WO2013035710A1 - Composé polymère et élément de conversion photoélectrique organique - Google Patents

Composé polymère et élément de conversion photoélectrique organique Download PDF

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WO2013035710A1
WO2013035710A1 PCT/JP2012/072523 JP2012072523W WO2013035710A1 WO 2013035710 A1 WO2013035710 A1 WO 2013035710A1 JP 2012072523 W JP2012072523 W JP 2012072523W WO 2013035710 A1 WO2013035710 A1 WO 2013035710A1
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上谷　保則
貴史 荒木
淳 藤原
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住友化学株式会社
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Definitions

  • the present invention relates to a polymer compound, and an organic photoelectric conversion element and an organic thin film transistor using the polymer compound.
  • An organic semiconductor material is used for organic photoelectric conversion elements, such as an organic solar cell and an optical sensor, for example.
  • organic photoelectric conversion elements such as an organic solar cell and an optical sensor
  • a high molecular compound is used among organic semiconductor materials
  • a thin film can be manufactured by an inexpensive coating method, and the manufacturing cost of the element can be reduced.
  • various polymer compounds have been studied for organic semiconductor materials constituting the element. For example, a polymer compound obtained by polymerizing 9,9-dioctylfluorene-2,7-diboronic acid ester and 5,5 ′′ ′′-dibromo-3 ′′, 4 ′′ -dihexyl- ⁇ -pentathiophene is proposed. (WO 2005/092947). However, the polymer compound has a problem that long-wavelength light is not sufficiently absorbed.
  • the present invention provides a polymer compound having a large absorbance of light having a long wavelength. That is, this invention provides the high molecular compound containing the repeating unit represented by the below-mentioned formula (A) and the repeating unit represented by Formula (B). Moreover, this invention provides the high molecular compound containing the repeating unit represented by below-mentioned formula (1).
  • 1 to 7 are diagrams showing absorption spectra of polymer compounds A to G, respectively.
  • 8 to 10 are diagrams showing absorption spectra of the polymer compounds J, K, and L, respectively.
  • the polymer compound of the present invention includes a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B).
  • R is the same or different and is a hydrogen atom, a fluorine atom, an alkyl group optionally substituted with a fluorine atom, an alkoxy group optionally substituted with a fluorine atom, An aryl group, a heteroaryl group, a group represented by the formula (2a), or a group represented by (2b) is represented.
  • Ar 1 and Ar 2 represent an optionally substituted trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms or a trivalent heterocyclic group having 4 to 60 carbon atoms.
  • Ar 3 represents an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms or a divalent heterocyclic group having 4 to 60 carbon atoms.
  • m1 represents an integer of 0 to 6
  • m2 represents an integer of 0 to 6.
  • R ′ represents an alkyl group, aryl group or heteroaryl optionally substituted with a fluorine atom. Represents a group.
  • m3 represents an integer of 0 to 6
  • m4 represents an integer of 0 to 6.
  • R ′′ represents an alkyl group, an aryl group, or a hetero atom optionally substituted with a fluorine atom. Represents an aryl group.
  • the alkyl group represented by R usually has 1 to 20 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group. Hexyl group, octyl group, iso-octyl group, decyl group, dodecyl group, pentadecyl group and octadecyl group.
  • the hydrogen atom in the alkyl group may be substituted with a fluorine atom.
  • Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, and a perfluorohexyl group. And a perfluorooctyl group.
  • the alkoxy group represented by R usually has 1 to 20 carbon atoms.
  • the hydrogen atom in the alkoxy group may be substituted with a fluorine atom.
  • alkoxy group substituted with a fluorine atom examples include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, and a perfluorohexyloxy group.
  • the aryl group represented by R is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon which may have a substituent.
  • the aryl group includes a group containing a benzene ring, a group containing a condensed ring having aromaticity, a group having a structure in which two or more benzene rings or a condensed ring having aromaticity are directly bonded, and two or more benzenes
  • Examples include a group in which a ring or an aromatic condensed ring is bonded via a group such as vinylene.
  • the aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • Examples of the substituent that the aromatic hydrocarbon may have include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group, and an alkoxy group.
  • the definitions and specific examples of the alkyl group and alkoxy group are the same as the definitions and specific examples of the alkyl group and alkoxy group represented by R.
  • the heteroaryl group represented by R is an atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic compound which may have a substituent.
  • heteroaryl group examples include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.
  • substituent that the aromatic heterocyclic compound may have include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group, and an alkoxy group.
  • the definitions and specific examples of the alkyl group and alkoxy group are the same as the definitions and specific examples of the alkyl group and alkoxy group represented by R.
  • m1 represents an integer of 0 to 6
  • m2 represents an integer of 0 to 6.
  • R ′ represents an alkyl group, an aryl group or a heteroaryl group which may be substituted with a fluorine atom.
  • the definitions and specific examples of the alkyl group, aryl group and heteroaryl group which may be substituted with a fluorine atom represented by R ′ are the alkyl group and aryl group which may be substituted with a fluorine atom represented by R.
  • the definition and specific examples of the heteroaryl group are the same.
  • m3 represents an integer of 0 to 6
  • m4 represents an integer of 0 to 6.
  • R ′′ represents an alkyl group, an aryl group or a heteroaryl group which may be substituted with a fluorine atom.
  • alkyl group, aryl group and heteroaryl group optionally substituted with a fluorine atom represented by R ′′ are an alkyl group optionally substituted with a fluorine atom represented by R, aryl
  • the definition and specific examples of the group and the heteroaryl group are the same.
  • R is an alkyl group which may be substituted with a fluorine atom or an alkoxy group which may be substituted with a fluorine atom, from the viewpoint of the solubility of the polymer compound in the solvent,
  • the number of carbon atoms is preferably 1-20, more preferably 2-18, and even more preferably 3-12.
  • Ar 1 and Ar 2 may have a substituent, a trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituent.
  • Ar 3 may have a divalent aromatic hydrocarbon group or substituent having 6 to 60 carbon atoms which may have a substituent.
  • a divalent heterocyclic group having 4 to 60 carbon atoms is shown.
  • an optionally substituted trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms is an aromatic carbon atom having 6 to 60 carbon atoms that may have a substituent.
  • excluding three hydrogen atoms on the aromatic ring in a hydrogen compound is shown.
  • the optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms refers to an aromatic hydrocarbon compound having 6 to 60 carbon atoms that may have a substituent.
  • excluding two hydrogen atoms on the aromatic ring in is shown.
  • the aromatic hydrocarbon compound may be a single ring or a condensed ring. Among these, since excellent solubility is obtained and production is easy, a condensed ring or a single ring in which five or less rings are condensed is preferable, and a condensed ring or a single ring in which two rings are condensed is preferable. A ring is more preferable, and a single ring is more preferable.
  • the aromatic hydrocarbon compound examples include benzene, naphthalene, anthracene, fluorene, pyrene, and perylene. Of these, benzene or naphthalene is preferable, and benzene is more preferable.
  • the aromatic hydrocarbon group has a substituent, the carbon number of the preferred aromatic hydrocarbon group described above does not include the carbon number of the substituent. Examples of the substituent include the same groups as those described above for R.
  • the trivalent heterocyclic group having 4 to 60 carbon atoms is a trivalent group excluding three hydrogen atoms on the heterocyclic ring in the heterocyclic compound having 4 to 60 carbon atoms which may have a substituent. Indicates.
  • the divalent heterocyclic group having 4 to 60 carbon atoms is a divalent heterocyclic group having 2 hydrogen atoms on the heterocyclic ring in the heterocyclic compound having 4 to 60 carbon atoms which may have a substituent. Indicates a group.
  • the heterocyclic compound may be a single ring or a condensed ring. Among these, since excellent solubility is obtained and production is easy, a condensed ring or a single ring in which five or less rings are condensed is preferable, and a condensed ring or a single ring in which two rings are condensed is preferable. Is more preferable, and a single ring is more preferable.
  • heterocyclic compound examples include pyridine, thiophene, thienothiophene, dithienothiophene, benzothiophene, benzodithiophene, dibenzothiophene, pyrrole, quinoline, and indole. Of these, thiophene, thienothiophene or pyridine is preferable, and thiophene is more preferable.
  • the heterocyclic group has a substituent, the carbon number of the preferable heterocyclic group described above does not include the carbon number of the substituent.
  • substituents examples include a halogen atom, a saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 60 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkanoyl group having 1 to 12 carbon atoms, Examples thereof include aryloxy groups having 6 to 60 carbon atoms, heterocyclic groups having 3 to 60 carbon atoms, amino groups, nitro groups, and cyano groups. Examples of these substituents include the same groups as those described above for R.
  • Ar 1 and Ar 2 are preferably trivalent groups excluding three hydrogen atoms on the aromatic ring in benzene or thiophene.
  • Ar 3 is preferably a divalent group excluding three hydrogen atoms on the aromatic ring in benzene or thiophene.
  • the repeating unit represented by the formula (A) include the following repeating units.
  • the repeating unit represented by the formula (B) include the following repeating units.
  • the polymer compound of the present invention preferably includes a repeating unit in which the repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) are directly bonded.
  • the total amount of the repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) contained in the polymer compound of the present invention is that of the organic photoelectric conversion element having a functional layer containing the polymer compound.
  • the polymer compound of the present invention is a polymer compound containing a repeating unit represented by the formula (1).
  • R represents the same meaning as described above.
  • 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 polystyrene equivalent weight average molecular weight 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.
  • 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 (A), the repeating unit represented by the formula (B), and the repeating unit represented by the formula (1).
  • the repeating unit include an arylene group and a heteroarylene group.
  • the arylene group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a pyrenediyl group, and a fluorenediyl group.
  • 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.
  • ligands such as triphenylphosphine, tri (2-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, diphenylphosphinopropane, tri (cyclohexyl) phosphine, tri (tert-butyl) phosphine
  • a polymerization reaction of a monomer having a group 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.
  • 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.
  • a monomer having a halogen atom such as a bromine atom, an iodine atom or a chlorine atom
  • a monomer having a sulfonate group such as a trifluoromethanesulfonate group or a p-toluenesulfonate group.
  • 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.
  • 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.
  • 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, a compound having a magnesium halide group and a halogen atom.
  • 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.
  • 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.
  • 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.
  • Solvents used in the Suzuki coupling reaction are organic solvents such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, and mixed solvents in which two or more of these solvents are mixed.
  • 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 an organic solvent such as tetrahydrofuran, toluene, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, or a mixed solvent in which two or more of these solvents are mixed.
  • a solvent is preferred.
  • the solvent used for the Yamamoto coupling reaction is preferably deoxygenated before the reaction in order to suppress side reactions.
  • 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.
  • 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.
  • 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.
  • a lower alcohol such as methanol
  • the polymer compound of the present invention 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.
  • 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.
  • the arylamino group include a phenylamino group and a diphenylamino group.
  • the monovalent heterocyclic group examples include thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, and isoquinolyl group.
  • the polymerization active group remaining at the terminal of the polymer compound may be replaced with a hydrogen atom instead of a stable group.
  • the stable group for protecting the terminal is a group imparting electron donating properties such as an arylamino group.
  • the polymer compound of the present invention is produced using Stille 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.
  • R represents the same meaning as described above.
  • Plural Rs may be the same or different.
  • Z represents a bromine atom, an iodine atom or a chlorine atom. May be the same or different.
  • R represents the same meaning as described above.
  • Two Rs may be the same or different.
  • Z 2 represents an organotin residue.
  • Z is preferably a bromine atom or a chlorine atom, and more preferably a bromine atom, from the viewpoint of increasing the reactivity during polymerization.
  • the compound represented by the formula (3) can be synthesized, for example, using the method described in Organic Electronics 2010, 11, 1740-1745.
  • 2,4-dibromo-3,4-dicarboxylic acid obtained by bromine under glacial acetic acid with 3,4-thiophenedicarboxylic acid in a solvent such as halogenated hydrocarbons such as chloroform and dichloromethane
  • a chlorinating agent such as thionyl chloride or oxalyl dichloride
  • R an acid chloride compound obtained by reacting a chlorinating agent such as thionyl chloride or oxalyl dichloride is reacted with R in the presence of a Lewis acid, for example, aluminum (III) chloride, in a halogenated hydrocarbon such as chloroform or dichloromethane. It can be synthesized by reacting a defined substituted benzene (Friedel-Crafts reaction).
  • Z 2 is -SnMe 3, preferably a -SnEt 3 or -SnBu 3.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group.
  • the compound represented by the formula (4) is prepared by, for example, reacting the compound represented by the formula (5) with an organolithium compound to produce an intermediate, and then reacting the intermediate with a trialkyltin halide. Can be manufactured.
  • Examples of the organic lithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium, and lithium diisopropylamide. Of the organic lithium compounds, n-butyllithium is preferable.
  • Examples of the trialkyltin halide include trimethyltin chloride, triethyl chloride, and tributyl chloride.
  • the temperature for reacting the organolithium compound with the compound represented by formula (5) is usually ⁇ 100 to 50 ° C., preferably ⁇ 80 to 0 ° C.
  • the time for reacting the organolithium compound with the compound represented by the formula (5) is usually 1 minute to 10 hours, preferably 30 minutes to 5 hours.
  • the amount of the organolithium compound to be reacted is usually 2 to 5 molar equivalents (hereinafter, the molar equivalent is simply referred to as equivalent), preferably 2 to 3 with respect to the compound represented by the formula (5). Is equivalent.
  • the temperature at which the intermediate and the trialkyltin halide are reacted is usually ⁇ 100 to 100 ° C., preferably ⁇ 80 ° C. to 50 ° C.
  • the reaction time of the intermediate and the trialkyltin halide is usually 1 minute to 30 hours, preferably 1 to 10 hours.
  • the amount of the trialkyltin halide to be reacted is usually 2 to 6 equivalents, preferably 2 to 3 equivalents, relative to the compound represented by the formula (5).
  • normal post-treatment can be performed to obtain the compound represented by the formula (4). 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 product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.
  • the compound represented by the formula (5) can be produced, for example, by reacting the compound represented by the formula (6) in the presence of an acid.
  • R represents the same meaning as described above.
  • the acid used in the reaction for producing the compound represented by the formula (5) from the compound represented by the formula (6) may be Lewis acid or Bronsted acid, Hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, benzoic acid, boron fluoride, aluminum chloride, tin chloride (IV), iron chloride (II), titanium tetrachloride, Examples include benzenesulfonic acid, p-toluenesulfonic acid and mixtures of these compounds.
  • the reaction for producing the compound represented by formula (5) from the compound represented by formula (6) is preferably carried out in the presence of a solvent.
  • the reaction temperature is preferably from ⁇ 80 ° C. to the boiling point of the solvent.
  • Solvents used in the reaction include saturated hydrocarbon solvents such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbon solvents such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane and bromobutane.
  • Halogenated saturated hydrocarbon solvents such as chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methanol, ethanol, propanol, Alcohol solvents such as isopropanol, butanol, tert-butyl alcohol, carboxylic acid solvents such as formic acid, acetic acid, propionic acid, dimethyl ether, diethyl ether Ether, methyl -tert- butyl ether, tetrahydrofuran, tetrahydropyran, ether solvents such as dioxane.
  • Halogenated saturated hydrocarbon solvents such as chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohe
  • the reaction can be used alone or in combination.
  • normal post-treatment can be performed to obtain the compound represented by the formula (5).
  • the reaction is stopped by adding water, the product is extracted with an organic solvent and the solvent is distilled off.
  • the product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.
  • the compound represented by the formula (6) can be produced, for example, by reacting the compound represented by the formula (7) with a Grignard reagent or an organolithium compound.
  • methyl magnesium chloride methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, propyl magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, hexyl magnesium bromide, octyl magnesium bromide
  • Examples include decylmagnesium bromide, allylmagnesium chloride, allylmagnesium bromide, benzylmagnesium chloride, phenylmagnesium bromide, naphthylmagnesium bromide, and tolylmagnesium bromide.
  • Examples of the organic lithium compound include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, phenyl lithium, naphthyl lithium, benzyl lithium, and tolyl lithium.
  • the reaction for producing the compound represented by the formula (6) from the compound represented by the formula (7) and a Grignard reagent or an organolithium compound may be carried out in an inert gas atmosphere such as nitrogen or argon. preferable. Moreover, it is preferable to implement this reaction in presence of a solvent.
  • the reaction temperature is preferably from ⁇ 80 ° C. to the boiling point of the solvent.
  • Solvents used in the reaction include saturated hydrocarbon solvents such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbon solvents such as benzene, toluene, ethylbenzene and xylene, dimethyl ether, diethyl ether, methyl-tert-butyl ether, Ether solvents such as tetrahydrofuran, tetrahydropyran, dioxane and the like can be mentioned. These solvents may be used alone or in combination. After the reaction, normal post-treatment can be performed to obtain the compound represented by the formula (6).
  • saturated hydrocarbon solvents such as pentane, hexane, heptane, octane and cyclohexane
  • unsaturated hydrocarbon solvents such as benzene, toluene, ethylbenzene and xylene, dimethyl ether
  • the compound represented by the formula (7) can be produced, for example, by reacting the compound represented by the formula (8) with a peroxide.
  • the peroxide include sodium perborate, m-chloroperbenzoic acid, hydrogen peroxide, and benzoyl peroxide. Preferred are sodium perborate and m-chloroperbenzoic acid, and particularly preferred is sodium perborate.
  • the reaction for producing the compound represented by the formula (7) from the compound represented by the formula (8) and the peroxide is carried out in the presence of a carboxylic acid solvent such as acetic acid, trifluoroacetic acid, propionic acid and butyric acid. It is preferable.
  • a carboxylic acid solvent such as acetic acid, trifluoroacetic acid, propionic acid and butyric acid. It is preferable.
  • a mixed solvent in which one or more solvents selected from the group consisting of carbon tetrachloride, chloroform, dichloromethane, benzene, and toluene are mixed with a carboxylic acid solvent. It is preferable to carry out the reaction.
  • the reaction temperature is preferably 0 ° C. or higher and 50 ° C. or lower.
  • the polymer compound of the present invention may contain a structural unit represented by the formula (C-1) to the formula (C-12) as a third structural unit.
  • X represents a sulfur atom, an oxygen atom or a selenium atom.
  • the plurality of Xs may be the same or different.
  • R represents the same as those shown above.
  • the plurality of Rs may be the same or different.
  • the organic photoelectric conversion device of the present invention has a pair of electrodes and a functional layer between the electrodes, and the functional layer contains the electron-accepting compound and the polymer compound of the present invention.
  • an electron-accepting compound fullerene or a fullerene derivative is preferable.
  • 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 the polymer compound of the present invention; 2.
  • An organic photoelectric conversion element comprising a pair of electrodes and a functional layer between the electrodes, the functional layer containing an electron-accepting compound and the polymer compound of the present invention, wherein the electron-accepting compound is a fullerene
  • at least one of the pair of electrodes is transparent or translucent.
  • 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. It is preferably 20 to 500 parts by weight. In addition, 2.
  • 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 parts by weight. 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 preferred is 80 to 120 parts by weight.
  • 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.
  • the electron-accepting compound and the polymer compound of the present invention have an absorption region that can efficiently absorb the spectrum of desired incident light. It is important that the heterojunction interface includes many heterojunction interfaces in order to efficiently separate excitons, and that the heterojunction interface has a charge transporting property for quickly transporting charges generated by the heterojunction interface to the electrode. From such a viewpoint, as the organic photoelectric conversion element, the above 1. , 2.
  • the organic photoelectric conversion element is preferable.
  • the organic photoelectric conversion element is more preferable.
  • an additional layer may be provided between at least one electrode and the functional layer in the element.
  • 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.
  • a metal, a conductive polymer, or the like can be used as a material for the pair of electrodes.
  • the material of one of the pair of electrodes is preferably a material having a low work function.
  • metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and those metals
  • An alloy with metal, graphite, a graphite intercalation compound, or the like is used.
  • the alloy examples 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.
  • the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, a film formed using a conductive material made of indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium zinc oxide, etc., which is a composite thereof, NESA Gold, platinum, silver, and copper are used, and ITO, indium / zinc / oxide, and tin oxide are preferable.
  • Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like.
  • organic transparent conductive films such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.
  • 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.
  • fine particles of an inorganic semiconductor such as titanium oxide can be used.
  • an organic thin film containing the polymer compound of the present invention and an electron-accepting compound can be used as the functional layer in the organic photoelectric conversion element of the present invention.
  • the organic thin film generally has a thickness of 1 nm to 100 ⁇ m, 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.
  • 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 of the present invention include, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and its derivatives, polyvinylcarbazole and its Derivatives, polysilanes 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, polythienylene vinylene and derivatives thereof Is mentioned.
  • 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 level of the energy level of these compounds.
  • Fullerenes and derivatives thereof include C 60 , C 70 , C 84 and derivatives thereof.
  • a fullerene derivative represents a compound in which at least a part of fullerene is modified.
  • Examples of the fullerene derivative include a compound represented by 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).
  • R a is an alkyl group, aryl group, heteroaryl group or group having an ester structure optionally substituted with a fluorine atom.
  • a plurality of R a are the same.
  • R b represents an alkyl group or an aryl group which may be substituted with a fluorine atom, and a plurality of R b may be the same or different.
  • the definition and specific examples of the alkyl group, aryl group and heteroaryl group optionally substituted with a fluorine atom represented by R a and R b are the alkyl group optionally substituted with a fluorine atom represented by R
  • the definition and specific examples of the aryl group and heteroaryl group are the same.
  • Examples of the group having an ester structure represented by Ra include a group represented by the formula (V).
  • u1 represents an integer of 1 to 6
  • u2 represents an integer of 0 to 6
  • R c represents an alkyl group, aryl group or heteroaryl optionally substituted with a fluorine atom. Represents a group.
  • the definitions and specific examples of the alkyl group, aryl group and heteroaryl group which may be substituted with a fluorine atom represented by R c are as follows: the alkyl group and aryl group which may be substituted with a fluorine atom represented by R And the definition and specific examples of the heteroaryl group are the same.
  • Specific examples of the C 60 derivative include the following.
  • Specific examples of the C 70 derivative include the following.
  • the organic thin film may be produced by any method.
  • 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, butylbenzene, sec-butylbenzene, tert-butylbenzene, and other unsaturated hydrocarbon solvents, 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.
  • 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.
  • the organic photoelectric conversion element 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.
  • Organic thin film transistor of the present invention includes a source electrode, a drain electrode, an organic semiconductor layer, and a gate electrode.
  • the organic semiconductor layer is represented by the repeating unit represented by the formula (A) and the formula (B).
  • the polystyrene equivalent weight average molecular weight of the polymer compound was determined by size exclusion chromatography (SEC). Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6 mm Id ⁇ 15 cm); Detector: RI (SHIMADZU RID-10A); Mobile phase: Tetrahydrofuran (THF) Reference Example 1 (Synthesis of Compound 2) A homogeneous solution containing 2.00 g (9.60 mmol) of Compound 1 synthesized by the method described in WO2011 / 052709A1 and 60 mL of dehydrated THF (tetrahydrofuran) in a 200 mL four-necked flask in which the gas in the flask is replaced with argon.
  • SEC size exclusion chromatography
  • the obtained oily substance was purified by a silica gel column whose developing solvent was hexane.
  • silica gel of the silica gel column silica gel previously immersed in hexane containing 5 wt% triethylamine for 5 minutes and then rinsed with hexane was used. After purification, 3.77 g (4.13 mmol) of compound 4 was obtained.
  • Example 1 Synthesis of Polymer Compound A
  • 273 mg (0.300 mmol) of compound 4 162 mg (0.300 mmol) of compound 11 synthesized in Reference Example 8, and 8.2 mg of tris (2-tolyl) phosphine (0.027 mmol) and 23 ml of dehydrated toluene were added to obtain a uniform solution.
  • the resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 4.1 mg (0.0045 mmol) of tris (dibenzylideneacetone) dipalladium was added to the toluene solution, stirred at 105 ° C.
  • the polymer remaining in the cylindrical filter paper was dissolved in 15 mL of toluene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours. After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated.
  • Example 2 Synthesis of polymer compound B
  • 316 mg (0.300 mmol) of compound 13 synthesized by the method described in WO2011 / 052709A1, 162.1 mg (0.300 mmol) of compound 11, tris (2-tolyl) ) 8.2 mg (0.027 mmol) of phosphine and 25 ml of dehydrated toluene were added to obtain a uniform solution.
  • the resulting toluene solution was bubbled with argon for 30 minutes.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 12 mL of toluene, 0.26 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours.
  • the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol.
  • Example 3 Synthesis of Polymer Compound C
  • 158 mg (0.150 mmol) of compound 13 and 178 mg (0.150 mmol) of compound 14 as a starting material were synthesized using the compound synthesized by the method described in WO2011 / 052709A1.
  • tris (2-tolyl) phosphine (8.2 mg, 0.027 mmol) were added to obtain a homogeneous solution.
  • the resulting toluene solution was bubbled with argon for 30 minutes.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours, respectively, using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 15 mL of toluene, 0.26 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours.
  • polymer compound C After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 13 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 233 mg of a purified polymer.
  • this polymer is referred to as polymer compound C.
  • Example 4 Synnthesis of polymer compound D
  • 299 mg (0.300 mmol) of compound 15 synthesized using the same method as the method of synthesizing compound 4 from compound 1 and 162 mg (0.300 mmol) of compound 11 were synthesized.
  • the flask was cooled to room temperature, and the reaction solution was poured into a mixed solution of 200 mL of methanol and 20 mL of concentrated hydrochloric acid.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 12 mL of toluene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 3 hours.
  • polymer compound D After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 11 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 176 mg of a purified polymer.
  • this polymer is referred to as polymer compound D.
  • Example 5 Synthesis of polymer compound E
  • 273 mg (0.300 mmol) of compound 4 196 mg (0.300 mmol) of compound 12
  • 8.2 mg (0.027 mmol) of tris (2-tolyl) phosphine 24 ml of dehydrated toluene was added to make a uniform solution.
  • the resulting toluene solution was bubbled with argon for 30 minutes.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 12 mL of toluene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 2 hours.
  • the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol.
  • Example 6 (Synthesis of Polymer Compound F) 302 mg (0.300 mmol) of Compound 16 synthesized using the same method as the method of synthesizing Compound 4 from Compound 1 and 196 mg (0.300 mmol) of Compound 12 in a 100 mL flask in which the gas in the flask was replaced with argon Then, 8.2 mg (0.027 mmol) of tris (2-tolyl) phosphine and 26 ml of dehydrated toluene were added to obtain a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol and acetone for 3 hours using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 14 mL of toluene, 0.25 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 1.5 hours.
  • the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol.
  • Example 7 Synthesis of polymer compound G
  • 3.6 mg (0.012 mmol) of tris (2-tolyl) phosphine, and 11 ml of dehydrated toluene were added to obtain a uniform solution.
  • the resulting toluene solution was bubbled with argon for 30 minutes.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 6 mL of toluene, 0.11 g of sodium diethyldithiocarbamate and 1.0 mL of water were added, and the mixture was stirred at 90 ° C. for 2.5 hours.
  • polymer compound G After removing the aqueous layer, the organic layer was washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 5 mL of toluene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 244 mg of a purified polymer.
  • this polymer is referred to as polymer compound G.
  • Example 8 Synthesis of Polymer Compound K
  • the flask was cooled, and the reaction solution was poured into 200 mL of a 10 wt% hydrogen chloride methanol solution.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 9 mL of orthodichlorobenzene, 0.17 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 2 hours.
  • polymer compound K After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was poured into methanol. A polymer was precipitated. The polymer was filtered and dried, and the resulting polymer was dissolved again in 10 mL of orthodichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 73 mg of a purified polymer.
  • this polymer is referred to as polymer compound K.
  • Example 9 Synthesis of Polymer Compound L
  • 210.6 mg (0.200 mmol) of compound 13 81.6 mg (0.200 mmol) of compound 18, and 5.6 mg of tris (2-tolyl) phosphine were placed in a 100 mL three-necked flask equipped with a reflux tube. (9.0 mol%) and 16 mL (2.0 wt%) of dehydrated toluene were added to obtain a uniform solution.
  • the reaction solution was cooled to room temperature, poured into 200 mL of a 10 wt% hydrogen chloride methanol solution, and the precipitated polymer was collected by filtration.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and washed with methanol, acetone and hexane for 3 hours using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 8.0 mL of orthodichlorobenzene, 0.17 g of sodium diethyldithiocarbamate and 3.0 mL of water were added, and the mixture was stirred at 90 ° C. for 2 hours.
  • polymer compound L After removing the aqueous layer, the organic layer was washed twice with 50 mL of water, then twice with 50 mL of a 3.0 wt% aqueous acetic acid solution, then twice with 50 mL of water, and the resulting solution was taken up in methanol. The polymer was precipitated by pouring. The polymer was filtered and dried, and the obtained polymer was redissolved in 7.0 mL of orthodichlorobenzene and passed through an alumina / silica gel column. The obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and dried to obtain 83 mg of a purified polymer.
  • this polymer is referred to as polymer compound L.
  • Reference Example 12 Synthesis of polymer compound J
  • the weight average molecular weight of polymer compound J in terms of polystyrene is 1.1 ⁇ 10 5 Met.
  • Measurement Example 1 Measurement of absorbance of organic thin film
  • the polymer compound A was dissolved in o-dichlorobenzene at a concentration of 0.75% by weight and 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
  • 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, 800 nm, and 900 nm.
  • Measurement example 2 Measurement of absorbance of organic thin film
  • An organic thin film was formed in the same manner as in Measurement Example 1 except that the polymer compound B was used in place of the polymer compound A, and the absorption spectrum thereof was measured. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.
  • Measurement Example 3 Measurement of absorbance of organic thin film
  • An organic thin film was formed in the same manner as in Measurement Example 1 except that the polymer compound C was used instead of the polymer compound A, and the absorption spectrum thereof was measured.
  • the measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.
  • Measurement Example 4 Measurement of absorbance of organic thin film
  • the absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound D was used instead of the polymer compound A.
  • the measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.
  • Measurement Example 5 Measurement of absorbance of organic thin film
  • the absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound E was used instead of the polymer compound A.
  • the measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.
  • Measurement Example 6 Measurement of absorbance of organic thin film
  • the absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound F was used instead of the polymer compound A.
  • the measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.
  • Measurement Example 7 Measurement of absorbance of organic thin film
  • the absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound G was used instead of the polymer compound A.
  • the measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.
  • Measurement Example 8 Measurement of absorbance of organic thin film
  • the absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound K was used instead of the polymer compound A.
  • the measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.
  • Measurement Example 9 Measurement of absorbance of organic thin film
  • the absorption spectrum of the organic thin film was measured in the same manner as in Measurement Example 1 except that the polymer compound L was used instead of the polymer compound A.
  • the measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.
  • Comparative Example 1 Measurement of absorbance of organic thin film
  • Polymer compound J was dissolved in o-dichlorobenzene at a concentration of 0.5% by weight and 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
  • 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.
  • Example 10 (Production and Evaluation of Organic Thin Film Solar Cell) Fullerene derivative C70PCBM (Phenyl C71-butylic acid methyl ester, manufactured by American Dye Source, Inc., trade name: ADS71BFA (lot number 10K037E), which is an electron-accepting compound, and polymer compound A, which is an electron-donating compound, 2: The mixture was dissolved in o-dichlorobenzene so that the concentration of the mixture was 2.25% by weight, and the resulting solution was filtered through a Teflon filter having a pore size of 0.5 ⁇ m. A coating solution 1 was prepared.
  • 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.
  • 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. It was created.
  • the coating solution 1 was applied onto the ITO film 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.
  • 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 is all 1-9x10 -3 Pa.
  • the shape of the organic thin film solar cell thus obtained was a square of 2 mm ⁇ 2 mm.
  • a solar simulator (trade name OTENTO-SUNII: AM1.5G filter, irradiance 100 mW / cm, manufactured by Spectrometer Co., Ltd.) was applied to the obtained organic thin film solar cell. 2 ) was used to irradiate constant light, and the generated current and voltage were measured.
  • Example 11 Provide and Evaluation of Organic Thin Film Solar Cell
  • An organic thin film solar cell was prepared and evaluated in the same manner as in Example 10 except that the polymer compound G was used instead of the polymer compound A.
  • the photoelectric conversion efficiency is 6.25%
  • Jsc (short circuit current density) is 13.2 mA / cm.
  • 2 Voc (open end voltage) was 0.88 V
  • FF (fill factor) was 0.54.
  • Example 12 (Production and Evaluation of Organic Thin Film Solar Cell) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 10 except that tetralin was used instead of o-dichlorobenzene. The photoelectric conversion efficiency is 6.33%, and Jsc (short circuit current density) is 15.2 mA / cm. 2 Voc (open end voltage) was 0.76 V, and FF (fill factor) was 0.55.
  • Example 13 (Production and Evaluation of Organic Thin Film Solar Cell) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 8 except that the polymer compound K was used instead of the polymer compound A. The photoelectric conversion efficiency is 6.14%, and Jsc (short circuit current density) is 16.2 mA / cm. 2 Voc (open end voltage) was 0.76 V, and FF (fill factor) was 0.50.
  • the polymer compound of the present invention has a large absorbance for light having a long wavelength and can be used for an organic photoelectric conversion device.

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Abstract

La présente invention concerne un composé polymère comprenant des unités répétitives représentées par la formule (A) et des unités répétitives représentées par la formule (B) présentant une haute absorbance de la lumière de longue longueur d'onde, et pouvant être utilisé dans un dispositif de conversion photoélectrique organique. (Dans la formule (A) et la formule (B), R peut être identique ou différent, et représente un atome d'hydrogène, un atome de fluor, un groupe alkyle qui peut être substitué par un atome de fluor, un groupe alcoxy qui peut être substitué par un atome de fluor, un groupe aryle, un groupe hétéroaryle, un groupe représenté par la formule (2a), ou un groupe représenté par la formule (2b) ; et Ar1, Ar2 et Ar3 représentent un groupe hydrocarboné aromatique en C6-60 ou un groupe hétérocyclique en C4-60 qui peut présenter un substituant.)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013100457A (ja) * 2011-09-07 2013-05-23 Sumitomo Chemical Co Ltd 高分子化合物及びそれを用いた有機光電変換素子
JP2014189721A (ja) * 2013-03-28 2014-10-06 Sumitomo Chemical Co Ltd 高分子化合物
JP2014205737A (ja) * 2013-04-11 2014-10-30 住友化学株式会社 化合物及びそれを用いた電子素子
CN109776767A (zh) * 2018-12-29 2019-05-21 华南理工大学 一种含二氟萘并噻吩二酮吸电子单元的共轭聚合物及其合成方法与应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6379074B2 (ja) * 2015-06-30 2018-08-22 富士フイルム株式会社 光電変換素子及び太陽電池

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008109144A (ja) * 2007-11-05 2008-05-08 Toshiba Corp 回路基板の製造方法および回路基板の検査方法
WO2009051275A1 (fr) * 2007-10-19 2009-04-23 Sumitomo Chemical Company, Limited Composé de type polymère et convertisseur photoélectrique organique l'utilisant
WO2011052712A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Élément de conversion photoélectrique
WO2011052709A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Composé polymère
WO2011052711A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Élément de conversion photoélectrique
WO2011052710A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Composé polymère
WO2011052702A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Composé polymère et élément électronique

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4999334B2 (ja) * 2005-02-28 2012-08-15 住友化学株式会社 色素化合物、該化合物を用いた光電変換素子及び光電気化学電池
WO2009125647A1 (fr) * 2008-04-11 2009-10-15 東レ株式会社 Matériau organique donneur d’électrons, matériau pour élément photovoltaïque, et élément photovoltaïque
JP2010192863A (ja) * 2008-05-23 2010-09-02 Sumitomo Chemical Co Ltd 有機光電変換素子およびその製造方法
JP2010034494A (ja) * 2008-06-30 2010-02-12 Sumitomo Chemical Co Ltd 有機光電変換素子
JP2011168747A (ja) * 2010-02-22 2011-09-01 Kyoto Univ 共役系高分子、該共役系高分子を用いた有機薄膜太陽電池
WO2012050070A1 (fr) * 2010-10-13 2012-04-19 住友化学株式会社 Composé de masse moléculaire élevée et élément de conversion photoélectrique organique l'utilisant
WO2012070390A1 (fr) * 2010-11-26 2012-05-31 住友化学株式会社 Élément de conversion photoélectrique organique
JP5747789B2 (ja) * 2011-07-05 2015-07-15 住友化学株式会社 高分子化合物及びそれを用いた有機光電変換素子
JP6003399B2 (ja) * 2011-09-07 2016-10-05 住友化学株式会社 高分子化合物及びそれを用いた有機光電変換素子

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009051275A1 (fr) * 2007-10-19 2009-04-23 Sumitomo Chemical Company, Limited Composé de type polymère et convertisseur photoélectrique organique l'utilisant
JP2008109144A (ja) * 2007-11-05 2008-05-08 Toshiba Corp 回路基板の製造方法および回路基板の検査方法
WO2011052712A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Élément de conversion photoélectrique
WO2011052709A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Composé polymère
WO2011052711A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Élément de conversion photoélectrique
WO2011052710A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Composé polymère
WO2011052702A1 (fr) * 2009-10-29 2011-05-05 住友化学株式会社 Composé polymère et élément électronique

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHAOHUA CUI, ET AL.: "A D-A copolymer of dithienosilole and a new acceptor unit of naphtho[2,3-c]thiophene-4,9-dione for efficient polymer solar cells", CHEM. COMMUN., vol. 47, 14 September 2011 (2011-09-14), pages 11345 - 11347 *
KOUICHI SHIRAISHI AND TAKAKAZU YAMAMOTO: "Synthesis and Electrochemical Properties of New Main Chain Type Polyquinones Constituted of Thiophene-Fused Benzoquinone and Transformation of the Polymers to a Dicyanoquinonediimine Type Polymer", POLYMER JOURNAL, vol. 34, no. 10, 2002, pages 727 - 735 *
POMERANTZ M: "Planar 2,2'-bithiophenes with 3,3'- and 3,3',4,4'-substituents. A computational study", TETRAHEDRON LETTERS, vol. 44, no. 8, 2003, pages 1563 - 1565, XP004405271 *
QING T. ZHANG, ET AL.: "Alternating Donor/Acceptor Repeat Units in Polythiophenes. Intramolecular Charge Transfer for Reducing Band Gaps in Fully Substituted Conjugated Polymers", J. AM. CHEM. SOC., vol. 120, no. 22, 1998, pages 5355 - 5362, XP002614086, DOI: doi:10.1021/ja972373e *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013100457A (ja) * 2011-09-07 2013-05-23 Sumitomo Chemical Co Ltd 高分子化合物及びそれを用いた有機光電変換素子
JP2014189721A (ja) * 2013-03-28 2014-10-06 Sumitomo Chemical Co Ltd 高分子化合物
JP2014205737A (ja) * 2013-04-11 2014-10-30 住友化学株式会社 化合物及びそれを用いた電子素子
CN109776767A (zh) * 2018-12-29 2019-05-21 华南理工大学 一种含二氟萘并噻吩二酮吸电子单元的共轭聚合物及其合成方法与应用
CN109776767B (zh) * 2018-12-29 2021-08-10 华南理工大学 一种含二氟萘并噻吩二酮吸电子单元的共轭聚合物及其合成方法与应用

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