption spectrum of the thin film.
In the absorption spectrum of the thin film, the vertical axis represents the absorbance of the compound, and the horizontal axis represents the wavelength. It is desirable to adjust the thickness of the thin film so that the absorbance at the largest absorption peak is about 0.5 to 2. The absorbance of the absorption peak with the longest wavelength among the absorption peaks is defined as 100%, and the intersection of the absorption peak and a straight line parallel to the horizontal axis (wavelength axis) including the absorbance of 50% of the absorption peak. The intersection point that is longer than the peak wavelength is taken as the first point. The intersection point between the absorption peak and a straight line parallel to the wavelength axis containing 25% of the absorbance, which is longer than the peak wavelength of the absorption peak, is defined as a second point. The intersection of the straight line connecting the first point and the second point and the reference line is defined as the light absorption terminal wavelength. Here, the reference line is the intersection of the absorption peak and the straight line parallel to the wavelength axis including the absorbance of 10% at the absorption peak of the longest wavelength, where the absorbance of the absorption peak is 100%. The third point on the absorption spectrum that is 100 nm longer than the reference wavelength and the absorption spectrum that is 150 nm longer than the reference wavelength with reference to the wavelength of the intersection that is longer than the peak wavelength of the absorption peak A straight line connecting the top and the fourth point.
The photoelectric conversion element of the present invention has one or more active layers containing a compound having a structural unit represented by the formula (1) between a pair of electrodes at least one of which is transparent or translucent.
As a preferable form of the photoelectric conversion element of the present invention, it has an active layer formed of a pair of electrodes, at least one of which is transparent or translucent, and an organic composition of a p-type organic semiconductor and an n-type organic semiconductor. . The compound having the structural unit represented by the formula (1) is preferably used as a p-type organic semiconductor.
The photoelectric conversion element of the present invention is usually formed on a substrate. The substrate may be any substrate that does not chemically change when the electrodes are formed and the 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.
In another aspect of the photoelectric conversion element of the present invention, a first active layer containing the compound used in the present invention is adjacent to the first active layer between a pair of electrodes, at least one of which is transparent or translucent. Thus, the photoelectric conversion element includes a second active layer containing an electron-accepting compound such as a fullerene derivative.
Examples of the transparent or translucent electrode material 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 Alternatively, gold, platinum, silver, copper, or the like is 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.
One electrode may not be transparent, and as the electrode material of the electrode, a metal, a conductive polymer, or the like can be used. Specific examples of the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. And one or more alloys selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin. Examples include alloys with metals, graphite, graphite intercalation compounds, polyaniline and derivatives thereof, and polythiophene and derivatives thereof. 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.
An additional intermediate layer other than the active layer may be used as a means for improving the photoelectric conversion efficiency. Examples of the material used for the intermediate layer include alkali metals such as lithium fluoride, halides of alkaline earth metals, oxides such as titanium oxide, and PEDOT (poly-3,4-ethylenedioxythiophene).
The active layer may contain the compound having the structural unit represented by the formula (1) alone or in combination of two or more. In order to improve the hole transport property of the active layer, a compound other than the compound having the structural unit represented by the formula (1) is mixed as an electron donating compound and / or an electron accepting compound in the active layer. Can also be used. The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.
As the electron-donating compound, in addition to the compound having the structural unit represented by the formula (1), for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and Derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amine residues in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene And derivatives thereof.
As the electron-accepting compound, in addition to the compound having the structural unit represented by the formula (1), for example, carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, Benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline And derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine), fullerene, hula Include alkylene derivatives, preferably, titanium oxide, carbon nanotubes, fullerene, a fullerene derivative, particularly preferably a fullerene, a fullerene derivative.
Fullerene and C as fullerene derivatives₆₀, C₇₀, C₇₆, C₇₈, C₈₄And derivatives thereof. The fullerene derivative represents a compound in which at least a part of fullerene is modified.
Examples of the fullerene derivative include a compound represented by formula (I), a compound represented by formula (II), a compound represented by formula (III), and a compound represented by formula (IV).

(In the formulas (I) to (IV), R^aIs an alkyl group which may be substituted, an aryl group which may be substituted, a heteroaryl group or a group having an ester structure. Multiple R^aMay be the same or different. R^bRepresents an optionally substituted alkyl group or an optionally substituted aryl group. Multiple R^bMay be the same or different. )
R^aAnd R^bDefinitions and specific examples of the optionally substituted alkyl group and the optionally substituted aryl group represented by¹The definition and specific examples of the alkyl group which may be substituted and the aryl group which may be substituted are the same.
R^aExamples of the heteroaryl group represented by: include a thiophenediyl group, a pyridinediyl group, a furandiyl group, and a pyrrolediyl group.
R^aExamples of the group having an ester structure represented by the formula (V) include a group represented by the formula (V).

(Wherein u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, R^cRepresents an optionally substituted alkyl group, an optionally substituted aryl group or heteroaryl group. )
R^cDefinitions and specific examples of the optionally substituted alkyl group, the optionally substituted aryl group and the heteroaryl group represented by^aThe definition and specific examples of the alkyl group which may be substituted, the aryl group and the heteroaryl group which may be substituted are the same.
C₆₀Specific examples of the derivatives include the following.

C₇₀Specific examples of the derivatives include the following.

Examples of fullerene derivatives include [6,6] phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6] -phenyl C61 butyric acid methyl ester), [6,6] phenyl-C71 butyric acid methyl ester (C70PCBM). [6,6] -Phenyl C71 butyric acid methyl ester), [6,6] Phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6] -Phenyl C85 butyric acid methyl ester), [6,6] And C61 butyric acid methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).
When the active layer contains the compound having the structural unit represented by formula (1) and the fullerene derivative, the ratio of the fullerene derivative is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the compound. 20 to 500 parts by weight is more preferable.
The thickness of the active layer is usually preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and more preferably 20 nm to 200 nm.
The method for producing the active layer may be produced by any method, and examples thereof include film formation from a solution containing a compound having the structural unit of formula (1), and film formation by vacuum deposition.
A preferred method for producing a photoelectric conversion element is a method for producing an element having a first electrode and a second electrode, and having an active layer between the first electrode and the second electrode, Applying a solution (ink) containing a compound having the structural unit of formula (1) and a solvent on the first electrode by a coating method to form an active layer; and forming a second electrode on the active layer It is the manufacturing method of the element which has the process to form.
When the photoelectric conversion element of the present invention contains a polymer compound having the structural unit represented by the formula (1), the solvent used for film formation from a solution dissolves the polymer compound used in the present invention. If it is. Examples of the solvent include unsaturated hydrocarbons such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane. , Halogenated saturated hydrocarbons such as chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, tetrahydrofuran, tetrahydropyran And ethers. The polymer compound used in the present invention can usually be dissolved in the solvent in an amount of 0.1% by weight or more.
When forming a film using a solution, slit coating method, knife coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, Spray coating method, screen printing method, gravure printing method, flexographic printing method, offset printing method, ink jet coating method, dispenser printing method, nozzle coating method, capillary coating method etc. can be used, slit coating method, capillary A coating method, a gravure coating method, a micro gravure coating method, a bar coating method, a knife coating method, a nozzle coating method, an inkjet coating method, and a spin coating method are preferable.
From the viewpoint of film formability, the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.
The compound used in the present invention can also be used in an organic thin film transistor. The organic thin film transistor has a configuration including a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path. The organic semiconductor layer is constituted by the organic thin film described above. Examples of such an organic thin film transistor include a field effect type and an electrostatic induction type.
A field effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, a gate electrode for controlling the amount of current passing through the current path, and an organic semiconductor layer and a gate electrode It is preferable to provide an insulating layer disposed between the two. In particular, the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer (active layer), and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween. In the field effect organic thin film transistor, the organic semiconductor layer is constituted by an organic thin film containing the polymer compound used in the present invention.
The electrostatic induction organic thin film transistor which is one embodiment of the organic thin film transistor of the present invention controls a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, and an amount of current passing through the current path. It is preferable to have a gate electrode, and this gate electrode is provided in the organic semiconductor layer. In particular, it is preferably provided in contact with the source electrode and the drain electrode. Here, the structure of the gate electrode may be a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. An electrode is mentioned. In the static induction organic thin film transistor, the organic semiconductor layer is composed of an organic thin film containing the compound used in the present invention. The thickness of the active layer is usually preferably 1 nm to 100 μm, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, more preferably 20 nm to 200 nm.
The photoelectric conversion element of the present invention can be operated as an organic thin film solar cell by generating a photovoltaic force between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.
Also, by applying light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes or in a state where no voltage is applied, 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.
Organic thin-film solar cells can have basically the same module structure as conventional solar cell modules. The solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side. Specifically, a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known. The module structure of the organic thin film solar cell of the present invention can be appropriately selected depending on the purpose of use, the place of use and the environment.
In a typical super straight type or substrate type module, cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are connected by metal leads or flexible wiring. The current collector electrode is connected to the outer edge portion, and the generated power is taken out to the outside. Various types of plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filling resin depending on the purpose in order to protect the cell and improve the current collection efficiency. In addition, when used in a place where it is not necessary to cover the surface with a hard material such as a place where there is little impact from the outside, the surface protection layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin. It is possible to eliminate the supporting substrate on one side. The periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material. In addition, if a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface. In the case of a solar cell using a flexible support such as a polymer film, cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material. Thus, the battery body can be produced. Also, a module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 may be used. Furthermore, a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Reference Example 1 (Synthesis of 3,3′-dibromo-5,5′-tetramethylsilyl-2,2′-bithiophene (1))

In a 200 mL flask in which the air in the flask was replaced with argon, Heterocycles, 1991, Vol. 32, No. 9, p. 5.00 g (10.4 mmol) of 3,3′5,5′-tetrabromo-2,2′-bithiophene synthesized by the method described in 1805 and dehydrated tetrahydrofuran (hereinafter sometimes referred to as THF) 100 mL was added to obtain a uniform solution. The flask was cooled to −78 ° C., and 7.98 mL (20.74 mmol) of a hexane solution of 2.6 M butyllithium (n-BuLi) was added dropwise. The reaction solution was stirred at −78 ° C. for 2 hours, and then 2.50 g (23.0 mmol) of tetramethylchlorosilane was added dropwise. The flask was warmed to room temperature over 1 hour, and 50 mL of water was added to stop the reaction. Thereafter, ethyl acetate was added to the reaction solution to extract an organic layer containing the reaction product, the extracted organic layer was dried over sodium sulfate, filtered, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product is purified by a silica gel column whose developing solvent is hexane, and the obtained solid is recrystallized using ethanol to obtain the desired 3,3′-dibromo-5,5′-tetramethylsilyl- 3.5 g of 2,2′-bithiophene (1) was obtained.
¹ H NMR: 7.12 (S, 2H), 0.34 (S, 18H)
Reference Example 2 (Synthesis of Compound (2))

0.424 g (0.905 mmol) of compound (1) and 20 mL of dehydrated THF were added to a 100 mL flask in which the air in the flask was replaced with argon to obtain a uniform solution. The flask was cooled to −78 ° C., and 0.71 mL (1.85 mmol) of 2.6M n-BuLi in hexane was added dropwise over 5 minutes. The reaction solution was stirred at -78 ° C for 30 minutes and then stirred at -30 ° C for 30 minutes. Thereafter, the flask was cooled to −78 ° C., and 0.535 g (2.91 mmol) of anhydrous magnesium bromide was added. The reaction solution was stirred at -78 ° C for 30 minutes and then stirred at 0 ° C for 2 hours. Thereafter, the flask was cooled to −78 ° C., and 0.25 g (0.905 mmol) of 2,4,6-triisopropylphenyldimethoxyborane was added. The reaction solution was stirred at -78 ° C for 30 minutes and then stirred at 0 ° C for 7 hours. Thereafter, 100 mL of water was added to the reaction solution to stop the reaction, ethyl acetate was added to the reaction solution, and the organic layer was extracted. The organic layer was dried over sodium sulfate and filtered. Thereafter, the solvent in the filtrate was distilled off using an evaporator. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 4: 1 (volume ratio)) to obtain 281 mg of compound (2).
¹ H NMR: 7.07 (s, 2H), 6.92 (s, 2H), 2.94 (m, 1H), 2.75 (m, 2H), 1.35 (d, 6H), 1 .23 (d, 12H), 0.29 (s, 18H)
Reference Example 3 (Synthesis of Compound (3))

In a 100 mL flask in which the air in the flask was replaced with argon, 281 mg (0.538 mmol) of compound (2) and 10 mL of dichloromethane were added to obtain a homogeneous solution. The flask was cooled to −30 ° C., and a solution in which 100 mg of bromine was dissolved in 5 mL of dichloromethane was added dropwise over 30 minutes. After the dropping, the reaction solution was stirred at −10 ° C. for 1 hour, then stirred at 0 ° C. for 2 hours, and then stirred at 20 ° C. for 4 hours. After stirring, 50 mL of water was added to the reaction solution to stop the reaction, dichloromethane was added to the reaction solution, and the organic layer was extracted. The organic layer was dried over sodium sulfate and filtered, and then the solvent in the filtrate was distilled off using an evaporator. The remaining solid was purified with a silica gel column (hexane: ethyl acetate = 9: 1 (volume ratio)) to obtain 132 mg (0.246 mmol) of the desired compound (3).
¹ H NMR: 7.07 (s, 2H), 6.64 (s, 2H), 1.22 (s, 18H)
Example 1 (Synthesis of polymer (A))

In a 100 mL flask in which the air in the flask was replaced with argon, 69 mg (0.129 mmol) of compound (3) and compound (4) (4,7-bis (4,4,5,5-tetramethyl-1,3,3) were added. 2-dioxabolol-2-yl) -2,1,3-benzothiadiazole) (Aldrich) 50 mg (0.129 mmol), methyltrialkylammonium chloride (trade name Aliquat 336 (registered trademark), Aldrich) 35 mg In addition, it was dissolved in 10 mL of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 0.43 mg of palladium acetate, 2.38 mg of tris (2-methoxyphenyl) phosphine) and 1 mL of 16.7 wt (wt)% aqueous sodium carbonate solution were added to the toluene solution. And stirring at 100 ° C. for 8 hours. Thereafter, 1 g of sodium diethyldithiocarbamate and 10 mL of water were added to the reaction solution, and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the reaction solution was cooled to around room temperature (25 ° C.), and then the obtained reaction solution was allowed to stand and a separated toluene layer was recovered. The toluene layer was washed twice with 10 mL of water, twice with 10 mL of 3% by weight acetic acid aqueous solution and twice with 10 mL of water, and the obtained toluene layer was poured into methanol, and the deposited precipitate was recovered. The precipitate was dried under reduced pressure and then dissolved in chloroform. Next, the obtained liquid was filtered to remove insoluble matters, and then passed through an alumina column for purification. The obtained chloroform solution was concentrated under reduced pressure, poured into methanol and precipitated, and the generated precipitate was collected. The precipitate was washed with methanol and then dried under reduced pressure to obtain 25 mg of a polymer. Hereinafter, this polymer is referred to as a polymer (A).
Example 2 (Measurement of ionization potential of organic thin film)
Polymer A was dissolved in o-dichlorobenzene at a concentration of 1.0% by weight to prepare a coating solution. The obtained coating solution was applied onto a glass substrate by spin coating. The coating operation was performed at 23 ° C. Then, it baked at 120 degreeC under air | atmosphere for 5 minutes, and obtained the organic thin film with a film thickness of about 70 nm. When the ionization potential of the organic thin film obtained was measured using an atmospheric photoelectron spectrometer (AC-2, manufactured by Riken Keiki Co., Ltd.), the ionization potential was 5.2 eV.
Since the ionization potential of the polymer A is high, the open-circuit voltage of the organic photoelectric conversion element including the polymer A in the active layer is high.
Reference Example 4 (Synthesis of Compound (6))

In a 200 mL flask in which the air in the flask was replaced with argon, 1.78 g (10.0 mmol) of compound (5), 5.83 g (25.0 mmol) of 2-ethylhexyl bromide, and 41.5 mg (0 .25 mmol) and 1.68 g (30.0 mmol) of potassium hydroxide were dissolved in 35 mL of dimethyl sulfoxide and stirred at room temperature (25 ° C.) for 24 hours. After the reaction, 100 mL of water was added to the reaction solution, hexane was further added to extract the organic layer containing the product, and purification was performed with a silica gel column whose developing solvent was hexane to obtain 2.61 g of Compound (6).
Reference Example 5 (Synthesis of Compound (7))

To a 200 mL flask in which the air in the flask was replaced with argon, 1.31 g (3.25 mmol) of compound (6) and 25 mL of dimethylformamide (DMF) were added, the flask was cooled to 0 ° C., and N-bromosuccinimide (NBS) was added. ) Was added and stirred for 12 hours. 100 mL of water was added to the reaction solution to stop the reaction, and diethyl ether was added to the reaction solution to extract an organic layer containing the product. Purification was performed on a silica gel column in which the developing solvent was hexane to obtain 1.70 g of compound (7).
Reference Example 6 (Synthesis of Polymer B)

In a 200 mL flask in which the air in the flask was replaced with argon, 561 mg (1.00 mmol) of compound (7), 388.1 mg (1.00 mmol) of compound (4), methyltrialkylammonium chloride (trade name Aliquat 336 (registered) (Trademark) and Aldrich) were added in an amount of 202 mg, dissolved in 20 ml of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Then, 2.25 mg of palladium acetate, 12.3 mg of tris (2-methoxyphenyl) phosphine (Tris (2-methoxyphenyl) phosphine), 6.5 mL of 16.7 wt% sodium carbonate aqueous solution were added to the reaction solution, and 100 Stirring was carried out at 5 ° C. for 5 hours. Thereafter, 50 mg of phenylboric acid was added to the reaction solution, and further reacted at 70 ° C. for 2 hours. Thereafter, 2 g of sodium diethyldithiocarbamate and 20 mL of water were added to the reaction solution, followed by stirring under reflux for 2 hours. After removing the aqueous layer, the organic layer was washed twice with 20 ml of water, then twice with 20 mL of 3% by weight acetic acid aqueous solution, and further washed twice with 20 mL of water. The resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the obtained polymer was redissolved in 30 mL of o-dichlorobenzene, passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate the polymer. The polymer was filtered and dried to obtain 280 mg of a purified polymer. Hereinafter, this polymer is referred to as polymer B.
Comparative Example 1 (Measurement of ionization potential of organic thin film)
Polymer B was dissolved in o-dichlorobenzene at a concentration of 1.0% by weight to prepare a coating solution. The obtained coating solution was applied onto a glass substrate by spin coating. The coating operation was performed at 23 ° C. Then, it baked for 5 minutes at 120 degreeC in air | atmosphere, and obtained the organic thin film with a film thickness of about 100 nm. When the ionization potential of the organic thin film obtained using an atmospheric photoelectron spectrometer (AC-2 manufactured by Riken Keiki Co., Ltd.) was measured, the ionization potential was 5.0 eV.

The photoelectric conversion element of the present invention has a high open end voltage and is useful.

Claims

A first electrode and a second electrode; an active layer between the first electrode and the second electrode; and a structural unit represented by formula (1) in the active layer: A photoelectric conversion element containing an organic compound.

(In the formula, R 1 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, 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, arylalkylthio group which may be substituted, substituted Arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group, Represents an amide group, a carboxyl group, a nitro group or a cyano group, and the D ring and the E ring are each independently Represents an aromatic ring optionally having a substituent.)
The organic compound is further a structural unit represented by the formula (A-1), a structural unit represented by the formula (B-1), a structural unit represented by the formula (C-1), and the formula (D-1). The photoelectric conversion element of Claim 1 containing the at least 1 sort (s) of structural unit chosen from the group which consists of the structural unit represented by and the structural unit represented by Formula (E-1).

(In formulas (A-1) to (E-1), Q 1 represents a sulfur atom, an oxygen atom, a selenium atom, —N (R 30 ) — or —CR 31 ═CR 32 —. R 30 , R 31 and R 32 each independently represents a hydrogen atom or a substituent, R 20 to R 25 each independently represents a hydrogen atom or a substituent, and R 20 and R 21 are linked to form a cyclic structure. (G ring to N ring each independently represents an aromatic ring which may have a substituent.)
The photoelectric conversion device according to claim 1, wherein at least one of the D ring and the E ring is an aromatic heterocyclic ring which may have a substituent.
The photoelectric conversion element according to claim 3, wherein at least one of the D ring and the E ring is a thiophene ring.
A solar cell module comprising the photoelectric conversion element according to any one of claims 1 to 4.
An image sensor comprising the photoelectric conversion element according to any one of claims 1 to 4.
An organic thin film transistor having a gate electrode, a source electrode, a drain electrode, and an active layer, and containing an organic compound containing a structural unit represented by formula (1) in the active layer.

(In the formula, R 1 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, 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, arylalkylthio group which may be substituted, substituted Arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group, Represents an amide group, a carboxyl group, a nitro group or a cyano group, and the D ring and the E ring are each independently Represents an aromatic ring optionally having a substituent.)
Formula (1-1)

Wherein R 1 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, 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, arylalkylthio group which may be substituted, substituted Arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group, Represents an amide group, a carboxyl group, a nitro group or a cyano group, wherein the D ″ ring and the E ″ ring are each independently May have a substituent represents an thiophene ring.)
A structural unit represented by formula (A-1), a structural unit represented by formula (B-1), a structural unit represented by formula (C-1), A polymer compound comprising at least one structural unit selected from the group consisting of a structural unit represented by formula (D-1) and a structural unit represented by formula (E-1).

(In formulas (A-1) to (E-1), Q 1 represents a sulfur atom, an oxygen atom, a selenium atom, —N (R 30 ) — or —CR 31 ═CR 32 —. R 30 , R 31 and R 32 each independently represents a hydrogen atom or a substituent, R 20 to R 25 each independently represents a hydrogen atom or a substituent, and R 20 and R 21 are linked to form a cyclic structure. (G ring to N ring each independently represents an aromatic ring which may have a substituent.)
A compound represented by formula (1-2).

Wherein R 1 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, 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, arylalkylthio group which may be substituted, substituted Arylalkenyl group which may be substituted, arylalkynyl group which may be substituted, amino group, substituted amino group, silyl group, substituted silyl group, silyloxy group, substituted silyloxy group, heterocyclic group, acyl group, acyloxy group, An amide group, a carboxyl group, a nitro group or a cyano group, each of the D ′ ring and the E ′ ring independently; .W 1 and W 2 representing an aromatic heterocyclic ring optionally having a substituent are each independently a hydrogen atom, a halogen atom, a sulfonic acid residue, a boric acid ester residue, a monohalogenated methyl group, (Represents a dihydroxyboryl group, a formyl group, a vinyl group or a substituted stannyl group.)
The compound according to claim 9, wherein at least one of the D ′ ring and the E ′ ring is a thiophene ring.