TW201229087A - Photoelectric conversion element - Google Patents

Abstract

This invention provides a high molecular compound comprising a repeating unit represented by formula (1) and a repeating unit represented by formula (2), having high optical density at long wave length, and useful in a photoelectric conversion element. [wherein, R represents hydrogen atom, fluorine atom, an alkyl optionally substituted by fluorine, an alkoxyl optionally substituted by fluorine, an optionally substituted aryl, an optionally substituted heteroaryl or a group represented by formula (3), and the four Rs may be the same or different, (wherein, m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6. R' represents an alkyl optionally substituted by fluorine, an optionally substituted aryl or an optionally substituted heteroaryl. The hydrogen atom in the formula represented by (CH2)m1 or (CH2)m2 may be substituted by fluorine]; [wherein, R represents the same meaning as above mentioned].

Description

201229087 • Description of the Invention: [Technical Field of the Invention] The present invention relates to a polymer compound and an organic photoelectric conversion element using the same. Organic Organics [Prior Art] Photoelectric conversion can be used for organic semiconductor materials such as organic solar cells and optical sensors. When a polymer compound == material is used, a functional layer can be produced by an inexpensive coating method. The characteristics of the electric conversion element are also discussed as an organic semiconductor material which can be used for various polymer compounds of the organic electroconversion element. At present, the existing proposals are, for example, a polymer compound in which 9,9_dioctyl-rich dioctyl ester and 5,5,,,--di-di- _3,,, 4,-dihexyl-de-== polymerized compound (10) Yunshi) as an organic semiconductor material. [Fa = Rongxi molecular compound is not sufficient for long-wavelength absorption. , hair: can provide long-wavelength light material with a large polymer compound.矣-二明 can provide a polymer compound containing a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2).

[In the formula, R represents a hydrogen atom, a fluorine κ; .^ ^ ^ # 齓 atom, an alkyl group which may be substituted by fluorine, an alkoxy group which may be substituted by fluorine, a substituted group, a substituted impurity Aryl or 323637 5 201229087 The group represented by formula (3).

—(CH2)—C-0—(CH2)1^—R Ο (3) (wherein ml represents an integer from 0 to 6, m2 represents an integer from 0 to 6. R' represents an alkane which may be substituted by fluorine. a aryl group which may be substituted or a heteroaryl group which may be substituted. The argon atom in the formula represented by (CH2)nn or (CH2)m2 may also be substituted by fluorine). The four Rs can be the same or different.

R

[wherein R represents the same as defined above]. Specific examples of the polymer compound include R as a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 20 carbon atoms which may be substituted by fluorine or The substituted phenyl group, wherein the substituent of the phenyl group is a _ element atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Meanwhile, the present invention can provide an organic photoelectric conversion element having a pair of electrodes and a functional layer provided between the electrodes, the functional layer containing an electron-accepting compound and the above-mentioned polymer compound. [Embodiment] Hereinafter, the present invention will be described in detail. The polymer compound of the present invention contains a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2). In the formula (1) and the formula (2), the alkyl group represented by R may, for example, be a chain or a ring of 323637 201229087 • an alkyl group such as a decyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a different group. Dingwu, second butyl, tert-butyl, pentyl, hexyl, octyl, isooctyl, decyl, dodecyl, pentadecyl, octadecyl. The hydrogen atom in the alkyl group may also be substituted by a fluorine atom. The alkyl group substituted with a fluorine atom may, for example, be a trimethyl sulfhydryl group, a penta-ethyl group, a perfluorobutyl group, an all-gas hexyl group or a perfluorooctyl group. In the formula (1) and the formula (2), the alkoxy group represented by R may, for example, be a chain or a cyclic alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or a butyl group. Oxyl, isobutoxy, second butoxy, tert-butoxy, pentyloxy, hexyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, oxime Base, decyloxy, 3,7-didecyloctyloxy. The hydrogen atom in the alkoxy group may also be substituted with a neofluoro atom. The alkoxy group substituted by a fluorine atom may, for example, be a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group or a perfluorooctyloxy group. In the formulae (1) and (2), the aryl group represented by R is an atomic group obtained by removing a hydrogen atom from an aromatic hydrocarbon. The aryl group includes a group containing a stupid ring, a group containing an aromatic condensed ring, a structure having two or more stupid rings or an aromatic condensed ring directly bonded, and having two or more benzene rings. The aryl group having an aromatic condensed ring bonded via a group such as a vinyl group preferably has a carbon number of from 6 to 60 and preferably from 6 to 30. Aryl, for example, phenyl, 1-naphthyl, 2-naphthyl. The aryl group may also have a substituent. The substituent which the aryl group may have is, for example, a halogen atom such as a fluorine atom, a carbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 2 carbon atoms. Examples of the heteroaryl group represented by 'R in the formula (1) and the formula (2) include a thiophene group, a material group, and a gnashing group. Heteroaryl also has 323637 7 201229087 which may have a substituent. The substituent which the heteroaryl group may have is, for example, a fluorinated atom such as a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. In the group represented by the formula (3), ml represents an integer of 〇 to 6, and m2 represents an integer of 0 to 6. R' represents an alkyl group which may be substituted by fluorine, a fluorene-substituted aryl group or a substituted heteroaryl group. R, a fluorine-substituted alkyl group, a substituted aryl group or a substituted heteroaryl group, and a specific example, which is a fluorine-substituted alkyl group and a substituted aromatic group represented by R The definition of a radical or a substituted heteroaryl group is the same as the specific example. The hydrogen atom in the formula represented by (CH2)n14(CH2)»2 may also be substituted by fluorine. That is, CH2 can also be replaced with a base represented by CHF or CF2. In the formulae (1) and (2), when R is an alkyl group or an alkoxy group, the carbon number of the alkyl group or the alkoxy group is preferably from 1 to 20 in terms of the solubility of the polymer compound in the solvent. 2 to 18 are preferred, and 3 to 12 are more preferred. The repeating unit represented by the formula (1) may, for example, be the following repeating unit.

The repeating unit represented by the formula (2) can be, for example, the following repeating unit. 8 323637 201229087

The photoelectric conversion efficiency of the organic photoelectric conversion element having the functional layer containing the polymer compound is a formula contained in the polymer compound of the present invention with respect to the total amount of the repeating units contained in the polymer compound ( The sum of the amount of the repeating unit represented by the formula (2) and the amount of the repeating unit represented by the formula (2) is preferably from 20 to 100 mol%, and preferably from 30 to 100 mol%. The amount of the repeating unit represented by the formula (1) contained in the polymer compound of the present invention is preferably from 10 to 50 mol%, and is from 15 to 50 mol, based on the total amount of the repeating units contained in the polymer compound. Ear % is preferred. The amount of the repeating unit represented by the formula (2) contained in the polymer compound of the present invention is preferably from 10 to 50 mol%, and is from 15 to 50 mol, based on the total amount of the repeating units contained in the polymer compound. Ear % is preferred. The polymer compound of the present invention may contain a repeating unit represented by the formula (1) or a repeating unit other than the repeating unit represented by the formula (2). The repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) include an extended aryl group and a heteroaryl group, and the repeating unit represented by the formula (1) and the formula (2) are not mentioned. Repeating units of heteroaryl groups and the like. As the aryl group, a phenylene group, a naphthyldiyl group, a fluorenyldiyl group, a pyridyldiyl group, a fluorenyldiyl group and the like can be given. The heteroaryl group may, for example, be a furanyl group, a pyrrole diyl group or a pyridyldiyl group. The heteroaryl group may have a substituent, and examples of the substituent include a γ atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. A preferred embodiment of the polymer compound of the present invention is a polymer compound containing a repeating unit represented by the formula (4).

(wherein R represents the same as the foregoing). The polymer compound of the present invention has a weight average molecular weight in terms of polystyrene, preferably from 1 3 to 108, preferably from 1 3 to 1 7 and more preferably from 1 3 to 106. The polymer compound of the present invention is preferably a conjugated polymer compound. Here, the conjugated polymer compound means a compound which constitutes a substantially common atom of the main chain of the polymer compound. The polymer compound of the present invention can 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 in accordance with the requirements, and an alkali or a catalyst is used. A well-known aryl coupling reaction such as a ligand can be polymerized and synthesized. The synthesis of the monomers described in the previous 10 323 637 201229087 can be carried out by referring to the method of ^ usp2 / 145571, Japanese Patent Laid-Open. In the polymerization of the square-based coupling reaction, for example, a polymerization using a Stilled reaction, a polymerization using an sU2uki coupling reaction, a polymerization using a Ya_to surface reaction, and a polymerization using an application-light reaction are used. The polymerization using Stille's reaction is the use of [tetrakis(triphenylphosphine)][一(""*benzylidene~)], acetic acid ίε, bis(triphenylphosphine) palladium II As a catalyst, a palladium complex such as a chloride is added as needed, and triphenylphosphine, tris(2-cytoylphenyl)phosphine, tris(2-methoxyphenyl)phosphine, diphenylscaledipropene, and trisole are added as required. After a ligand such as (cyclohexyl)phosphine or tris(t-butyl)phosphine, a monomer having an organotin residue and a monomer having a dentate atom such as a (iv), a meal, or a gas atom, or Wei 33 base, a monomer such as a benzoic acid vinegar group and the like. The details of the polymerization using the Stille reaction are described, for example, in Angewandte Chemie International Edition '2005, Vol. 44, pp. 4442 to 4489. The polymerization using the Suzuki coupling reaction is carried out by using a palladium complex or a nickel complex as a catalyst in the presence of an inorganic base or an organic base, and adding a ligand after the addition, to have a boronic acid residue or a boronic ester a monomer having a residue and a monomer having a bromine atom, an iodine atom, a gas atom or the like, or a monomer having a sulfonate group such as a trifluorosulfonate group or a p-toluenesulfonate group; The reaction is polymerized. The inorganic base may, for example, be sodium carbonate, potassium carbonate, carbonic acid planer, or phosphoric acid 323637 11 201229087 _, fluorinated unloading. The organic test may, for example, be tetrabutylammonium, vaporized tetrabutylammonium, tetrabutylammonium bromide or tetraethylammonium hydroxide. The palladium complex compound may, for example, be palladium [tetrakis(triphenylphosphine)], [tris(diphenylideneacetone)dipalladium, acetic acid, or bis(diphenylphosphine) dichloride. The nickel complex compound may, for example, be bis(cyclooctadiene)nickel. The ligand may, for example, be triphenylphosphine, tris(2-nonylphenyl)phosphine, bis(2-methoxyphenyl)phosphine, diphenylphosphinepropane, tris(cyclohexyl)phosphine, tri ( Third butyl) phosphine. The details of the polymerization using the Suzuki coupling reaction are described, for example, in Journal of Polymer Science: Part A: Polymer Chemistry, 2001, Vol. 39, pp. 1533 to 1556. The polymerization using the Yamamoto coupling reaction is a reaction between a monomer having a halogen atom or a monomer having a sulfonate group such as a trifluorosulfonate group or the like by using a catalyst and a reducing agent. The monomer having a halogen atom is polymerized by reacting with a monomer having a repeating acid group. The catalyst may be a catalyst formed of a ligand such as a nickel zero-valent complex such as bis(cyclooctadienyl)nickel and a dipyridine, or a [bis(diphenylphosphino)ethane]nickel dihydrate. And a nickel complex other than a nickel zero-valent complex such as [bis(diphenylphosphino)propane]nickel dihydride and triphenylphosphine, diphenylphosphonazo, and tris(cyclohexyl)phosphine a catalyst formed by a ligand such as tris(t-butyl)phosphine. The reducing agent may, for example, be zinc or magnesium. The polymerization using the Yamamoto coupling reaction may use a dehydrated solvent in the reaction, or may be carried out in an inert gas atmosphere, or a dehydrating agent may be added to the reaction system. The details of the polymerization using the Yamamoto coupling reaction are described, for example, in Macromolecules, 1992, Vol. 25, pages 1214 to 1223, 12 323637 201229087*. The polymerization using Kumada-Tamao is carried out by using a nickel catalyst such as [bis(diphenylphosphino)ethane]nickel dichloride or [bis(diphenylphosphino)propane]nickel dichloride to have a halogenation. The magnesium-based compound is polymerized by reacting with a compound having a || atom. This reaction may be carried out by using a dehydrated solvent in the reaction or in an inert gas atmosphere, or a dehydrating agent may be added to the reaction system. In the polymerization in which the aforementioned aryl coupling reaction is applied, a solvent can usually be used. The solvent is selected in consideration of the polymerization reaction to be used, the solubility of the monomer and the polymer, and the like. Specifically, 'tetrahydrofuran, toluene, 1> 4_dioxane, dimethoxyethane, N,N-dimethylacetamide, N,N-didecylguanamine, mixing, etc. An organic solvent such as a solvent of two or more kinds of solvents, and a two-phase solvent having an organic solvent phase and an aqueous phase. The solvent used in the Stilie coupling reaction is preferably subjected to deoxidation treatment before the reaction to suppress side reactions. The solvent used in the Suzuki stalk reaction is preferably tetrahydrogen]*ββ, 曱 benzene, 1 ββ 院, 曱 曱 炫 ι Ν, Ν, Ν--methylethyl amine, ν, II Methyl amide, an organic solvent such as a mixed solvent of two or more kinds of these solvents, and a solvent having a two phase of an organic solvent phase and an aqueous phase. The solvent used in the Suzuki coupling reaction is preferably subjected to deoxidation treatment before the reaction to suppress side reactions. The solvent used in the coupling reaction of Yamam〇1;0 is preferably tetrahydrofuran, indene, hydrazine, 4-di. An organic solvent such as a cacao, a dimethoxyethane, an N,N-methyletheneamine, an n,n-diindenylamine, or a mixed solvent of two or more of these solvents, and an organic solvent phase A solvent for the aqueous phase. The solvent used in the Suzuki light-bonding reaction is preferably subjected to a deoxidation treatment before the reaction to suppress side reactions. 323637 13 201229087 In the polymerization of the aryl coupling reaction, from the viewpoint of reactivity, it is preferred that the polymerization method using the Stille coupling reaction, the polymerization method using the Suzuki synthesis reaction, and the polymerization method using the Yamamoto coupling reaction are preferred. The polymerization method using a Stille coupling reaction polymerization method, a Suzuki synthesis reaction method, and a Yamam〇t〇 coupling reaction using a nickel zero-valent complex is preferred. From the viewpoint of reactivity, the lower limit of the reaction temperature of the above-mentioned aryl coupling reaction is preferably -1 Torr (TC, preferably -2 〇 °c, and particularly preferably. The stability of the monomer and the polymer compound) From the viewpoint of the reaction temperature, the upper limit of the reaction temperature is preferably 200 C, and is preferably i5 〇 °c, and more preferably i2 〇 °c. In the polymerization using the aforementioned aryl coupling reaction, the reaction is terminated by the reaction/valley. The method of taking out the polymer compound of the present invention in the liquid is a well-known method. For example, the reaction solution is added to a lower alcohol such as methanol, the precipitate precipitated is filtered, and the filtrate is dried to obtain the present invention. When the purity of the obtained polymer compound is low, recrystallization, Soxhlet extractor continuous extraction, column chromatography, etc. can be used. The polymer compound of the present invention is used for organic photoelectric conversion. In the production of the element, when the polymerizable active group remains at the terminal of the polymer compound, the properties such as durability of the organic photoelectric conversion device are lowered, so that it is preferable to protect the terminal of the southern molecular compound with a stable group. The stabilizing group at the end of the protective layer may, for example, be an alkyl group, an alkoxy group, a fluorinated alkyl group, a fluorinated alkoxy group, an aryl group, an arylamino group or a fluorene-containing heterocyclic group. A heterocyclic amino group, a diphenylamino group, etc., and a heterocyclic ring of 323637 14 201229087, which may be exemplified by a porphinyl group, a ρ ratio group, a fluorenyl group, a σ ratio bite group, a fluorene group, or a different group. At the same time, the polymerization active group remaining at the terminal of the polymer compound may be substituted with an argon atom instead of the stabilizer. From the viewpoint of improving the transportability of the hole, the stability of the protective terminal is preferably an arylamine group. When the polymer compound is a total of a polymer compound, it is preferred to use a conjugated structure having a main chain of a polymer compound and a conjugated structure of a terminal which protects the terminal to become a total The group to which the yoke bond is bonded serves as a stabilizer for protecting the terminal. Examples of the group include an aryl group and an aromatic monovalent heterocyclic group. When a polymer compound of the present invention is produced by Stille coupling reaction, for example, The compound represented by the formula (5) is represented by the formula (6) Polymerizable compound, the polymer compound of the present invention can be manufactured.

(wherein R represents the same as the above. Z represents a bromine atom, an iodine atom or a chlorine atom. The two Z's may be the same or different).

(In the formula, R represents the same as the above. Z2 represents an organotin residue. Two Z2 may be the same or different). 15 323637 201229087 The compound represented by the formula (5) is exemplified by the following compounds.

From the viewpoint of improving the polymerization reactivity using Stille coupling, Z in the formula (5) is preferably a bromine atom or a chlorine atom, and more preferably a bromine atom. The compound represented by the formula (5) can be synthesized by, for example, the method described in Macromolecules, 2009, 16 323 637 201229087 • Volume 42, No. 17, pp. 6564 to 6571. The compound represented by the formula (6) may, for example, be the following compound.

17 323637 K; 201229087 (wherein Bu represents CH3(CH2)3 base). From the viewpoint of the ease of synthesis of the compound represented by the formula (6), Z2 in the formula (6) is preferably -SnMe3, -SnEt3 or -SnBu3. Here, Me3 represents a CH3 group, Ets represents a CH3CH2 group, and Bu3 represents a CH3(CH2)3 group. The production of the compound represented by the formula (6) can be carried out, for example, by reacting a compound represented by the formula (7) with an organolithium compound to prepare an intermediate, and then reacting the intermediate with a trialkyltin halide.

(wherein R represents the same as the foregoing). The organolithium compound may, for example, be butyllithium (n-BuLi), second butyl (sec-BuLi), tert-butyl (tert-BuLi) or lithium diisopropylamide. Among the organolithium compounds, n-butyllithium is preferred. As the trialkyltin halide, for example, trimethylsulfide tin, triethyltin chloride, or tributyltin oxide can be mentioned. The reaction of the compound represented by the formula (7) with an intermediate of the organolithium compound production and the reaction of the intermediate with the trialkyltin halide to produce the compound represented by the formula (6) are usually carried out in a solvent. As the solvent, it is preferred to use a sufficiently dehydrated tetrahydrofuran, a sufficiently dehydrated 1,4-dioxane, and a fully dehydrated dick. The temperature at which the organolithium compound is reacted with the compound represented by the formula (7) is usually -100 to 50 °C, and preferably -80 to 0 °C. The time during which the organolithium compound reacts with the compound represented by the formula (7) of 18 323 637 201229087 is usually from 1 minute to 10 hours, and preferably from 30 minutes to 5 hours. The amount of the organolithium compound to be reacted is usually 2 to 5 equivalents, and preferably 2 to 3 equivalents, based on the compound represented by the formula (7). The temperature at which the intermediate is reacted with trialkyltin, usually from -loo to loot, and preferably from -8 to 5 (rc. The reaction time of the aforementioned intermediate with the trialkyltin halide is usually 1 minute to 30 hours, and preferably i to 10 hours. The amount of the trialkyltin halide in the reaction is usually 2 to 6 equivalents, and preferably 2 to 3 equivalents based on the compound represented by the formula (7). After the reaction, a general post-treatment is carried out to obtain a compound represented by the formula (6). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. For purification, a method of preparing or recrystallizing by a chromatograph or the like can be carried out. The production of the compound represented by the formula (?) can be obtained, for example, by reacting a compound represented by the formula (8) in the presence of an acid.

HO R

(8) (wherein R represents the same as the above). The acid used in the reaction of the compound represented by the formula (7) to produce a compound represented by the formula (7), for example, Lewis acid, Bronsted Acid (Bronstedacid), hydrochloric acid, acid, fluoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid, boron fluoride, aluminum chloride, gasification 19 323637 201229087 tin (IV), chlorination Iron (II), titanium tetra-titanate, phthalic acid, p-toluic acid and mixtures of such compounds. The reaction of the compound represented by the formula (7) to produce a compound represented by the formula (7) is preferably carried out in the presence of a solvent. When the reaction is carried out in the presence of a solvent, the temperature of the reaction is preferably a temperature below -8 ° C above the boiling point of the solvent. Examples of the solvent used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane, and unsaturated hydrocarbons such as stupid, toluene, ethylbenzene, and diphenylbenzene. Chloroform, dioxane, gas butane, bromobutane, gas bromide, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, gas stupid, dichloro stupid, trichloro Toothed hydrocarbons such as benzene, alcohols such as decyl alcohol, ethanol, 1-propanol, propanol, butanol, and butanol, carboxylic acids such as formic acid, acetic acid, and propionic acid, dimethyl ether, diethyl ether, and thiol. An ether such as tributyl ether, tetrahydrofuran, tetrahydropyran or dioxane. The solvent may be used singly or in combination. After the reaction, a general post treatment is carried out to obtain a compound represented by the formula (7). For example, after the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off. The separation and purification of the product can be carried out by a method of preparation or recrystallization by a chromatograph. The production of the compound represented by the formula (8) can be obtained, for example, by reacting a compound represented by the formula (9) with a Grignard reagent or an organolithium compound.

323637

20 (9) 201229087 As for the Glina reagent used in the above reaction, thiol-magnesium, mercapto-magnesium bromide, ethylmagnesium chloride, ethyl-alcohol, propyl chloride: propyl propyl Magnesium oxide, butyl gasification town, butyl magnesium oxide, hexyl desertification town, octyl desertification magnesium, sulfhydryl desertification town, propyl propyl magnesium hydride, propyl propyl magnesium, benzene曱 base gas butterfly, stupid bromine, naphthalene magnesium, phenyl phenyl desertification and so on. The organic clock compound may, for example, be a f-base clock, an ethyl group, a propyl group, a butyl group, a stupid wire, a phenyl group chain, or a benzene m f stupid chain. The reaction of the compound represented by the formula (9) with the Grignard reagent or the organolithium compound to produce the compound represented by the formula (8) is preferably carried out in an inert gas atmosphere such as nitrogen or argon. The reaction is preferably carried out in the presence of a solvent. When the reaction is carried out in the presence of a solvent, the reaction temperature of the reaction is preferably a temperature not higher than the boiling point of the solvent of 8% or more. Examples of the solvent used in the reaction include saturated hydrocarbons such as pentyl alcohol, hexane, heptane, octane, and cyclohexane; and unsaturated hydrocarbons such as benzene, toluene, ethyl benzene, and xylene; diterpene ether and diethyl ether. An ether such as methyl-tert-butyl ether, tetrahydrofuran, tetrahydropyrene or dioxane. The solvent may be used singly or in combination. After the reaction, a general post-treatment is carried out to obtain a compound represented by the formula (8). For example, after adding water to stop the reaction, the product is extracted with an organic solvent, and the solvent is post-treated. A method of preparing or recrystallizing by a layerer can be carried out by the formation and refining of the substance. The production of the compound represented by the formula (9) can be obtained, for example, by reacting a compound represented by the formula (1) with a peroxide. 323637 21 201229087

The peroxide may, for example, be sodium perborate, m-benzoic acid, hydrogen peroxide, orthoformyl peroxide, etc., and is preferably sodium perborate or m-benzoic acid. Sodium borate is especially preferred. The reaction of the compound represented by the formula (10) with the peroxide to produce the compound represented by the formula (9) is preferably carried out in the presence of a carboxylic acid solvent such as acetic acid, trifluoroacetic acid, propionic acid or butyric acid. In order to increase the solubility of the compound represented by the formula (10), it is preferred to mix one or more solvents selected from the group consisting of tetra-gasified carbon, chloroform, dichlorosilane, benzene, and fluorene in a carboxylic acid solvent. The reaction is carried out in a mixed solvent. The reaction temperature of the reaction is preferably hydrazine. (3 or more than 50 ° C. After the reaction, a general post-treatment is carried out to obtain a compound represented by the formula (9). For example, after adding water to stop the reaction, the product is extracted with an organic solvent and the solvent is distilled off. The method of preparing or recrystallizing the product can be carried out by separating and purifying the product. The polymer compound of the present invention can improve the absorbance of light length/skin length light of 6 〇〇 nm. Since the solar light can be effectively absorbed, the short-circuit current density of the organic photoelectric conversion element produced by using the polymer compound of the present invention can be increased. The organic photoelectric conversion device of the present invention has a pair of electrodes and a functional layer provided between the electrodes, The functional layer contains an electron-accepting compound and a polymer compound 323637 22 201229087 comprising a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2). Specific examples of the organic photoelectric conversion element include 1. An organic photoelectric conversion element for a functional layer between the electrode and the electrode, 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 functional layer between a pair of electrodes and an electrode, the functional layer containing an electron accepting compound and a polymer compound containing a repeating unit represented by the formula (1), the electron accepting compound being An organic photoelectric conversion device of a fullerene derivative, wherein at least one of the counter electrodes is usually transparent or translucent, and an example of the above-described organic photoelectric conversion device includes an electron-accepting compound and In the functional layer of the polymer compound, the amount of the electron-accepting compound is preferably 10 to 1,000 parts by weight, and preferably 20 to 500 parts by weight, based on 100 parts by weight of the polymer compound. In the organic photoelectric conversion device according to the above aspect, in the functional layer containing the fullerene derivative and the polymer compound, the amount of the fullerene derivative is preferably 10 to 1 based on 100 parts by weight of the polymer compound. 10,000 parts by weight, and preferably 20 to 500 parts by weight. The amount of the fullerene derivative in the functional layer from the viewpoint of improving photoelectric conversion efficiency It is preferably 20 to 400 parts by weight, and preferably 40 to 250 parts by weight, more preferably 80 to 120 parts by weight, based on 100 parts by weight of the above polymer compound. The functional layer is improved from the viewpoint of increasing the short-circuit current density. The amount of the fullerene derivative is preferably 20 to 250 parts by weight, and preferably 40 to 120 parts by weight, based on 100 parts by weight of the polymer compound. In order to impart high photoelectric conversion efficiency to the organic photoelectric conversion element. , package 23 323637 201229087 The polymer compound containing the above electron accepting compound and the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) must have an absorption capable of efficiently absorbing the spectrum of the desired incident light. Domain, and in order to effectively separate the excitons, the heterojunction interface must contain multiple heterojunction interfaces, and the heterojunction interface must have charge transport properties that can rapidly transport the generated charges to the electrodes. In view of the above, the organic photoelectric conversion element is preferably the organic photoelectric conversion element of the above-mentioned 1. The organic photoelectric conversion element of the above-mentioned 2. The organic photoelectric conversion element of the above 2. Meanwhile, in the organic photoelectric conversion device of the present invention, an additional layer may be provided between at least one of the electrodes and the functional layer in the element. As the additional layer, a charge transport layer, a buffer layer, and the like which transport holes or electrons can be cited. The organic photoelectric conversion device of the present invention is usually formed on a substrate. The substrate may have no chemical change when the organic layer is formed after the electrode is formed. The material of the substrate may, for example, be glass, plastic, high molecular weight film or germanium. In the case of an opaque substrate, it is preferred that the other electrode, that is, the electrode farther from the substrate, be transparent or opaque. As the material of 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 small work function. For example, it is possible to use metals such as Li, Na, K, Y, I, M, M, M, 钡, I, 铳, Xun, Zinc, Ji, Indium, Jin, 钐, 铕, 铽, 镱, etc. An alloy of two or more metals in a metal, or an alloy of one or more metals of the metals and one or more metals selected from the group consisting of gold, silver, platinum, copper, lanthanum, titanium, Ming, Lu, He, and tin. Graphite, graphite intercalation compounds, and the like. As for the alloy example, 24 323637 201229087 may include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, etc. . The material of the transparent or translucent electrode may be a conductive metal oxide film or a translucent metal film. Specifically, a film made of a conductive material formed of indium/tin/oxide (ΙΤ0), indium/zinc/oxide, or the like of a composite of indium oxide, zinc oxide, tin oxide, or the like may be used. NESA, gold, platinum, silver, copper, and should be ιτο, indium / zinc / oxide, tin oxide. Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, and a key method. Meanwhile, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof can also be used as the electrode material. As the charge transporting layer of the additional layer, that is, the material for the hole transporting layer or the electron transporting layer, an electron-donating compound or an electron-accepting compound to be described later can be used. As the material used for the buffer layer of the additional layer, an alkali metal or an alkaline earth metal halide or oxide such as lithium fluoride can be used. At the same time, fine particles of an inorganic semiconductor such as titanium oxide can also be used. In the functional layer in the organic photoelectric conversion device of the present invention, for example, an organic film containing the polymer compound of the present invention and an electron-accepting compound can be used. The film thickness of the above organic thin film is usually from 1 nm to 100 #m, preferably from 2 nm to 1 Å, and preferably from 5 nm to 500 nm, more preferably from 20 nm to 200 nm. The organic film may contain one kind of the above-mentioned polymer compound alone, and 25 323637 201229087 may contain a combination of two or more kinds. Meanwhile, in order to improve the hole transportability of the organic thin film, a low molecular compound and/or a polymer compound other than the polymer compound may be used as the electron donating compound in the organic thin film. In addition to the polymer compound containing the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), the electron-donating compound which the organic film may contain may, for example, be a β-pyroline derivative or an arylamine. Derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophenes and derivatives thereof, polyvinyl carbazole and its derivatives, polydecane and its derivatives, side chains or main chains having aromatic amines Polyoxane derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, poly(extended benzene) ethylene and its derivatives, poly-stretching ethylene and its derivatives . As the electron accepting compound, for example, an oxadiazole derivative, anthracene dioxane and a derivative thereof, benzoquinone and a derivative thereof, naphthoquinone and a derivative thereof, an anthracene and a derivative thereof, and a tetracyano group may be mentioned. Dioxane and its derivatives, 苐_derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone quinone and its derivatives, 8-meridene and its derivatives The metal complex of the substance, the polyphthalocyanine and its derivatives, polyphosphonium and its derivatives, polyfluorene and its derivatives, C6. Fullerene and its derivatives, carbon nanotubes, phenanthrene derivatives such as 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthrene, and preferably fullerenes and their derivatives . The electron-donating compound and the electron-accepting compound are determined by the relative order of the energy levels of the compounds. Examples of fullerenes and derivatives thereof include C60, C70, C84 and derivatives thereof. 26 323637 201229087 Tianleene organism, representing at least a portion of a modified compound of fullerene. The olefin derivative may, for example, be a compound represented by the formula, a compound represented by the formula (11), a compound represented by the formula (IH), or a compound represented by the formula (IV).

(In the formulae (1) to (IV), 'R is a group having a decyl group, an aryl group, a heteroaryl group or a vinegar structure. When there are several Ra's, they may be the same or different. Rb represents an alkyl group or an aryl group. There are several ^, which can be the same or different.

The definitions and specific examples of the alkyl group, the aryl group and the heteroaryl group represented by Rb are the same as the definitions and specific examples of the alkyl group, the aryl group and the heteroaryl group represented by R. The group having an ester structure represented by 1^ may, for example, be a group represented by the formula (v).

~(CH2>^r~i-°-(CH2)^-RC ° (V) (wherein ul represents an integer from 1 to 6, and u2 represents an integer from 0 to 60. Expanding means alkyl, aryl or hetero Aryl).

The definitions and specific examples of the alkyl group, the aryl group or the heteroaryl group represented by Re are the same as the definitions and specific examples of the alkyl group, the aryl group and the heteroaryl group represented by r. Specific examples of the derivative of Go include the following structural formulas. 323637 27 201229087

28 323637 201229087 • Specific examples of the derivatives of C?G include the following structural formulas.

The above organic thin film can be produced by any method, for example, by a method of forming a film containing a polymer compound of the present invention, or by an organic thin film by vacuum evaporation. A method for producing an organic thin film from a solution film formation is, for example, a method in which the solution is applied to one side of an electrode, and then the solvent is evaporated to produce an organic thin film. The solvent used in the film formation from the solution is not particularly limited as long as it can dissolve the polymer compound of the present invention. The solvent may, for example, be benzene, dimethyl, mesitylene, tetrahydronaphthalene, decahydronaphthalene, bicyclohexanthene, butane: an unsaturated hydrocarbon such as benzene, carbon tetrachloride, gas, and nitrogen (tetra) Ether, gas, sulphur, sulphur, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, stupid (four), tetrahydrogen, tetrahydrogen (tetra) and other ethers. Ben: Molecular compound, usually dissolved in the above solvent, 01% by weight or more, from solution to 'can be used by spin coating method, binding pressure:: micro-cavity coating method, concave sheet method, secret coating method, dip = (4), front coating method, offset printing, mouth ink printing method, dispensing squeegee method, nozzle coating method, capillary coating method, etc., and transfer coating method, flexographic coating method, inkjet printing method and I-aligner The printing method is Jia Gray 323637 29 201229087 The organic photoelectric conversion element is formed by a transparent or translucent electrode by irradiating light such as sunlight to generate a photoelectromotive force between the electrodes, thereby functioning as an organic thin film solar cell. Several organic thin film solar cells can also be assembled for use as an organic thin film solar cell module. At the same time, in the state where a voltage is applied between the electrodes, the transparent or translucent electrode illuminates the light to cause the photocurrent to flow, thereby functioning as an organic photosensor. It is also possible to use several organic photo sensors as an organic image sensor. (Embodiment) Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the scope of the embodiments. The weight average molecular weight of the polymer compound in terms of polystyrene is determined by size exclusion chromatography 'SEC. Separation column: TOSOH TSKgel SuperHM-H (2 pieces) + TSKgel SuperH2000 (4. 6mml.d.xl5cm); detector: RI (SHIMADZU RID-10A); mobile phase: tetrahydro α-methane reference example 1 (compound 1 synthesis)

In a four-necked flask of 1000 mL of argon gas, the gas in the flask was replaced with 3- Desert Benzene 13. 0 g (80·Ommol), and the second test was 80 mL, and 30 323637 201229087

Become a homogeneous solution. The solution was maintained at -78. To the solution, a 2.6 M solution of butyllithium (n-BuLi) in hexane (31 mL) was obtained. After reacting at -781 for 2 hours, a solution of 8.96 g of 3-thiophenaldehyde (80·Ommol) dissolved in 20 mL of diethyl ether was added dropwise to the reaction mixture. After the dropwise addition, the reaction solution was stirred at -78 ° C for 30 minutes and then stirred at room temperature (25 ° C) for 30 minutes. After the reaction mixture was cooled to -78 ° C, a hexane solution of 2.6 M n-butyllithium (yield: 62 mL, 161 mmol) was added dropwise over 15 minutes. After the dropwise addition, the reaction solution was stirred at -25 ° C for 2 hours, and then stirred at room temperature (25 ° C. for 1 hour. Then, after cooling the reaction solution to -25 ° C, it was dropped into 60 g in 30 minutes). Iodine (236 mmol) was dissolved in a solution of 100 mL of diethyl ether. After the dropwise addition, the reaction mixture was stirred at room temperature (25 ° C) for 2 hours, then 5 N mL of 1N aqueous sodium thiosulfate solution was added to stop the reaction. After adding diethyl ether and extracting the reaction product, the organic layer containing the reaction product was dried over magnesium sulfate, and concentrated to obtain 35 g of a crude product. The crude product was recrystallized and purified by chloroform to obtain 28 g of a compound. 1. Reference Example 2 (Synthesis of Compound 2)

In a 300 mL four-necked flask, 10 g (22.3 mmol) of diiodothiophene sterol (Compound 1) and 150 mL of dioxane were placed, and a homogeneous solution was obtained. To the solution, 7.50 g (34.8 mmol) of pyridine chromic acid chrome rust was added, and the mixture was stirred at room temperature (25 ° C) for 10 hours. The reaction solution was filtered to remove the insoluble material, 31 323637 201229087, and the filtrate was concentrated to give Compound 2 (12.4 mmol). Reference Example 3 (Synthesis of Compound 3)

In the 300 mL flask in which the gas in the flask has been replaced with argon, '1. 0 g (22.3 〇1) of the compound 2, copper powder 6. 〇S (94. 5 mmol), dehydrated N, N-di The base amine 120 mL' was stirred at 120 ° C for 4 hours. After the reaction, the flask was cooled to room temperature (25 ° C), and the reaction liquid was passed through a cartridge column to remove insoluble components. Then, 50 mL of water was added to the reaction mixture, and then gas imitation was added to extract an organic layer containing the reaction product. The organic layer was dried over magnesium sulfate and concentrated to give a crude material. The compound 3 was obtained in an amount of 3.26 g, after purification by a ruthenium tube. Reference Example 4 (Synthesis of Compound 4)

In a 300 mL four-necked flask equipped with a mechanical stirrer and the gas in the flask was replaced with argon, 3.85 g (20.0 mmol) of compound 3, 50 mL of gas, and 5 mL of trifluoroacetic acid were added, and uniformed. The solution. To the solution was added 5.99 g (60 mm 〇1) of sodium perborate sodium hydrate, and the mixture was stirred at room temperature (25 ° C) for 45 minutes. Then, 2 mL of water, 32 323637 201229087, and chloroform were added to the reaction mixture, and the reaction product was extracted. After passing the organic layer containing the reaction product through the ruthenium tube column, the solvent was removed by an evaporator. The residue was recrystallized from decyl alcohol to give 534 mg of Compound 4. 1 H NMR in CDC|3 (PPm): 7.64 (d, 1H), 7.4 3 (d, 1H), 7·27 (d, 1H), 7·1〇 (d% 1H) Reference Example 5 (Compound 5 Synthesis)

The gas in the flask was replaced with a x1 mL four-necked flask, and 1.00 g (4.80 mmol) of Compound 4 and 30 mL of dry tetrahydrofuran were added to make a homogeneous solution. 7毫升。 The flask was held at a temperature of -2 ° C, while adding 1 M 3,7-dimethyloctylmagnesium bromide ether solution 丨 2. 7mL. The temperature of the mixture was raised to -5 ° C over 30 minutes and stirred at -5 ° C for 30 minutes. 5小时。 Then, the temperature was raised to 〇 ° C in 10 minutes, 〇 t: stirring 1. 5 hours. Then, water was added to the reaction solution to stop the reaction, and then ethyl acetate was further added to extract the reaction product. The organic layer containing the reaction product was dried over sodium sulfate, passed through a silica gel column, and the solvent was evaporated to give 1.5 g of compound 5. 1H NMR in CDCl3 (ppm): 8.42 (b% 1H), 7.25 (d' 1H), 7.20 (d, 1H), 6_99 (d, 1H), 6.76 (d, 1H ), 2. 73 (b, 1H), 1.90 (m, 4H), 1. 58-1. 0 2 (b, 20H), 〇· 9 2 (s, 6H), 0. 88 (s' 12H) 33 323637 201229087 Reference Example 6 (Synthesis of Compound 6)

In a 200 mL flask in which the gas in the flask was replaced with argon, 1.50 g of Compound 5 and 30 mL of toluene were added to make a homogeneous solution. 5小时。 The solution was added to the p-toluene sulphate monohydrate l 〇〇 mg, and the mixture was stirred at l ° ° C for 1.5 hours. The reaction solution was cooled to room temperature (25 ° C), 50 mL of water was added, and toluene was added, and the reaction product was extracted. The organic layer containing the reaction product was dried over sodium sulfate, and the solvent was evaporated. The crude product obtained by the purification of the ruthenium colloidal column using hexane as a developing solvent gave 1.33 g of the compound 6. Do this several times. 'H NMR in CDC 丨3 (ppm) : 6 9 8 (d,, (1) 6 μ (d' 1Η)' 6· 68 (d. 1Η). 6. 59 (d. 1H). K 89 (m 4H ), L 58".00 (b, 2〇H), 〇87 (s' a), 〇8 6 (s, 1 2 H ) Reference Example 7 (synthesis of compound 7) 323637 34 201229087

In a 200 mL flask in which the gas in the flask was replaced with argon, 2·16 g (4.55 mmol) of Compound 6 and 100 mL of dry tetrahydrofuran were added, and a homogeneous solution was obtained. The solution was kept at -78 ° C, and 4.37 mL (ll. 4 mmol) of a 2.6 M n-butyl quinone solution was added dropwise to the solution over 10 minutes. After the dropwise addition, the reaction solution was stirred at -78 °C for 30 minutes, and then stirred at room temperature (25 ° C) for 2 hours. Then, the flask was cooled to -783⁄4, and dibutylphosphonium chloride 4. 7 g (1.25 mmol) was added to the reaction mixture. After the addition, the reaction solution was stirred at -78 C for 30 minutes, followed by stirring at room temperature (25 ° C) for 3 hours. Then, 200 mL of water was added to the reaction solution to stop the reaction, and ethyl acetate was added to extract the reaction product. The organic layer containing the reaction product was dried over sodium sulfate, and the solvent was distilled off with an evaporator. An oily substance obtained by purifying 0 was obtained from a silica gel column using hexane as a developing solvent. The broken rubber column (4) glue is a Shishi gum which has been previously immersed in a immersion bath containing 5 wt% of triethylamine for 5 minutes. After purification, 3.52 g (3.34 mmol) of Compound 7 was obtained. Example 1 (Synthesis of Polymer Compound 1) 323637 35 201229087

In a 100 mL flask in which the gas in the flask was replaced with argon, 198.9 mg (0. 189 mmol) of the compound 7, 90 mg (0. 182 mmol) of the compound 8 (manufactured by Luminescence Technology Corporation), and 14 mL of a solution were added. And make it a homogeneous solution. The resulting toluene solution was bubbled with argon for 30 minutes. Then, the benzene solution was added to a solution of bis (diphenylene propyl)-palladium 2. 59 mg (0·00283 mmol) and tris(2-indolylphenyl) phosphine 5. 2 mg (0.017 mmol) at 100 ° C. Stir for 6 hours. Then, 271 mg of brominated benzene was added to the reaction mixture, and the mixture was further stirred for 5 hours. Then, after cooling the flask to 25 ° C, the reaction solution was poured into 300 mL of methanol. After the precipitated polymer was filtered, the obtained polymer was placed in a cylindrical filter paper, and each was extracted with decyl alcohol, propylene ketone, and hexazone for 5 hours using a Soxhlet extractor. The polymer remaining in the cylindrical filter paper was dissolved in 100 mL of o-dichlorobenzene, and 2 g of sodium diethyldithiocarbamate and 40 mL of water were added, followed by mixing under reflux for 8 hours. After removing the water layer, the organic layer was washed twice with 50 mL of water, followed by washing twice with 50 mL of a 3 wt% aqueous acetic acid solution, followed by washing twice with 50 mL of water, followed by washing twice with 50 mL of a 5% potassium fluoride solution, followed by washing twice. After washing twice with 5 mL of water, the resulting solution was poured into decyl alcohol to precipitate a polymer. After filtering and drying the polymer, the obtained polymer is dissolved in the hidden-second gas stupid 323637

36 201229087 In 50mL, pass it through the alumina/tantalum tube column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain a purified polymer compound 72 Å. Hereinafter, this polymer is referred to as polymer compound 1. Reference Example 8 (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 the compound (E), 13. 〇〇g (17.60 mmol) of the compound (F), trioctane was added. Acryl ammonium chloride (trade name: Anquat 336 (registered trademark)' Sigma Aldrich, CH3N[(CH2)7CH3]3C1, density 0. 884g/mL '25°C) 4. 979g and toluene 405mL, while stirring Argon gas was bubbled in the reaction system for 30 minutes. Dioxane bis(triphenylphosphine)palladium(11)〇.〇2 was added to the flask to lighten the temperature to 1 〇5. (: After that, a 2 mol/L sodium carbonate aqueous solution 42. 2 mL was added while stirring, and after the dropwise addition, the reaction was allowed to proceed for 5 hours, and then 2.6 g of phenylboric acid and 1.8 mL of toluene were added, followed by stirring at 105 ° C. Then, 2〇〇mL of anthraquinone 7〇〇raL and 7.5 wt% of sodium diethyldithiocarbamate trihydrate aqueous solution were added to the reaction solution, and the mixture was shaken at 8 5 C for 3 hours. After removing the aqueous layer of the reaction liquid, the organic layer was washed twice with 300 mL of ion-exchanged water at 6 ° C, and once with 300 mL of 3% by weight of 300 mL of acetic acid, and washed three times with 300 mL of ion-exchanged water at 60 ° C. The organic layer is passed through a column of 323637 37 201229087 which has been filled with celite, alumina and oxidized stone, to obtain an eluate. Then, the column is cleaned with hot toluene, and the washed toluene solution and dissolution are performed. The liquids were combined. After the resulting solution was concentrated to 700 mL, the concentrated solution was added to 2 L of methanol to reprecipitate the polymer. After the polymer was passed through, 'then, 5 liters of methanol, 5 liters of acetone, 5 GGmL The methanol is washed sequentially in the polymer. The polymer is dried in 5 vacuums - late after the 'available x 嗔 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The polymer compound 1 was dissolved in o-dichlorobenzene at a concentration of 0.5% by weight to prepare a coating solution, and the obtained coating liquid was applied to a glass substrate by a spin coating method. The coating operation was 23 <> Then, the organic film of the organic film was measured by a spectrophotometer (manufactured by JASCO Corporation, trade name, V~67〇), and the film was baked for 5 minutes under the conditions of 120 Torr. The measured spectrum is as shown in Figure 1. The absorbance at 600 nm and 650 nm is shown in Table 1. 匕 Comparative Example 1 (Measurement of absorbance of organic film) In addition to the use of polymer compound 2 in place of polymer compound The same operation as in the measurement example 1 was carried out, and the absorption spectrum of the far-end enthalpy was measured after the organic film was produced. The measured spectrum is shown in Fig. 2. Table 1 shows the absorbance at 600 nm and 650 nm. 3 8 201229087 * [Table 1] Absorbance of polymer compound 600 nm 吸 absorbance at 650 nm Example 1 Polymer compound 1 0. 54 0.38 Comparative Example 1 Polymer compound 2 0. 09 0.07 Example 2 (Production of organic thin film solar cell) And evaluation)

A fullerene derivative C60PCBM (phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co., Ltd., trade name: E-100) as an electron-accepting compound and an electron-donating compound The polymer compound 1 was mixed in o-diphenylbenzene in a weight ratio of 3:1 to make the concentration of the mixture 2% by weight. The obtained solution was filtered through a Teflon (registered trademark) filter having a pore size of 1. Oym to prepare a coating solution 1. A glass substrate with a ruthenium film formed by applying a sputtering method at a thickness of 105 nm was subjected to ozone UV treatment for surface treatment. Next, a PED0T:PSS solution (CleviosP VP AI4083, manufactured by HC Starck Co., Ltd.) was applied to the ΙΤ0 film by a spin coating method, and 12 (the TC was heated for 10 minutes, and then a hole injection layer having a film thickness of 50 nm was formed. The coating layer 1 is applied to the ΙΤ0 film by a spin coating method to obtain a functional layer of the organic thin film solar cell. The thickness of the functional layer is 1 〇〇 nm. Then, a vacuum coating machine is used to deposit a film having a thickness of 4 nm, followed by evaporation. After depositing aluminum having a thickness of 1 〇〇 nm, an organic thin film solar cell is produced. The total vacuum degree at the time of vapor deposition is i to 9 χ l 〇 -3 Pa. The shape of the organic thin film solar cell thus obtained is a square of 2 mm x 2 mm. The obtained organic thin film solar cell was irradiated with a certain amount of light by a solar simulator (manufactured by a spectrometer, trade name 39 323637 201229087 0TENT0-SUNII: AM 1.5G filter, illuminance: 100 mW/cm 2 ). The measured current and voltage were measured. The photoelectric conversion efficiency was 2.3%, and the Jsc (short-circuit current density) was 6. 7 mA/cm2 'V〇c (open-end voltage) was 0.80 ¥'? , 11€&(:1:〇1') is 〇.44. (Probability of industrial application) The polymer preparation of the present invention can be used because of its large absorbance of long-wavelength light. Organic photoelectric conversion element [Simplified description of the drawing] Fig. 1 is a view showing the absorption spectrum of the polymer compound 1. Fig. 2 is a view showing the absorption spectrum of the polymer compound 2. [Explanation of main component symbols] No 323637

40

Claims (1)

201229087 VII. Patent Application Range: 1. A polymer compound comprising a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2). Wherein R represents an argon atom, a fluorine atom, an alkyl group which may be substituted by fluorine, an alkoxy group which may be substituted by fluorine, a substituted aryl group, a substituted heteroaryl group or a formula (3) Base, 4 R's may be the same or different] -(CH2)m^~R 〇(3) (wherein ml represents an integer from 0 to 6, m2 represents an integer from 0 to 6, and R' represents a fluorine-substituted alkyl group, a substituted aryl group or a substituted heteroaryl group, and a hydrogen atom in the formula represented by (CH2)ml 4(CH2)ra2 may also be substituted by fluorine)] [wherein R represents the same as defined above]. The polymer compound according to claim 1, wherein R is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by fluorine, and a carbon number of 1 to 20 which may be substituted by fluorine. The alkoxy group or the phenyl group which may be substituted, wherein the substituent of the phenyl group is a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. 2. 201229087 3. An organic photoelectric conversion element having a pair of electrodes and a functional layer provided between the electrodes, the functional layer comprising an electron accepting compound and the polymer compound according to claim 1 of the patent application. 4. The organic photoelectric conversion device according to claim 3, wherein the amount of the electron-accepting compound contained in the functional layer is from 10 to 1,000 parts by weight based on 100 parts by weight of the polymer compound. 5. The organic photoelectric conversion device according to claim 3, wherein the electron accepting compound is a fullerene derivative.