JP5810837B2 - Polymer compound and organic photoelectric conversion device using the same - Google Patents

Description

  The present invention relates to a polymer compound and an organic photoelectric conversion device using the same.

  Organic semiconductor materials are expected to be applied to organic photoelectric conversion elements such as organic solar cells and optical sensors. In particular, when a polymer compound is used as the organic semiconductor material, the functional layer can be manufactured by an inexpensive coating method. In order to improve various characteristics of the organic photoelectric conversion element, use of organic semiconductor materials that are various polymer compounds for the organic photoelectric conversion element has been studied. As an organic semiconductor material, for example, 9,9-dioctylfluorene-2,7-diboronic acid ester and 5,5 ″ ″-dibromo-3 ″, 4 ″ -dihexyl-α-pentathiophene are polymerized. A polymer compound has been proposed (Patent Document 1).

Special table 2007-529596 gazette

  However, the polymer compound has a problem that long-wavelength light is not sufficiently absorbed.

  Then, an object of this invention is to provide the high molecular compound with the large light absorbency of long wavelength light.

（１）
〔式中、Ｑ及びＲは、同一又は相異なり、水素原子、フッ素原子、フッ素置換されていてもよいアルキル基、フッ素置換されていてもよいアルコキシ基、置換されていてもよいアリール基、置換されていてもよいヘテロアリール基又は式（２）で表される基を表す。２個あるＱは、同一でも相異なってもよい。１２個あるＲは、それぞれ同一でも相異なってもよい。

（２）
（式中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、フッ素置換されていてもよいアルキル基、置換されていてもよいアリール基又は置換されていてもよいヘテロアリール基を表す。Ｘ^１及びＸ^２は、同一又は相異なり、−ＣＨ_２−、ＣＨＦ−又は−ＣＦ_２−を表す。Ｘ^１が複数個ある場合、それらは同一でも相異なってもよい。Ｘ^２が複数個ある場合、それらは同一でも相異なってもよい。）〕 That is, the present invention first provides a polymer compound containing a repeating unit represented by the formula (1).

(1)
[Wherein, Q and R are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group which may be substituted with fluorine, an alkoxy group which may be substituted with fluorine, an aryl group which may be substituted, substituted Represents a heteroaryl group which may be substituted or a group represented by the formula (2). Two Qs may be the same or different. The 12 Rs may be the same or different.

(2)
(In the formula, m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group which may be substituted with fluorine, an aryl group which may be substituted, or a substituted group. X ¹ and X ² are the same or different and represent —CH ₂ —, CHF— or —CF ₂ —, and when there are a plurality of X ¹ , they may be the same or different. And when there are a plurality of X ² , they may be the same or different.)]

  Secondly, the present invention provides an organic photoelectric conversion device having a pair of electrodes and a functional layer provided between the electrodes, wherein the functional layer includes an electron accepting compound and the polymer compound.

  The polymer compound of the present invention is extremely useful because it has a large absorbance for light having a long wavelength.

1 is a diagram showing an absorption spectrum of polymer compound 1. FIG. 2 is a graph showing an absorption spectrum of polymer compound 2. FIG.

  Hereinafter, the present invention will be described in detail.

（１）
〔式中、Ｑ及びＲは、同一又は相異なり、水素原子、フッ素原子、フッ素置換されていてもよいアルキル基、フッ素置換されていてもよいアルコキシ基、置換されていてもよいアリール基、置換されていてもよいヘテロアリール基又は式（２）で表される基を表す。２個あるＱは、同一でも相異なってもよい。１２個あるＲは、それぞれ同一でも相異なってもよい。

（２）
（式中、ｍ１は、０〜６の整数を表し、ｍ２は、０〜６の整数を表す。Ｒ’は、フッ素置換されていてもよいアルキル基、置換されていてもよいアリール基又は置換されていてもよいヘテロアリール基を表す。Ｘ^１及びＸ^２は、同一又は相異なり、−ＣＨ_２−、ＣＨＦ−又は−ＣＦ_２−を表す。Ｘ^１が複数個ある場合、それらは同一でも相異なってもよい。Ｘ^２が複数個ある場合、それらは同一でも相異なってもよい。）〕 <Polymer compound>
The polymer compound of the present invention includes a repeating unit represented by the formula (1).

(1)
[Wherein, Q and R are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group which may be substituted with fluorine, an alkoxy group which may be substituted with fluorine, an aryl group which may be substituted, substituted Represents a heteroaryl group which may be substituted or a group represented by the formula (2). Two Qs may be the same or different. The 12 Rs may be the same or different.

(2)
(In the formula, m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group which may be substituted with fluorine, an aryl group which may be substituted, or a substituted group. X ¹ and X ² are the same or different and represent —CH ₂ —, CHF— or —CF ₂ —, and when there are a plurality of X ¹ , they may be the same or different. And when there are a plurality of X ² , they may be the same or different.)]

  Examples of the alkyl group represented by Q or R include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and octyl group. , Isooctyl group, decyl group, dodecyl group, pentadecyl group and octadecyl group. A hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

  Examples of the alkoxy group represented by Q or R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. Cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, and 3,7-dimethyloctyloxy group. A hydrogen atom in the alkoxy group may be substituted with a fluorine atom. Examples of the alkoxy group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.

  When Q or R is an alkyl group or an alkoxy group, from the viewpoint of solubility of the polymer compound in a solvent, the alkyl group or alkoxy group preferably has 1 to 20 carbon atoms, and 2 to 18 More preferably, it is more preferably 3-12.

  The aryl group represented by Q or R has a structure in which a group containing a benzene ring, a group containing a condensed ring having aromaticity, two or more benzene rings, or a condensed ring having aromaticity are directly bonded. A group having a structure in which two or more benzene rings or aromatic condensed rings are bonded via a group such as vinylene. The aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms. As an aryl group, a phenyl group, 1-naphthyl group, and 2-naphthyl group are mentioned, for example. The aryl group may have a substituent. Examples of the substituent that the aryl group may have include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.

  Examples of the heteroaryl group represented by Q or R include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group. Examples of the substituent that the heteroaryl group may have include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.

In the group represented by the formula (2), m1 represents an integer of 0 to 6, and m2 represents an integer of 0 to 6. R ′ represents an alkyl group which may be substituted with fluorine, an aryl group which may be substituted or a heteroaryl group which may be substituted. The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R ′ are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R. X ¹ and X ² are the same or different and represent —CH ₂ —, CHF—, or —CF ₂ —. When there are a plurality of X ¹ , they may be the same or different. If X ² is a plurality, they may be the same or different.

  Examples of the repeating unit represented by the formula (1) include the following repeating units.

  The amount of the repeating unit represented by the formula (1) contained in the polymer compound of the present invention is selected from the viewpoint of increasing the photoelectric conversion efficiency of an organic photoelectric conversion device having a functional layer containing the polymer compound. The amount is preferably 20 to 100 mol%, more preferably 30 to 100 mol%, based on the total amount of repeating units contained in the compound.

The weight average molecular weight in terms of polystyrene of the polymer compound of the present invention is preferably 10 ³ to 10 ⁸ , more preferably 10 ³ to 10 ⁷ , and still more preferably 10 ³ to 10 ⁶ .

  The polymer compound of the present invention is preferably a conjugated polymer compound. Here, the conjugated polymer compound means a compound in which atoms constituting the main chain of the polymer compound are substantially conjugated.

  The polymer compound of the present invention may have a repeating unit other than the repeating unit represented by the formula (1). Examples of the repeating unit other than the repeating unit represented by the formula (1) include an optionally substituted arylene group and an optionally substituted heteroarylene group. Examples of the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a pyrenediyl group, and a fluorenediyl group. Examples of the substituent that the arylene group may have include a halogen atom, an alkyl group, and an alkoxy group. Examples of the heteroarylene group include a flangyl group, a pyrrole diyl group, a pyridinediyl group, and the like. Examples of the substituent that the heteroarylene group may have include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.

<Method for producing polymer compound>
The polymer compound of the present invention may be produced by any method. For example, after synthesizing a monomer having a functional group suitable for the polymerization reaction to be used, the monomer is dissolved in an organic solvent, if necessary, , And can be synthesized by polymerization using a known aryl coupling reaction using a catalyst, a ligand and the like. The synthesis of the monomer can be performed, for example, with reference to the methods disclosed in JP-A Nos. 2006-182920 and 2006-335933.

  Examples of the polymerization by the aryl coupling reaction include polymerization by Stille coupling reaction, polymerization by Suzuki coupling reaction, polymerization by Yamamoto coupling reaction, and polymerization by Kumada-Tamao coupling reaction.

  Polymerization by Stille coupling reaction is necessary using palladium complexes such as palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, bis (triphenylphosphine) palladium dichloride as catalysts. Depending on the ligand, ligands such as triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine A monomer having an organotin residue and a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a sulfonate group such as a trifluoromethanesulfonate group or a p-toluenesulfonate group. This is a polymerization in which the monomer is reacted. The details of the polymerization by the Stille coupling reaction are described in, for example, Angewante Chemie International Edition, 2005, Vol. 44, p. 4442-4489.

Polymerization by Suzuki coupling reaction uses a palladium complex or nickel complex as a catalyst in the presence of an inorganic base or an organic base, and a ligand is added as necessary to have a boronic acid residue or a boric acid ester residue. This is a polymerization in which a monomer is reacted with a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom, or a monomer having a sulfonate group such as a trifluoromethanesulfonate group or a p-toluenesulfonate group.
Examples of the inorganic base include sodium carbonate, potassium carbonate, cesium carbonate, tripotassium phosphate, and potassium fluoride. Examples of the organic base include tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetraethylammonium hydroxide. Examples of the palladium complex include palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, and bis (triphenylphosphine) palladium dichloride. Examples of the nickel complex include bis (cyclooctadiene) nickel. Examples of the ligand include triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, and tri (tert-butyl) phosphine. It is done.
Details of the polymerization by the Suzuki coupling reaction are described in, for example, Journal of Polymer Science: Part A: Polymer Chemistry (Part A: Polymer Chemistry), 2001, Vol. 39, p. 1533-1556.

Polymerization by Yamamoto coupling reaction uses a catalyst and a reducing agent to react monomers having halogen atoms, monomers having sulfonate groups such as trifluoromethanesulfonate groups, or monomers having halogen atoms and monomers having sulfonate groups. Polymerization.
Catalysts include nickel zero-valent complexes such as bis (cyclooctadiene) nickel and ligands such as bipyridyl, [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel. A catalyst comprising a nickel complex other than a nickel zero-valent complex such as dichloride and a ligand such as triphenylphosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine, if necessary. . Examples of the reducing agent include zinc and magnesium. Polymerization by the Yamamoto coupling reaction may be performed using a dehydrated solvent in the reaction, may be performed in an inert atmosphere, or may be performed by adding a dehydrating agent to the reaction system.
Details of the polymerization by Yamamoto coupling are described in, for example, Macromolecules, 1992, Vol. 25, p. 1214-1223.

  Polymerization by Kumada-Tamao coupling reaction uses a nickel catalyst such as [bis (diphenylphosphino) ethane] nickel dichloride, [bis (diphenylphosphino) propane] nickel dichloride, and a compound having a magnesium halide group and a halogen atom. Polymerization to react with the compound having For the reaction, a dehydrated solvent may be used for the reaction, the reaction may be performed in an inert atmosphere, or a dehydrating agent may be added to the reaction system.

  In the polymerization by the aryl coupling reaction, a solvent is usually used. The solvent may be selected in consideration of the polymerization reaction used, the solubility of the monomer and polymer, and the like. Specifically, organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, 1,2-dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and a mixed solvent obtained by mixing two or more of these solvents. Examples thereof include a solvent, a solvent having two phases of an organic solvent phase and an aqueous phase. The solvent used in the Stille coupling reaction is preferably an organic solvent such as tetrahydrofuran, toluene, N, N-dimethylformamide, a mixed solvent obtained by mixing two or more of these solvents, or a solvent having two phases of an organic solvent phase and an aqueous phase. . The solvent used for the Stille coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions. The solvent used for the Suzuki coupling reaction is tetrahydrofuran, toluene, 1,4-dioxane, 1,2-dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, a mixture of two or more of these solvents. An organic solvent such as a solvent and a solvent having two phases of an organic solvent phase and an aqueous phase are preferred. The solvent used for the Suzuki coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions. The solvent used for the Yamamoto coupling reaction is tetrahydrofuran, toluene, 1,4-dioxane, 1,2-dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and a mixture of two or more of these solvents. Organic solvents such as solvents are preferred. The solvent used for the Yamamoto coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions.

  Among the polymerizations by the aryl coupling reaction, from the viewpoint of reactivity, a method of polymerizing by a Stille coupling reaction, a method of polymerizing by a Suzuki coupling reaction, a method of polymerizing by a Yamamoto coupling reaction are preferable, and a Stille coupling reaction More preferred are a method of polymerizing, a method of polymerizing by a Suzuki coupling reaction, and a method of polymerizing by a Yamamoto coupling reaction using a nickel zero-valent complex.

  The lower limit of the reaction temperature of the aryl coupling reaction is preferably −100 ° C., more preferably −20 ° C., and particularly preferably 0 ° C. from the viewpoint of reactivity. The upper limit of the reaction temperature is preferably 200 ° C., more preferably 150 ° C., and particularly preferably 120 ° C. from the viewpoint of the stability of the monomer and the polymer compound.

  In the polymerization by the aryl coupling reaction, a known method can be used as a method for removing the polymer compound of the present invention from the reaction solution after completion of the reaction. For example, the polymer compound of the present invention can be obtained by adding a reaction solution to a lower alcohol such as methanol, filtering the deposited precipitate, and drying the filtrate. When the purity of the obtained polymer compound is low, it can be purified by recrystallization, continuous extraction with a Soxhlet extractor, column chromatography, or the like.

  When the polymer compound of the present invention is used for the production of an organic photoelectric conversion element, if a polymerization active group remains at the terminal of the polymer compound, characteristics such as durability of the organic photoelectric conversion element may be deteriorated. It is preferable to protect the terminal of the polymer compound with a stable group.

  Examples of the stable group for protecting the terminal include an alkyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkoxy group, an aryl group, an arylamino group, and a monovalent heterocyclic group. Examples of the arylamino group include a phenylamino group and a diphenylamino group. Examples of the monovalent heterocyclic group include thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, and isoquinolyl group. Further, the polymerization active group remaining at the terminal of the polymer compound may be replaced with a hydrogen atom instead of a stable group. From the viewpoint of enhancing hole transportability, it is preferable that the stable group for protecting the terminal is a group imparting electron donating properties such as an arylamino group. When the polymer compound is a conjugated polymer compound, the end of a group having a conjugated bond in which the conjugated structure of the main chain of the polymer compound and the conjugated structure of a stable group protecting the end are continuous is also protected. It can preferably be used as a stable group. Examples of the group include an aryl group and a monovalent heterocyclic group having aromaticity.

（３）
（式（３）中、Ｒは前述と同じ意味を表す。８個あるＲは、同一でも相異なってもよい。Ｔは、ホウ酸エステル残基を表す。２個あるＴは、同一でも相異なってもよい。）

（４）
（式（４）中、Ｑ及びＲは、前述と同じ意味を表す。２個あるＱは、同一でも相異なってもよい。４個あるＲは、それぞれ同一でも相異なってもよい。Ｚは、臭素原子、ヨウ素原子又は塩素原子を表す。２個あるＺは、同一でも相異なってもよい。） When the polymer compound of the present invention is produced using Suzuki coupling, for example, the polymer compound is produced by polymerizing the compound represented by the formula (3) and the compound represented by the formula (4). be able to.

(3)
(In formula (3), R represents the same meaning as described above. Eight Rs may be the same or different. T represents a borate residue. Two Ts may be the same or different. May be different.)

(4)
(In formula (4), Q and R represent the same meaning as described above. Two Qs may be the same or different. Four Rs may be the same or different. Z is Represents a bromine atom, an iodine atom or a chlorine atom, and two Zs may be the same or different.)

（式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。） In formula (3), the boric acid ester residue represented by T represents a group obtained by removing a hydroxyl group from boric acid diester, and specific examples thereof include groups represented by the following formula.

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)

As a compound represented by Formula (3), the following compound is mentioned, for example.

As a compound represented by Formula (4), the following compound is mentioned, for example.

<Organic photoelectric conversion element>
Since the polymer compound of the present invention has a high absorbance of light having a long wavelength such as 600 nm light and efficiently absorbs sunlight, an organic photoelectric conversion element manufactured using the polymer compound of the present invention has a short-circuit current. Density increases.

The organic photoelectric conversion device of the present invention includes a pair of electrodes, a functional layer between the electrodes, and the functional layer containing a polymer compound containing an electron-accepting compound and a repeating unit represented by the formula (1) To do. As an electron-accepting compound, fullerene and a fullerene derivative are preferable. As a specific example of the organic photoelectric conversion element,
1. An organic photoelectric conversion element having a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and a polymer compound containing a repeating unit represented by the formula (1);
2. An organic photoelectric conversion element having a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and a polymer compound containing a repeating unit represented by formula (1) An organic photoelectric conversion element in which the electron-accepting compound is a fullerene derivative;
Is mentioned. In general, at least one of the pair of electrodes is transparent or translucent. Hereinafter, this case will be described as an example.

  1 above. In the organic photoelectric conversion element, the amount of the electron-accepting compound in the functional layer containing the electron-accepting compound and the polymer compound is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. Is preferable, and it is more preferable that it is 20-500 weight part. In addition, 2. In the organic photoelectric conversion element, the amount of the fullerene derivative in the functional layer containing the fullerene derivative and the polymer compound is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound. More preferably, it is -500 weight part. From the viewpoint of increasing the photoelectric conversion efficiency, the amount of the fullerene derivative in the functional layer is preferably 20 to 400 parts by weight, and preferably 40 to 250 parts by weight with respect to 100 parts by weight of the polymer compound. More preferably, it is 80 to 120 parts by weight. From the viewpoint of increasing the short-circuit current density, the amount of the fullerene derivative in the functional layer is preferably 20 to 250 parts by weight, and preferably 40 to 120 parts by weight with respect to 100 parts by weight of the polymer compound. More preferred.

  In order for the organic photoelectric conversion element to have high photoelectric conversion efficiency, the electron-accepting compound and the polymer compound have an absorption region that can efficiently absorb a spectrum of desired incident light, In order that the heterojunction interface between the electron-accepting compound and the polymer compound efficiently separates excitons, the heterojunction interface is often included in the functional layer, and the charge generated by the heterojunction interface can be quickly absorbed. It is important that the electron-accepting compound and the polymer compound have a charge transporting property for transporting to the electrode.

  From such a viewpoint, as the organic photoelectric conversion element, the above 1. , 2. From the standpoint of including a large number of heterojunction interfaces, the organic photoelectric conversion element is preferable. The organic photoelectric conversion element is more preferable. Further, in the organic photoelectric conversion element of the present invention, an additional layer may be provided between at least one electrode and the functional layer in the element. Examples of the additional layer include a charge transport layer that transports holes or electrons, and a buffer layer.

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

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

  Examples of the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA , Gold, platinum, silver, and copper, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the electrode manufacturing method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.

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

<Organic thin film>
As the functional layer in the organic photoelectric conversion element of the present invention, for example, an organic thin film containing the polymer compound of the present invention and an electron-accepting compound can be used.

  The organic thin film has a thickness of usually 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.

  The organic thin film may contain the polymer compound alone or in combination of two or more. Moreover, in order to improve the hole transport property of the organic thin film, a low molecular compound and / or a high molecular compound other than the high molecular compound can be mixed and used as the electron donating compound in the organic thin film.

  Examples of the electron-donating compound that the organic thin film may contain in addition to the polymer compound having the repeating unit represented by the formula (1) include, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligos. Thiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof Derivatives, polythienylene vinylene and its derivatives.

Examples of the electron-accepting compound include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone derivatives. , diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerene and derivatives thereof such as C _60, carbon nanotube And phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, and fullerene and derivatives thereof are particularly preferable.

  The electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.

Examples of fullerenes include C ₆₀ fullerene, C ₇₀ fullerene, and C ₈₄ fullerene. Examples of the fullerene derivatives, C ₆₀ fullerene derivatives, C ₇₀ fullerene derivatives, C ₈₄ fullerene derivatives. A fullerene derivative represents a compound in which at least a part of fullerene is modified.

（Ｉ） （ＩＩ） （ＩＩＩ） （ＩＶ）

（式（Ｉ）〜（ＩＶ）中、Ｒ^ａは、フッ素置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいヘテロアリール基又はエステル構造を有する基である。複数個あるＲ^ａは、それぞれ同一であっても相異なってもよい。Ｒ^ｂはアルキル基又はアリール基を表す。複数個あるＲ^ｂは、それぞれ同一であっても相異なってもよい。） Examples of the fullerene derivative include a compound represented by the formula (I), a compound represented by the formula (II), a compound represented by the formula (III), and a compound represented by the formula (IV).

(I) (II) (III) (IV)

(In the formulas (I) to (IV), R ^a is an alkyl group which may be fluorine-substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted, or a group having an ester structure. there. plurality is R ^a is, R ^b good .R ^b be different from each be the same with. plurality represents an alkyl group or an aryl group each may be respectively or mutually different and the same .)

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

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

(V)
(Wherein, u1 represents an integer of 1 to 6, u2 represents an integer of Less than six, R ^c is fluorine optionally substituted alkyl group, an optionally substituted aryl group or a substituted Represents an optionally substituted heteroaryl group.)

Definitions and specific examples of the optionally substituted fluorine group represented by R ^c , the optionally substituted aryl group and the optionally substituted heteroaryl group are as follows: The definition and specific examples of the alkyl group which may be substituted, the aryl group which may be substituted and the heteroaryl group which may be substituted are the same.

Specific examples of the C ₆₀ fullerene derivative include the following compounds.

Specific examples of C ₇₀ fullerene derivatives include the following compounds.

<Method for producing organic thin film>
The organic thin film may be produced by any method. For example, the organic thin film may be produced by a film formation method from a solution containing the polymer compound of the present invention, or an organic thin film may be formed by a vacuum deposition method. Good. Examples of the method for producing an organic thin film by film formation from a solution include a method of producing an organic thin film by applying the solution on one electrode and then evaporating the solvent.

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

  For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method Coating methods such as a printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, a capillary coating method can be used, and a spin coating method, a flexographic printing method, an ink jet printing method, and a dispenser printing method are preferable.

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

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

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

The number average molecular weight in terms of polystyrene was determined by size exclusion chromatography (SEC).
Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6 mm Id x 15 cm); Detector: RI (SHIMADZU RID-10A); Mobile phase: Tetrahydrofuran (THF)

化合物（Ａ−１） Synthesis example 1
(Synthesis of Compound (A-1))
6.65 g of 2,7-dibromo-9-fluorenone was placed in a 500 ml three-necked flask where the gas in the flask was replaced with nitrogen, and dissolved in 140 ml of a mixed solvent of trifluoroacetic acid and chloroform. The ratio of the weight of chloroform to the weight of trifluoroacetic acid in the mixed solvent was 1. Sodium perborate monohydrate was added to the resulting solution and stirred for 20 hours. The reaction solution was filtered through celite, and the residue was washed with toluene. The filtrate was washed with water, sodium bisulfite, and saturated saline in this order, and then dried with sodium sulfate. Thereafter, the solvent was distilled off to obtain 6.11 g of a crude product.
The crude product was recrystallized using toluene to obtain a product. Further, the product was recrystallized using chloroform to obtain 1.19 g of compound (A-1).

Compound (A-1)

(Preparation of C ₈ H ₁₇ MgBr)
1.33 g of magnesium was placed in a 100 ml three-necked flask, and the flask was heated with a heat gun. Thereafter, the gas in the flask was replaced with argon. To the flask, 10 ml of tetrahydrofuran (THF) and 2.3 ml of 1-bromooctane were added and heated to start the reaction. The reaction solution was refluxed for 2.5 hours and then allowed to cool to room temperature to obtain a solution containing C ₈ H ₁₇ MgBr.

化合物（Ａ−２） (Synthesis of Compound (A-2))
1.00 g of compound (A-1) and 10 ml of tetrahydrofuran were placed in a 300 ml three-necked flask where the gas in the flask was replaced with nitrogen, and the compound (A-1) was suspended in tetrahydrofuran. The flask was cooled to 0 ° C. with a cold bath, and the solution containing C ₈ H ₁₇ MgBr prepared above was added. The cooling bath was removed from the flask, and the reaction solution was stirred for 5 hours under reflux. The reaction solution was allowed to cool, and 10 ml of water and 5 ml of hydrochloric acid were added. The reaction solution before adding hydrochloric acid was a suspension, but the reaction solution after adding hydrochloric acid was a two-phase solution. After separating the reaction solution, the organic phase was washed in this order with water and saturated brine. The organic phase thus obtained was dried using sodium sulfate and the solvent was distilled off to obtain 1.65 g of a crude product. The crude product was purified by silica gel column chromatography where the developing solvent was a mixed solvent of hexane and ethyl acetate to obtain 1.30 g of compound (A-2). The ratio of the volume of hexane to the volume of ethyl acetate in the developing solvent was 20.

Compound (A-2)

化合物（Ａ−３） (Synthesis of Compound (A-3))
In a 25 ml two-necked flask in which the gas in the flask was replaced with nitrogen, 0.20 g of compound (A-2) and 4 ml of toluene were placed, and compound (A-2) was dissolved in toluene. To this solution, 0.02 g (0.06 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at 100 ° C. for 11 hours. The resulting reaction solution was allowed to cool and then washed in this order with water, 4N aqueous sodium hydroxide solution, water and saturated brine. Then, the solvent was distilled off and 0.14g of compounds (A-3) were obtained.

Compound (A-3)

化合物（Ｃ） (Synthesis of Compound (C))
Under a nitrogen atmosphere, 1.0 g (1.77 mmol) of compound (A-3), 0.945 g (3.72 mmol) of bis (pinacolato) diboron, [1,1′-bis (diphenylphosphino) ) Ferrocene] 0.078 g (0.11 mmol) of palladium dichloride, 0.059 g (0.11 mmol) of 1,1′-bis (diphenylphosphino) ferrocene, and 15 ml of 1,4-dioxane were added to the reaction solution. Was bubbled with argon gas for 30 minutes. Thereafter, 1.043 g (10.6 mmol) of potassium acetate was added to the reaction solution and reacted at 95 ° C. for 13.5 hours under a nitrogen atmosphere. After completion of the reaction, the obtained reaction solution was filtered to remove insoluble matters. The reaction solution was purified with an alumina short column, the solvent was removed, and the solid content was dissolved in toluene. Activated carbon was added to the resulting solution and stirred, and then filtered. The obtained filtrate was purified with an alumina short column, and activated carbon was added to the purified solution and stirred, followed by filtration. Toluene was removed from the obtained filtrate, and then 2.5 ml of hexane was added and recrystallized to obtain 0.28 g of compound (C).

Compound (C)

化合物（Ｃ） 化合物（Ｄ）

フラスコ内の気体をアルゴンで置換した１００ｍＬフラスコに、化合物（Ｃ）を０．１４０ｇ（０．２１３ｍｍｏｌ）、化合物（Ｄ）（Ｌｕｍｉｎｅｓｃｅｎｃｅ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏｒｐｏｒａｔｉｏｎ社製）を０．１２０ｇ（０．１９２ｍｍｏｌ）、メチルトリオクチルメチルアンモニウムクロリド（商品名Ａｌｉｑｕａｔ３３６（登録商標）、シグマアルドリッチジャパン社製）を６５．０ｍｇ加え、トルエン１３ｍＬに溶解させ、得られたトルエン溶液をアルゴンで３０分バブリングした。その後、反応液に酢酸パラジウムを０．７２ｍｇ、トリス(２−メトキシフェニル)ホスフィン（Ｔｒｉｓ（２−ｍｅｔｈｏｘｙｐｈｅｎｙｌ）ｐｈｏｓｐｈｉｎｅ）を３．９ｍｇ、１６．７重量（ｗｔ）％の炭酸ナトリウム水溶液を１．３ｍＬ加え、１００℃で７時間攪拌を行った。その後、反応液にフェニルブロミドを１００ｍｇ加え、１００℃でさらに３時間攪拌した。その後、反応液にジエチルジチオカルバミン酸ナトリウムを１ｇ、及び、水を１０ｍＬ加え、１００℃で３時間攪拌を行った。反応終了後、反応液を室温（２５℃）付近まで冷却した後、得られた反応液を静置し、分液したトルエン層を回収した。該トルエン層を水１０ｍＬで２回、３％酢酸水１０ｍＬで２回、さらに水１０ｍＬで２回洗浄し、得られたトルエン層をメタノール中に注ぎ込み、析出した沈殿物を回収した。この沈殿物を減圧乾燥した後、トルエンに溶解させた。次に、得られたクロロホルム溶液をろ過し、不溶物を除去した後、ろ液をシリカゲル／アルミナカラムに通し、精製した。得られたクロロホルム溶液を減圧濃縮した後、メタノール中に注ぎ込み、生成した沈殿を回収した。該沈殿をメタノールで洗浄した後、減圧乾燥して、重合体５５ｍｇを得た。以下、この重合体を高分子化合物１と呼称する。高分子化合物１は、ポリスチレン換算の重量平均分子量（Ｍｗ）が１１２００であり、ポリスチレン換算の数平均分子量（Ｍｎ）が４８００であった。 Example 1
(Synthesis of polymer compound 1)

Compound (C) Compound (D)

In a 100 mL flask in which the gas in the flask was replaced with argon, 0.140 g (0.213 mmol) of the compound (C), 0.120 g (0.192 mmol) of the compound (D) (produced by Luminescence Technology Corporation), 65.0 mg of octylmethylammonium chloride (trade name Aliquat 336 (registered trademark), manufactured by Sigma-Aldrich Japan) was added and dissolved in 13 mL of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 0.72 mg of palladium acetate, 3.9 mg of tris (2-methoxyphenyl) phosphine (Tris (2-methoxyphenyl) phosphine), and 1.3 mL of 16.7 wt (wt)% aqueous sodium carbonate solution were added to the reaction solution. In addition, the mixture was stirred at 100 ° C. for 7 hours. Thereafter, 100 mg of phenyl bromide was added to the reaction solution, and the mixture was further stirred at 100 ° C. for 3 hours. Thereafter, 1 g of sodium diethyldithiocarbamate and 10 mL of water were added to the reaction solution, and the mixture was stirred at 100 ° C. for 3 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% aqueous acetic acid and twice with 10 mL of water, and the obtained toluene layer was poured into methanol, and the deposited precipitate was collected. The precipitate was dried under reduced pressure and then dissolved in toluene. Next, after the obtained chloroform solution was filtered to remove insoluble matters, the filtrate was passed through a silica gel / alumina column for purification. The obtained chloroform solution was concentrated under reduced pressure, poured into methanol, and the generated precipitate was recovered. The precipitate was washed with methanol and dried under reduced pressure to obtain 55 mg of a polymer. Hereinafter, this polymer is referred to as polymer compound 1. The polymer compound 1 had a polystyrene-equivalent weight average molecular weight (Mw) of 11200 and a polystyrene-equivalent number average molecular weight (Mn) of 4800.

フラスコ内の気体をアルゴンで置換した２Ｌ四つ口フラスコに、化合物（Ｅ）を７．９２８ｇ（１６．７２ｍｍｏｌ）、化合物（Ｆ）を１３．００ｇ（１７．６０ｍｍｏｌ）、トリオクチルメチルアンモニウムクロリド（商品名Ａｌｉｑｕａｔ３３６（登録商標）、シグマアルドリッチジャパン社製、CH₃N[(CH₂)₇CH₃]₃Cl、density 0.884g/ml、25℃）を４．９７９ｇ、及びトルエンを４０５ｍｌ入れ、撹拌しながら反応系内を３０分間アルゴンバブリングした。フラスコ内にジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）を０．０２ｇ加え、１０５℃に昇温し、撹拌しながら２ｍｏｌ／Ｌの炭酸ナトリウム水溶液４２．２ｍｌを滴下した。滴下終了後５時間反応させ、その後、フェニルボロン酸２．６ｇとトルエン１．８ｍｌとを加え、１０５℃で１６時間撹拌した。その後、反応液にトルエン７００ｍｌ及び７．５ｗｔ％のジエチルジチオカルバミン酸ナトリウム三水和物水溶液２００ｍｌを加え、８５℃で３時間撹拌した。反応液の水層を除去後、有機層を６０℃のイオン交換水３００ｍｌで２回、６０℃の３ｗｔ％酢酸３００ｍｌで１回、さらに６０℃のイオン交換水３００ｍｌで３回洗浄した。有機層をセライト、アルミナ及びシリカを充填したカラムに通し、溶出液を集めた。その後、熱トルエン８００ｍｌでカラムを洗浄し、洗浄後のトルエン溶液を溶出液に加えた。得られた溶液を７００ｍｌまで濃縮した後、濃縮した溶液を２Ｌのメタノールに加え、重合体を沈殿させた。重合体をろ過して単離し、５００ｍｌのメタノール、５００ｍｌのアセトン、５００ｍｌのメタノールで洗浄した。重合体を５０℃で一晩真空乾燥することにより、ペンタチエニル−フルオレンコポリマー（高分子化合物２）１２．２１ｇを得た。高分子化合物２のポリスチレン換算の重量平均分子量は１．１×１０⁵であった。 Synthesis example 2
(Synthesis of polymer compound 2)

In a 2 L four-necked flask in which the gas in the flask was replaced with argon, 7.928 g (16.72 mmol) of compound (E), 13.00 g (17.60 mmol) of compound (F), trioctylmethylammonium chloride ( Product name Aliquat 336 (registered trademark), Sigma-Aldrich Japan, CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, density 0.884 g / ml, 25 ° C.) 4.979 g and toluene 405 ml are stirred and stirred Then, argon was bubbled through the reaction system for 30 minutes. 0.02 g of dichlorobis (triphenylphosphine) palladium (II) was added to the flask, the temperature was raised to 105 ° C., and 42.2 ml of a 2 mol / L sodium carbonate aqueous solution was added dropwise with stirring. After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours, and then 2.6 g of phenylboronic acid and 1.8 ml of toluene were added and stirred at 105 ° C. for 16 hours. Thereafter, 700 ml of toluene and 200 ml of a 7.5 wt% sodium diethyldithiocarbamate trihydrate aqueous solution were added to the reaction solution, followed by stirring at 85 ° C. for 3 hours. After removing the aqueous layer of the reaction solution, the organic layer was washed twice with 300 ml of ion exchange water at 60 ° C., once with 300 ml of 3 wt% acetic acid at 60 ° C., and further three times with 300 ml of ion exchange water at 60 ° C. The organic layer was passed through a column filled with celite, alumina and silica, and the eluate was collected. Thereafter, the column was washed with 800 ml of hot toluene, and the washed toluene solution was added to the eluate. After concentrating the obtained solution to 700 ml, the concentrated solution was added to 2 L of methanol to precipitate a polymer. The polymer was isolated by filtration and washed with 500 ml methanol, 500 ml acetone, 500 ml methanol. The polymer was vacuum-dried at 50 ° C. overnight to obtain 12.21 g of a pentathienyl-fluorene copolymer (polymer compound 2). The weight average molecular weight in terms of polystyrene of the polymer compound 2 was 1.1 × 10 ⁵ .

Measurement example 1
(Measurement of absorbance of organic thin film)
Polymer compound 1 was dissolved in chloroform at a concentration of 0.5% 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 on 120 degreeC conditions in air | atmosphere, and obtained the organic thin film with a film thickness of about 100 nm. The absorption spectrum of the organic thin film was measured with a spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, and 800 nm.

Comparative Example 1
(Measurement of absorbance of organic thin film)
An organic thin film was prepared in the same manner as in Measurement Example 1 except that the high molecular compound 2 was used instead of the high molecular compound 1 and o-dichlorobenzene was used as the solvent, and the absorption spectrum of the organic thin film was measured. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, and 800 nm.

Example 2
(Production and evaluation of organic thin-film solar cells)
Fullerene derivative C60PCBM (Phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co., Ltd., trade name: E100), which is an electron-accepting compound, and polymer compound 1, which is an electron-donating compound, at a weight ratio of 3: 1. The mixture was dissolved in a mixed solvent of chloroform / o-dichlorobenzene = 95/5 (weight ratio) so that the concentration of the mixture was 2% by weight. The obtained solution was filtered through a Teflon (registered trademark) filter having a pore size of 1.0 μm to prepare a coating solution 1.

A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, a PEDOT: PSS solution (CleviosP VP AI4083 manufactured by HC Starck Co., Ltd.) is applied onto the ITO film by spin coating, and heated at 120 ° C. for 10 minutes in the atmosphere to thereby form a hole injection layer having a thickness of 50 nm. Was made. Next, the coating solution 1 was applied onto the hole injection layer by spin coating to obtain a functional layer of an organic thin film solar cell. The film thickness of the functional layer was 100 nm. Then, the organic thin film solar cell was produced by vapor-depositing calcium with a film thickness of 4 nm with a vacuum evaporation machine, and vapor-depositing aluminum with a film thickness of 100 nm. The degree of vacuum at the time of vapor deposition was 1 × 10 ^{−3 to} 9 × 10 ⁻³ Pa. The shape of the organic thin film solar cell thus obtained was a square of 2 mm × 2 mm. The obtained organic thin film solar cell is irradiated with a certain amount of light using a solar simulator (trade name: OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW / cm ² ), and the generated current and voltage are measured. did. The photoelectric conversion efficiency is 1.1%, Jsc (short circuit current density) is 3.54 mA / cm ² , Voc (open circuit voltage) is 0.77 V, and FF (fill factor) is 0.40. there were.

Claims (4)

The high molecular compound containing the repeating unit represented by Formula (1).

(1)
[Wherein, Q and R are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group which may be substituted with fluorine, an alkoxy group which may be substituted with fluorine, an aryl group which may be substituted, substituted Represents a heteroaryl group which may be substituted or a group represented by the formula (2). Two Qs may be the same or different. The 12 Rs may be the same or different.

(2)
(In the formula, m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R ′ represents an alkyl group which may be substituted with fluorine, an aryl group which may be substituted, or a substituted group. X ¹ and X ² are the same or different and represent —CH ₂ —, CHF— or —CF ₂ —, and when there are a plurality of X ¹ , they may be the same or different. And when there are a plurality of X ² , they may be the same or different.)]   An organic photoelectric conversion element comprising a pair of electrodes and a functional layer provided between the electrodes, wherein the functional layer includes an electron-accepting compound and the polymer compound according to claim 1.   The organic photoelectric conversion element according to claim 2, wherein the amount of the electron-accepting compound contained in the functional layer is 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound.   The organic photoelectric conversion device according to claim 2 or 3, wherein the electron-accepting compound is a fullerene derivative.

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