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WO2012147564A1 - Composé de poids moléculaire élevé et élément électronique le contenant - Google Patents

Composé de poids moléculaire élevé et élément électronique le contenant Download PDF

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WO2012147564A1
WO2012147564A1 PCT/JP2012/060355 JP2012060355W WO2012147564A1 WO 2012147564 A1 WO2012147564 A1 WO 2012147564A1 JP 2012060355 W JP2012060355 W JP 2012060355W WO 2012147564 A1 WO2012147564 A1 WO 2012147564A1
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二軍 周
敬介 但馬
橋本　和仁
吉村　研
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a polymer compound having a specific structure and an electronic device using the same.
  • the organic thin film solar cell which is one aspect of the photoelectric conversion element can omit the high-temperature and high-vacuum process used in the manufacturing process of the silicon-based solar cell, and can be manufactured at low cost only by the coating process.
  • a polymer compound used for an organic thin film solar cell a polymer compound composed of a repeating unit (A) and a repeating unit (B) has been proposed (Patent Document 1).
  • a photoelectric conversion element having an organic layer containing the polymer compound does not necessarily have a short-circuit current density.
  • An object of the present invention is to provide a polymer compound capable of increasing the short-circuit current density when used in an organic layer constituting an electronic element such as a photoelectric conversion element, and an electronic element using the same.
  • Ar 11 and Ar 12 each independently represent a trivalent group obtained by removing three hydrogen atoms from an aromatic ring, and the aromatic ring may have a substituent.
  • A represents a divalent group represented by formulas (1-1) to (1-12).
  • R 1 to R 15 each independently represents a hydrogen atom or a substituent
  • Ar 21 , Ar 22 and Ar 23 each independently represent an arylene group which may have a substituent or a heteroarylene group which may have a substituent.
  • Ar 31 represents an arylene group having a substituent or a heteroarylene group having a substituent.
  • the repeating unit represented by formula (3) is different from the repeating unit represented by formula (1) and the repeating unit represented by formula (2).
  • a plurality of repeating units represented by the formula (3) are included, they may be the same or different.
  • the arylene group which may have a substituent represented by Ar 23 or the heteroarylene group which may have a substituent is represented by formulas (2-1) to (2-8).
  • X 2a1 and X 2a2 each independently represent a sulfur atom, an oxygen atom or a selenium atom.
  • R 21 and R 22 represent the same meaning as described above.
  • R 40 to R 43 each independently represents a hydrogen atom or a substituent.
  • A represents the same meaning as described above.
  • X 1a1 and X 1a2 each independently represent a sulfur atom, an oxygen atom, a selenium atom, or —N (R) —.
  • R is a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide Represents a group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group.
  • Ar 3a represents an arylene group which may have a substituent or a heteroarylene group which may have a substituent.
  • n is an integer of 1 to 10.
  • X 3a When there are a plurality of X 3a , they may be the same or different.
  • Ar 3a s they may be the same or different.
  • [6] The polymer compound according to any one of [1] to [5] above, wherein the light absorption terminal wavelength is 700 nm or more.
  • [7] The polymer compound according to any one of [1] to [6], wherein the number average molecular weight in terms of polystyrene is 3000 or more.
  • a thin film comprising the polymer compound according to any one of [1] to [7] above.
  • a composition comprising the polymer compound according to any one of [1] to [7] above and an electron-accepting compound.
  • a thin film comprising the composition according to [9] or [10].
  • a solution comprising the polymer compound according to any one of [1] to [7] above or the composition according to [9] or [10] above and a solvent.
  • a first electrode and a second electrode are provided, and an active layer is provided between the first electrode and the second electrode, and the active layer according to the above [1] to [7]
  • the electronic device according to [13] which is a photoelectric conversion device.
  • a solar cell module comprising the photoelectric conversion element according to [14].
  • An image sensor comprising the photoelectric conversion element as described in [14] above.
  • a gate electrode, a source electrode, a drain electrode, and an active layer are provided, and the active compound includes the polymer compound according to any one of [1] to [7] or [9] ] Or the organic thin-film transistor containing the composition as described in [10].
  • the short circuit current density in an electronic device such as a photoelectric conversion device can be improved.
  • ADVANTAGE OF THE INVENTION According to this invention, a photoelectric conversion element with high photoelectric conversion efficiency can be provided by the improvement of a short circuit current density.
  • the polymer compound of the present invention has a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and a repeating unit represented by the formula (3).
  • Ar 11 and Ar 12 each independently represent a trivalent group obtained by removing three hydrogen atoms from an aromatic ring, and the aromatic ring may have a substituent.
  • A represents a divalent group represented by any one of formulas (1-1) to (1-12).
  • R 1 to R 15 each independently represents a hydrogen atom or a substituent
  • Ar 21 , Ar 22 and Ar 23 each independently represent an arylene group which may have a substituent or a heteroarylene group which may have a substituent.
  • Ar 31 represents an arylene group having a substituent or a heteroarylene group having a substituent.
  • the repeating unit represented by formula (3) is different from the repeating unit represented by formula (1) and the repeating unit represented by formula (2).
  • a plurality of repeating units represented by the formula (3) are included, they may be the same or different.
  • a group may have a substituent means that part or all of the hydrogen atoms of the group may be substituted by the substituent.
  • the term “optionally substituted” may be rephrased as “optionally substituted”.
  • a divalent organic group which may have a substituent means a divalent organic group in which part or all of the hydrogen atoms in the divalent organic group may be substituted with a substituent. It refers to a group and may be rephrased as “an optionally substituted divalent organic group”.
  • the “hydrocarbon group optionally having a substituent” means a hydrocarbon group in which part or all of the hydrogen atoms in the hydrocarbon group may be substituted with a substituent. It may be paraphrased as “an optionally substituted hydrocarbon group”.
  • R 1 to R 15 each independently represents a hydrogen atom or a substituent.
  • substituent represented by R 1 to R 15 include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, and an arylalkylthio group.
  • examples thereof include an oxy group, a heterocyclic thio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, a substituted carboxyl group, a nitro group, and a cyano group.
  • R 1 to R 15 are groups containing carbon atoms, the number of carbon atoms is usually about 1 to 60.
  • the alkyl group may be linear or branched, and may be a cycloalkyl group.
  • the number of carbon atoms in the alkyl group is usually about 1-30, preferably 1-20.
  • Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1 -Methylbutyl group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, Chain alkyl groups such as nonyl, decyl, unde
  • the alkyloxy group may be linear or branched, and may be a cycloalkyloxy group.
  • the number of carbon atoms of the alkyloxy group is usually about 1 to 20, preferably 1 to 15.
  • the alkyloxy group may have a substituent.
  • the substituent include a halogen atom and an alkyl group (for example, 1 to 20 carbon atoms).
  • Specific examples of the alkyloxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an iso-propoxy group, a butoxy group, an iso-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyl group.
  • the alkylthio group may be linear or branched, and may be a cycloalkylthio group.
  • the alkylthio group may have a substituent.
  • a halogen atom is mentioned as a substituent.
  • the number of carbon atoms of the alkylthio group which may have a substituent is usually about 1 to 20, preferably 1 to 15. Specific examples of the alkylthio group which may have a substituent include a methylthio group.
  • the aryl group usually has about 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms, and may have a substituent.
  • substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
  • Specific examples of the aryl group which may have a substituent include a phenyl group, a C1-C12 alkyloxyphenyl group, a C1-C12 alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a pentafluorophenyl group. Can be mentioned.
  • C1 to C12 represents the number of carbon atoms, and represents the number of carbon atoms of the group described immediately after the description. Therefore, “C1 to C12” included in the notation such as “C1 to C12 alkyloxyphenyl group” represents that the number of carbon atoms of “alkyl” is 1 to 12.
  • C1-C12 alkyl is preferably C1-C8 alkyl, more preferably C1-C6 alkyl.
  • Specific examples of C1-C12 alkyl, C1-C8 alkyl, and C1-C6 alkyl include those described and exemplified above for the alkyl group. The same applies to the following unless otherwise specified.
  • the aryloxy group usually has about 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms, and the carbon atoms contained in the aromatic ring may have a substituent.
  • substituents include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
  • Specific examples of the aryloxy group which may have a substituent include phenoxy group, C1-C12 alkyloxyphenoxy group, C1-C12 alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluoro A phenyloxy group is mentioned.
  • the arylthio group usually has about 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms, and the carbon atom contained in the aromatic ring may have a substituent.
  • substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
  • Specific examples of the arylthio group which may have a substituent include a phenylthio group, a C1-C12 alkyloxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and pentafluorophenyl.
  • a thio group is mentioned.
  • the arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms, and may have a substituent.
  • substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
  • Specific examples of the arylalkyl group which may have a substituent include a phenyl-C1-C12 alkyl group, a C1-C12 alkyloxyphenyl-C1-C12 alkyl group, and a C1-C12 alkylphenyl-C1-C12 alkyl group. 1-naphthyl-C1-C12 alkyl group, 2-naphthyl-C1-C12 alkyl group.
  • the arylalkyloxy group usually has about 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms, and may have a substituent.
  • substituents include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
  • the arylalkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 30 carbon atoms, and may have a substituent.
  • substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
  • Specific examples of the arylalkylthio group which may have a substituent include phenyl-C1-C12 alkylthio group, C1-C12 alkyloxyphenyl-C1-C12 alkylthio group, C1-C12 alkylphenyl-C1-C12 alkylthio group. 1-naphthyl-C1-C12 alkylthio group, and 2-naphthyl-C1-C12 alkylthio group.
  • Acyl group means a group obtained by removing a hydroxyl group from a carboxyl group (—COOH) in a carboxylic acid.
  • the acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms.
  • acyl group examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and an alkylcarbonyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom such as a trifluoroacetyl group, And a phenylcarbonyl group which may be substituted with a halogen atom such as a benzoyl group and a pentafluorobenzoyl group.
  • Acyloxy group means a group obtained by removing a hydrogen atom from a carboxyl group (—COOH) in a carboxylic acid.
  • the acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms.
  • Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.
  • An amide group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an amide.
  • the amide group usually has about 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms.
  • Specific examples of the amide group include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.
  • the acid imide group refers to a group obtained by removing a hydrogen atom bonded to a nitrogen atom from an acid imide.
  • Specific examples of the acid imide group include a succinimide group and a phthalimide group.
  • the substituted amino group is one in which one or two hydrogen atoms of the amino group are substituted, and the substituent is, for example, an alkyl group and an optionally substituted aryl group.
  • the alkyl group and the optionally substituted aryl group are the same as the specific examples of the alkyl group represented by R 1 and the optionally substituted aryl group.
  • the substituted amino group generally has about 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms.
  • substituent amino group examples include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, tert-Butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, nonylamino, decylamino, 3,7-dimethyloctylamino, laurylamino , Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino
  • a substituted silyl group is one in which 1, 2 or 3 of the hydrogen atoms of the silyl group are substituted, and in general, all three hydrogen atoms of the silyl group are substituted.
  • the substituent include an alkyl group and an optionally substituted aryl group. Specific examples of the alkyl group and the optionally substituted aryl group are the same as the specific examples of the alkyl group represented by R 1 and the optionally substituted aryl group.
  • substituted silyl group examples include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, and tribenzyl.
  • Examples include silyl group, diphenylmethylsilyl group, tert-butyldiphenylsilyl group, dimethylphenylsilyl group and the like.
  • the substituted silyloxy group is a group in which an oxygen atom is bonded to the above substituted silyl group.
  • Specific examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, tri-iso-propylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p -Xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, tert-butyldiphenylsilyloxy group, dimethylphenylsilyloxy group and the like.
  • the substituted silylthio group is a group in which a sulfur atom is bonded to the above substituted silyl group.
  • Specific examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, tri-iso-propylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, tri-p -Xylylsilylthio group, tribenzylsilylthio group, diphenylmethylsilylthio group, tert-butyldiphenylsilylthio group, dimethylphenylsilylthio group and the like.
  • the substituted silylamino group is a group in which one or two hydrogen atoms of the amino group are substituted with a substituted silyl group, and the substituted silyl group is as described above.
  • Specific examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, tri-iso-propylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p -Xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di ( Tripropylsilyl) amino group, di (tri-is
  • the monovalent heterocyclic group examples include furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, triazole, thiadiazole Oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline, chromene, Chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzimidazole, be
  • heterocyclic oxy group examples include a group represented by the formula (11) in which an oxygen atom is bonded to the monovalent heterocyclic group.
  • heterocyclic thio group examples include a monovalent group represented by the formula (12) in which a sulfur atom is bonded to the monovalent heterocyclic group.
  • Ar 7 represents a monovalent heterocyclic group.
  • the heterocyclic oxy group usually has about 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms.
  • the heterocyclic oxy group may have a substituent.
  • Specific examples of the heterocyclic oxy group which may have a substituent include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, Examples include imidazolyloxy group, pyrazolyloxy group, triazolyloxy group, oxazolyloxy group, thiazoleoxy group, and thiadiazoleoxy group.
  • the heterocyclic thio group generally has about 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms.
  • the heterocyclic thio group may have a substituent.
  • Specific examples of the heterocyclic thio group which may have a substituent include thienyl mercapto group, C1-C12 alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C1-C12 alkyl pyridyl mercapto group.
  • the arylalkenyl group usually has 8 to 20 carbon atoms, preferably 8 to 15 carbon atoms. Specific examples of the arylalkenyl group include a styryl group.
  • the arylalkynyl group usually has 8 to 20 carbon atoms, preferably 8 to 15 carbon atoms, and specific examples of the arylalkynyl group include a phenylacetylenyl group.
  • the substituted carboxyl group usually has 2 to 20 carbon atoms, and examples thereof include a group having a methyl ester structure, a group having an ethyl ester structure, and a group having a butyl ester structure.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Ar 11 and Ar 12 represent a group obtained by removing three hydrogen atoms from an aromatic ring.
  • the aromatic ring include a hydrocarbon ring having aromaticity and a heterocyclic ring having aromaticity.
  • the number of carbon atoms in the aromatic hydrocarbon ring is usually 6 to 60, preferably 6 to 20.
  • the hydrocarbon ring may have a substituent.
  • substituents examples include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an acyl group, an acyloxy group, and an amide.
  • the definitions and specific examples of the substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, arylalkenyl group, arylalkynyl group and substituted carboxyl group are the same.
  • the number of carbon atoms in the hydrocarbon ring having aromaticity does not include the number of carbon atoms in the substituent.
  • groups obtained by removing three hydrogen atoms from an aromatic hydrocarbon ring include the following groups.
  • the number of carbon atoms in the aromatic heterocyclic ring is usually 2 to 60, preferably 4 to 20.
  • the heterocyclic ring may have a substituent, and examples of the substituent include the same groups as those described as the substituent that the hydrocarbon ring may have.
  • the number of carbon atoms of the heterocyclic ring is the number of ring carbon atoms constituting the heterocyclic ring, and does not include the number of carbon atoms of the substituent.
  • the heterocycle refers to a ring in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron.
  • Examples of the group obtained by removing three hydrogen atoms from the aromatic heterocyclic ring include the following groups.
  • R ′ represents a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, An arylalkylthio group, a substituted amino group, an acyloxy group, an amide group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group, or a cyano group is represented.
  • R ′ When a plurality of R ′ are contained, they may be the same or different.
  • R ′ is a group containing a carbon atom, the number of carbon atoms is usually about 1 to 60.
  • R ′ halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide Group, arylalkenyl group, arylalkynyl group, and monovalent heterocyclic group and specific examples thereof are the halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group represented by R 1 described above.
  • R ′′ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group.
  • R ′′ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group.
  • R ′′ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group.
  • R ′′ represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group.
  • R ′′ represents a hydrogen atom, an alkyl group, an aryl group,
  • alkyl group, aryl group, arylalkyl group, substituted silyl group, and monovalent heterocyclic group represented by R ′′ are the alkyl group, aryl group, and aryl represented by the aforementioned R 1.
  • the definition and specific examples of the alkyl group, substituted silyl group and monovalent heterocyclic group are the same.
  • Ar 11 and Ar 12 are preferably groups in which three hydrogen atoms have been removed from a heterocyclic ring having aromaticity.
  • the repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1A) from the viewpoint of increasing the short circuit continuous density.
  • A represents the same meaning as described above.
  • X 1a1 and X 1a2 each independently represent a sulfur atom, an oxygen atom, a selenium atom, or —N (R) —.
  • R is a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide Represents a group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group.
  • R is a group containing a carbon atom, the number of carbon atoms is usually about 1 to 60.
  • Halogen atom represented by R alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide group
  • the definitions and specific examples of the arylalkenyl group, arylalkynyl group and monovalent heterocyclic group are the halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group represented by the aforementioned R 1 .
  • arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, acyloxy group, amide group, arylalkenyl group, arylalkynyl group and monovalent heterocyclic group are the same.
  • Preferred examples of the repeating unit represented by the formula (1A) include repeating units represented by the formulas (301) to (325).
  • R represents the same meaning as described above (explained in formula (1A)).
  • the repeating units represented by Formula (301) to Formula (325) from the viewpoint of increasing the conversion efficiency of the photoelectric conversion element, Formula (301), Formula (306), Formula (311), Formula (316) are preferable.
  • Examples of the substituent that the arylene group and the heteroarylene group may have include the same substituents as those represented by R 1 described above.
  • Ar 21 , Ar 22 , and Ar 23 each independently represent an arylene group that may have a substituent or a heteroarylene group that may have a substituent.
  • the number of carbon atoms of the arylene group is usually about 6 to 60, preferably 6 to 20.
  • the number of carbon atoms here is a ring carbon atom constituting an aromatic ring, and does not include the number of carbon atoms contained in the substituent when it has a substituent.
  • the arylene group also includes a group containing a benzene ring, a group containing a condensed ring, a group in which two or more independent benzene rings or two or more condensed rings are directly bonded, or a group bonded via a group such as vinylene.
  • the number of carbon atoms of the heteroarylene group is usually about 2 to 60, preferably 6 to 20.
  • the number of carbon atoms here is a ring carbon atom constituting a heterocyclic ring, and does not include the number of carbon atoms contained in the substituent when it has a substituent.
  • the heteroarylene group is an aromatic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring.
  • Ar 23 is preferably a heteroarylene group which may have a substituent.
  • arylene group which may have a substituent examples include a phenylene group which may have a substituent (for example, Formulas 1 to 3 in the following figure), and a naphthalenediyl group which may have a substituent (see the following figure).
  • Formulas 4 to 13 an anthracenediyl group optionally having a substituent (formulas 14 to 19 in the following figure), biphenyl-diyl group optionally having a substituent (formulas 20 to 25 in the figure below), Examples thereof include a terphenyl-diyl group (formulas 26 to 28 in the following figure) which may have a substituent, and condensed ring compound groups (formulas 29 to 38 in the following figure) which may have a substituent.
  • the fused ring compound group includes a fluorene-diyl group (formulas 36 to 38 in the following figure).
  • Divalent heterocyclic group containing nitrogen as a hetero atom a pyridine-diyl group optionally having a substituent (formulas 39 to 44 in the following figure).
  • a diazaphenylene group which may have a substituent (formulas 45 to 48 in the following figure).
  • a quinolinediyl group which may have a substituent (formulas 49 to 63 in the following figure).
  • a quinoxalinediyl group which may have a substituent (formulas 64-68 in the following figure).
  • An acridinediyl group which may have a substituent (formulas 69 to 72 in the following figure).
  • a bipyridyldiyl group optionally having a substituent (formulas 73 to 75 in the following figure).
  • a phenanthrolinediyl group which may have a substituent (formulas 76 to 78 in the following figure).
  • Groups having a fluorene structure containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 79 to 93 in the following figure).
  • 5-membered heterocyclic groups containing silicon, nitrogen, sulfur, selenium, etc. as heteroatoms (formulae 94-98 in the figure below).
  • 5-membered condensed heterocyclic groups containing silicon, nitrogen, sulfur, selenium and the like as a hetero atom (formulas 99 to 110 in the following figure).
  • a 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, and bonded to the ⁇ -position of the heteroatom to form a dimer or oligomer (formulas 111 to 112 in the figure below).
  • a 5-membered ring heterocyclic group containing silicon, nitrogen, sulfur, selenium, etc. as a heteroatom, and bonded to the phenyl group at the ⁇ -position of the heteroatom (Formula 113 to 119 in the following figure).
  • a group in which a benzene ring and a thiophene ring are condensed (FIGS. 120 to 122 below).
  • R represents the same meaning as described above (explained in the formula (1A)).
  • R 21 to R 38 each independently represents a hydrogen atom or a substituent.
  • substituent represented by R 21 to R 38 include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, and an arylalkylthio group.
  • R 21 to R 38 are groups containing carbon atoms, the number of carbon atoms is usually about 1 to 60.
  • An alkyl group represented by R 21 to R 38 an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group,
  • the definition and specific examples of the substituted amino group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, monovalent heterocyclic group, and substituted carboxyl group are the alkyl group represented by the aforementioned R 1 , alkyloxy Group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substitute
  • R 21 , R 22 and R 35 are preferably an alkyl group, an alkyloxy group and an alkylthio group, more preferably an alkyl group and an alkyloxy group, and particularly preferably an alkyl group.
  • the alkyl group may be linear or branched, but is preferably branched from the viewpoint of enhancing the solubility of the polymer compound of the present invention.
  • R 23 , R 24 , R 27 , R 28 , R 31 , R 32 , R 33 , R 34 , R 37 and R 38 are preferably halogen atoms or hydrogen atoms, more preferably fluorine atoms or hydrogen atoms. And particularly preferably a hydrogen atom.
  • R 25 , R 26 , R 29 and R 30 are preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an arylalkyl group, and more preferably a hydrogen atom or an arylalkyl group.
  • R 36 is preferably a hydrogen atom, a halogen atom, an acyl group or an acyloxy group, more preferably an acyl group or an acyloxy group.
  • X 21 to X 29 each independently represents a sulfur atom, an oxygen atom or a selenium atom.
  • Ar 23 is preferably a group represented by Formula (2-1) to Formula (2-8).
  • X 21 to X 29 each independently represent a sulfur atom, an oxygen atom or a selenium atom, and preferably sulfur from the viewpoint of increasing the short circuit continuous density.
  • Ar 23 is more preferably a group represented by Formula (2-1), Formula (2-2), or Formula (2-3), and more preferably Formula (2-1), Formula (2- 2), particularly preferably a group represented by (2-1).
  • Ar 21 and Ar 22 are preferably groups represented by the formulas 39 to 122, and more preferably groups represented by the formulas 94 to 98 and the formulas 111 to 113. More preferred are groups represented by formulas 94 to 98, more preferred are groups represented by formulas 96 to 98, and particularly preferred are groups represented by formula 97.
  • the repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2A) from the viewpoint of increasing the short circuit continuous density.
  • X 2a1 and X 2a2 each independently represent a sulfur atom, an oxygen atom or a selenium atom.
  • R 21 and R 22 represent the same meaning as described above.
  • R 40 to R 43 each independently represents a hydrogen atom or a substituent.
  • substituent represented by R 40 to R 43 include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, and an arylalkylthio group.
  • R 40 to R 43 are a group containing a carbon atom, the number of carbon atoms is usually about 1 to 60.
  • An alkyl group represented by R 40 to R 43 an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group,
  • the definition and specific examples of the substituted amino group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, monovalent heterocyclic group, and substituted carboxyl group are the alkyl group represented by the aforementioned R 1 , alkyloxy Group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substitute
  • repeating unit represented by formula (2) examples include repeating units represented by formula (2-1-1) to formula (2-1-9).
  • R 21 and R 22 represent the same meaning as described above.
  • the formulas (2-1-1) to (2-1-9) are preferable. It is a repeating unit.
  • Ar 31 represents an arylene group having a substituent or a heteroarylene group having a substituent.
  • the repeating unit represented by formula (3) is different from the repeating unit represented by formula (1) and the repeating unit represented by formula (2).
  • the arylene group or heteroarylene group in Ar 31 is the same as the arylene group or heteroarylene group in Ar 21 described above, and specific examples include the arylene group and heteroarylene group listed as Formula 122 from Formula 1 above. It is done.
  • Examples of the substituent of the arylene group or heteroarylene group in Ar 31 include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an arylalkyloxy group, an arylalkylthio group, an acyl group, an acyloxy group, an amide group, and an acid.
  • a halogen atom an alkyl group, an alkyloxy group, an alkylthio group, an arylalkyloxy group, an arylalkylthio group, an acyl group, an acyloxy group, an amide group, and an acid.
  • X 3a represents a direct bond, —CR 3a1 ⁇ CR 3a2 —, —C ⁇ C— , —O—, —S—, an alkylene group or an arylene group.
  • R 3a , R 3a1 and R 3a2 represent a hydrogen atom, a halogen atom or an alkyl group.
  • Ar 3a represents an arylene group which may have a substituent or a heteroarylene group which may have a substituent.
  • n is an integer of 1 to 10.
  • the substituent that can be the substituent of the arylene group or heteroarylene group in Ar 31 includes a substituent represented by the formula (3A).
  • X 3a in formula (3A) represents a direct bond, —CR 3a1 ⁇ CR 3a2 —, —C ⁇ C— , —O—, —S—, an alkylene group, or an arylene group.
  • the number of carbon atoms in the alkylene group is usually about 1-20.
  • the alkylene group having 3 or more carbon atoms may be linear or branched, and may have a substituent.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group, a butylene group, and an octylene group.
  • the number of carbon atoms in the arylene group is usually about 6 to 20.
  • the arylene group may have a substituent.
  • examples of the arylene group include a phenylene group, a biphenylene group, and a naphthylene group.
  • R 3a , R 3a1 and R 3a2 represent a hydrogen atom, a halogen atom or an alkyl group.
  • the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group may be linear or branched, and may be a cycloalkyl group.
  • the number of carbon atoms of the alkyl group in R 3a , R 3a1 and R 3a2 is usually 1-30 , preferably 1-20.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl.
  • hexyl group isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group
  • chain alkyl groups such as decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.
  • R 3a is preferably a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group.
  • R 3a1 and R 3a2 are preferably a hydrogen atom, a halogen atom, or an alkyl group, more preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom.
  • Ar 3a is preferably Formula 1, Formula 20, Formula 36, Formula 37, Formula 79, Formula 80, Formula 82, Formula 83, Formula 94, Formula 95, Formula 96, Formula 97, Formula 111, Formula 112, Formula 113. More preferably a group represented by Formula 1, Formula 36, Formula 79, Formula 82, Formula 97, Formula 111, and even more preferably a group represented by Formula 1, Formula 97. And particularly preferred is a group represented by Formula 97.
  • Ar 31 preferably has a substituent represented by formula (3A).
  • substituent represented by the formula (3A) are preferably groups represented by the formulas (3A-1) to (3A-23).
  • R 3a is as described in the formula (3A).
  • Preferred as formula (3A) are groups represented by formula (3A-1) to formula (3A-5), and more preferred are groups represented by formula (3A-2) to formula (3A-4). And particularly preferably a group represented by the formula (3A-3).
  • repeating unit represented by the formula (3) are preferably repeating units represented by the formulas (3-1) to (3-5) from the viewpoint of increasing the short circuit continuous density. .
  • R 3a is as described in formula (3A).
  • the repeating units represented by the formulas (3-1) to (3-5) preferred are repeating units represented by the formulas (3-2) to (3-4), and particularly preferred are the formulas It is a repeating unit represented by (3-3).
  • the polymer compound in the present invention refers to a compound having a weight average molecular weight of 1000 or more.
  • a polymer compound having a weight average molecular weight of 3,000 to 10,000,000 is preferable. If the weight average molecular weight is lower than 3000, defects may occur in film formation during device fabrication, and if it exceeds 10000000, solubility in a solvent and applicability during device fabrication may be degraded.
  • the weight average molecular weight of the polymer compound is more preferably 8000 to 5000000, and particularly preferably 10,000 to 1000000.
  • the weight average molecular weight in the present invention refers to a weight average molecular weight in terms of polystyrene calculated using a standard sample of polystyrene using gel permeation chromatography (GPC).
  • the polymer compound of the present invention When the polymer compound of the present invention is used in an element, it is desirable that the solubility in a solvent is high because of the ease of element production.
  • the polymer compound of the present invention preferably has a solubility capable of producing a solution containing 0.01% by weight (wt)% or more of the polymer compound, and a solution containing 0.1% by weight or more is produced. It is more preferable that it has the solubility which can be made, and it is further more preferable that it has the solubility which can produce the solution containing 0.4 wt% or more.
  • the method for producing the polymer compound of the present invention is not particularly limited, but a method using a Suzuki coupling reaction or a Stille coupling reaction is preferable from the viewpoint of ease of synthesis of the polymer compound.
  • E 1 represents a repeating unit represented by the formula (1)
  • Q 100 and Q 200 each independently represent a dihydroxyboryl group (—B (OH) 2 ) or a boric acid ester residue.
  • E 2 represents a repeating unit represented by the formula (2).
  • T 1 and T 2 each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group.
  • T 3 -E 3 -T 4 (300)
  • E 2 represents a repeating unit represented by the formula (3)
  • T 3 and T 4 each independently represent a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group.
  • the manufacturing method which has a process with which the compound represented by these is made to react in presence of a palladium catalyst and a base is mentioned.
  • the total number of moles of the compound represented by Formula (200) and the compound represented by Formula (300) used for the reaction is based on the number of moles of one or more compounds represented by Formula (100). An excess is preferred.
  • the total number of moles of the compound represented by the formula (200) and the compound represented by the formula (300) used in the reaction is 1 mole, the number of moles of the one or more compounds represented by the formula (100) is 0.00.
  • the amount is preferably 6 to 0.99 mol, and more preferably 0.7 to 0.95 mol.
  • the boric acid ester residue for example, the following formula: (In the formula, Me represents a methyl group, and Et represents an ethyl group.) The monovalent group etc. which are represented by these are illustrated. (In the above formula, “-” on the left side represents a connector.)
  • Examples of the halogen atom represented by T 1 and T 2 in Formula (200) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a bromine atom and an iodine atom are preferable, and a bromine atom is more preferable.
  • Examples of the alkyl sulfonate group represented by T 1 and T 2 in Formula (200) include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.
  • Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group.
  • a benzyl sulfonate group is illustrated as an arylalkyl sulfonate group.
  • Examples of the palladium catalyst used in the Suzuki coupling reaction include a Pd (0) catalyst, a Pd (II) catalyst, and the like.
  • palladium [tetrakis (triphenylphosphine)] palladium acetates, dichlorobis (Triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, etc. are mentioned, but from the viewpoint of ease of reaction (polymerization) operation and reaction (polymerization) rate.
  • Dichlorobis (triphenylphosphine) palladium, palladium acetate, and tris (dibenzylideneacetone) dipalladium are preferred.
  • the addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 mol to 0.5 mol with respect to 1 mol of the compound represented by the formula (100). The amount is preferably 0.0003 mol to 0.1 mol.
  • a phosphorus compound such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine is added as a ligand.
  • the addition amount of the ligand is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the palladium catalyst. is there.
  • Examples of the base used for the Suzuki coupling reaction include inorganic bases, organic bases, inorganic salts and the like.
  • examples of the inorganic base include potassium carbonate, sodium carbonate, barium hydroxide and the like.
  • examples of the organic base include triethylamine and tributylamine.
  • examples of the inorganic salt include cesium fluoride.
  • the addition amount of the base is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the compound represented by the formula (100). is there.
  • the Suzuki coupling reaction is performed in a reaction system in which the Pd (0) catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas.
  • an inert atmosphere such as argon gas or nitrogen gas.
  • it is performed in a system sufficiently deaerated with argon gas or nitrogen gas.
  • the inside of the polymerization vessel (reaction system) is sufficiently replaced with nitrogen gas and deaerated.
  • a compound represented by the formula (100), a compound represented by the formula (200), a compound represented by the formula (300), dichlorobis (triphenylphosphine) palladium (II) is charged into the polymerization container, Further, the polymerization vessel is sufficiently replaced with nitrogen gas and deaerated.
  • a solvent deaerated beforehand by bubbling with nitrogen gas for example, toluene
  • a base deaerated by bubbling with nitrogen gas in advance for example, an aqueous sodium carbonate solution
  • a base deaerated by bubbling with nitrogen gas in advance for example, an aqueous sodium carbonate solution
  • the formula (400) Q 300 -E 3 -Q 400 (400)
  • E 3 represents a repeating unit represented by the formula (1).
  • Q 300 and Q 400 each independently represent a substituted stannyl group.
  • a production method comprising a step of reacting one or more compounds represented by the formula (200) with the compound represented by the formula (200) and the compound represented by the formula (300) in the presence of a palladium catalyst. It is done.
  • Examples of the substituted stannyl group include a group represented by —SnR 100 3 .
  • R 100 represents a monovalent organic group.
  • Examples of the monovalent organic group include an alkyl group and an aryl group.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl.
  • aryl group examples include a phenyl group and a naphthyl group.
  • organotin residues -SnMe 3, -SnEt 3, -SnBu 3, an -SnPh 3, more preferably -SnMe 3, -SnEt 3, is -SnBu 3.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • Examples of the halogen atom represented by T 1 and T 2 in Formula (200) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In view of ease of synthesis of the polymer compound, a bromine atom and an iodine atom are preferable.
  • examples of the catalyst include a method of reacting in an arbitrary solvent under a palladium catalyst.
  • Examples of the palladium catalyst used in the Stille coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst.
  • Specific examples include palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, and bis (dibenzylideneacetone) palladium.
  • Palladium [tetrakis (triphenylphosphine)] and tris (dibenzylideneacetone) dipalladium are preferable from the viewpoints of easy reaction (polymerization) operation and reaction (polymerization) rate.
  • the addition amount of the palladium catalyst used in the Stille coupling reaction is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 per 1 mol of the compound represented by the formula (400). Mol to 0.5 mol, preferably 0.0003 to 0.2 mol.
  • a ligand and a promoter can be used as necessary.
  • the ligand include phosphorus compounds such as triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, tris (2-furyl) phosphine, triphenylarsine, and triphenoxyarsine.
  • Examples include arsenic compounds.
  • the cocatalyst include copper iodide, copper bromide, copper chloride, copper 2-thenoylate (I) and the like.
  • the amount of the ligand or cocatalyst added is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, relative to 1 mol of the palladium catalyst. More preferably, it is 1 mol to 10 mol.
  • the Stille coupling reaction is usually performed in a solvent.
  • the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, toluene, dimethoxyethane, tetrahydrofuran and the like. From the viewpoint of solubility of the polymer compound used in the present invention, toluene and tetrahydrofuran are preferred.
  • reaction time may be the end point when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.
  • the Stille coupling reaction is performed in a reaction system in which the Pd catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas.
  • an inert atmosphere such as argon gas or nitrogen gas.
  • it is performed in a system sufficiently deaerated with argon gas or nitrogen gas.
  • the inside of the polymerization vessel (reaction system) is sufficiently replaced with nitrogen gas and deaerated.
  • a compound represented by the formula (300), a compound represented by the formula (200), a compound represented by the formula (400), and a palladium catalyst are charged into this polymerization vessel, and the polymerization vessel is further filled with nitrogen gas. Replace well and degas.
  • the content of the repeating unit represented by the formula (1) in the polymer compound of the present invention is 10 to 10% from the viewpoint of increasing the photoelectric conversion efficiency with respect to the total of the repeating units of the polymer compound of the present invention. 80 mol% is preferred.
  • the content of the repeating unit represented by the formula (2) in the polymer compound of the present invention is preferably 10 to 80 mol% from the viewpoint of increasing the photoelectric conversion efficiency.
  • the content of the repeating unit represented by the formula (3) in the polymer compound of the present invention is preferably 5 to 50 mol% from the viewpoint of increasing the photoelectric conversion efficiency.
  • the polymer compound of the present invention preferably has a long light absorption terminal wavelength from the viewpoint of increasing the photoelectric conversion efficiency.
  • the light absorption terminal wavelength is preferably 700 nm or more, more preferably 800 nm or more, and particularly preferably 900 nm or more.
  • the light absorption terminal wavelength ( ⁇ th) is expressed as a wavelength value at the terminal on the long wavelength side of the light absorption wavelength.
  • the numerical value of the light absorption terminal wavelength in the present invention is specifically represented by a value obtained by the following method.
  • the light absorption terminal wavelength in this invention can be calculated
  • the intersection point closer to the longer wavelength than the absorption peak point is defined as the second point.
  • a straight line connecting the first point and the second point is taken as a first reference line.
  • the absorbance at the absorption peak point (maximum value) closest to the longest wavelength is 100%.
  • the wavelength at the intersection closer to the longer wavelength than the absorption peak point is used as a reference point.
  • a point on the absorption waveform at a wavelength 100 nm longer than the wavelength of the point is defined as a third point.
  • a point on the absorption waveform that is 150 nm longer than the wavelength of the reference point is defined as a fourth point.
  • a straight line connecting the third point and the fourth point is taken as a second reference line.
  • the polymer compound of the present invention can exhibit high electron and / or hole transport properties, when an organic thin film containing the compound is used in a device, electrons or holes injected from an electrode, or light absorption. The generated charge can be transported. Taking advantage of these characteristics, an organic thin film containing the compound can be suitably used for various devices such as a photoelectric conversion device, an organic thin film transistor, and an organic electroluminescence device. Hereinafter, these elements will be described individually.
  • composition of the present invention contains the polymer compound of the present invention and an electron-accepting compound.
  • the ratio of the electron-accepting compound is preferably 10 to 1000 parts by weight, more preferably 20 to 500 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention. .
  • the heteroaryl group represented by Ra usually has 3 to 60 carbon atoms, and examples thereof include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a quinolyl group, and an isoquinolyl group.
  • Examples of the group having an ester structure represented by Ra include a group represented by the formula (17). (Wherein u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, and R c represents an alkyl group, an aryl group, or a heteroaryl group.)
  • alkyl group, aryl group and heteroaryl group represented by R c are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R a .
  • C 70 fullerene derivative examples include the following.
  • Esters (C70PCBM, [6,6] -Phenyl C 71 butyric acid methyl ester), [6,6] Phenyl-C 85 butyric acid methyl ester (C84PCBM, [6,6] -Phenyl C 85 butyric acid methyl ester), [ 6,6] thienyl -C 61 butyric acid methyl ester ([6,6] -Thienyl C 61 butyric acid methyl ester) and the like.
  • the first aspect of the thin film of the present invention is a thin film containing the polymer compound of the present invention.
  • the 2nd aspect of the thin film of this invention is a thin film containing the composition of this invention.
  • the thickness of the thin film is preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.
  • the photoelectric conversion element having the polymer compound of the present invention has one or more active layers containing the polymer compound of the present invention between a pair of electrodes, at least one of which is transparent or translucent.
  • a preferred form of the photoelectric conversion element having the polymer compound of the present invention is formed from a pair of electrodes, at least one of which is transparent or translucent, and an organic composition of a p-type organic semiconductor and an n-type organic semiconductor. Having an active layer.
  • the polymer compound of the present invention is preferably used as a p-type organic semiconductor.
  • the operation mechanism of the photoelectric conversion element of this embodiment will be described.
  • Light energy incident from a transparent or translucent electrode is an electron-accepting compound (n-type organic semiconductor) such as a fullerene derivative and / or an electron-donating compound (p-type organic semiconductor) such as a polymer compound of the present invention. Absorbed, producing excitons in which electrons and holes are combined.
  • the photoelectric conversion element produced using the polymer compound of the present invention is usually formed on a substrate.
  • the substrate may be any substrate that does not chemically change when the electrodes are formed and the organic layer is formed.
  • Examples of the material for the substrate include glass, plastic, polymer film, and silicon.
  • the opposite electrode that is, the electrode far from the substrate
  • the first active layer containing the polymer compound of the present invention is interposed between a pair of electrodes, at least one of which is transparent or translucent, and the first A photoelectric conversion element including a second active layer containing an electron accepting compound such as a fullerene derivative adjacent to the active layer.
  • the transparent or translucent electrode material examples include a conductive metal oxide film and a translucent metal thin film.
  • transparent or translucent electrode materials include indium oxide, zinc oxide, tin oxide, and conductive materials made of indium / tin / oxide (ITO), indium / zinc / oxide, etc., which are composites thereof.
  • films include NESA, gold, platinum, silver, and copper. ITO, indium / zinc / oxide, and tin oxide are preferable.
  • the electrode manufacturing method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like.
  • an organic transparent conductive film such as polyaniline and derivatives thereof, polythiophene and derivatives thereof may be used.
  • Two or more alloys of these metals are two or more alloys of these metals; one selected from the group consisting of one or more of these metals and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin; Alloys with more than one metal; graphite and graphite intercalation compounds; polyaniline and derivatives thereof; and polythiophene and derivatives thereof.
  • Specific examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
  • the electron-donating compound in addition to the polymer compound of the present invention, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, Examples thereof include polysiloxane derivatives having an aromatic amine residue 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.
  • Examples of the electron-accepting compound include the aforementioned compounds in addition to the polymer compound of the present invention.
  • the ratio of the fullerene derivative is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention. More preferably, it is 500 parts by weight.
  • the thickness of the active layer is usually preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, more preferably 20 nm to 200 nm.
  • a preferred method for producing a photoelectric conversion element is a method for producing an element having a first electrode and a second electrode, and having an active layer between the first electrode and the second electrode, Applying a solution (ink) containing the polymer compound of the present invention and a solvent or a solution containing the composition of the present invention and a solvent on the first electrode by a coating method to form an active layer;
  • This is a method for manufacturing an element including a step of forming a second electrode on a layer.
  • the solvent used for film formation from a solution may be any solvent that dissolves the polymer compound of the present invention or the composition of the present invention.
  • the solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane.
  • the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.
  • a field effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, a gate electrode for controlling the amount of current passing through the current path, and an organic semiconductor layer and a gate electrode It is preferable to provide an insulating layer disposed between the two.
  • the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer (active layer), and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween.
  • the organic semiconductor layer is constituted by an organic thin film containing the polymer compound of the present invention.
  • an organic EL element an element having an anode, a light emitting layer, and a cathode, and an anode, a light emitting layer, and an electron having an electron transport layer containing an electron transport material adjacent to the light emitting layer between the cathode and the light emitting layer.
  • an element having an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode an element having an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.
  • the photoelectric conversion element using the polymer compound of the present invention is operated as an organic thin film solar cell by generating photovoltaic power between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. Can do. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.
  • a photocurrent flows by irradiating light from a transparent or translucent electrode in a state where a voltage is applied between the electrodes or in a state where no voltage is applied.
  • the above-mentioned organic thin film transistor can be used as a pixel driving element used for controlling the pixel of an electrophoretic display, a liquid crystal display, an organic electroluminescence display, etc., and controlling the uniformity of screen luminance and the screen rewriting speed. .
  • the organic thin film solar cell can basically have the same module structure as a conventional solar cell module.
  • the solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side.
  • a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known.
  • the organic thin-film solar cell manufactured using the polymer compound of the present invention can also be appropriately selected from these module structures depending on the purpose of use, place of use and environment.
  • the surface protection layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin. It is possible to eliminate the supporting substrate on one side.
  • the periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material.
  • a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.
  • a solar cell using a flexible support such as a polymer film
  • cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material.
  • the battery body can be produced.
  • a module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 may be used.
  • a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.
  • the number average molecular weight and the weight average molecular weight were determined by gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, trade name: Prominence system) in terms of polystyrene. Chloroform was used as the mobile phase of GPC.
  • Compound 4 was synthesized according to the method described in Macromolecules, 2008, Vol. 41, 8302-8305.
  • Compound 5 was synthesized according to the method described in Macromolecules, 2010, Vol. 43, pp. 821-826.
  • 30.6 mg (0.047 mmol) of compound 3 175 mg (0.235 mmol) of compound 4, 107.4 mg (0.188 mmol) of compound 5, and 10 ml of toluene A uniform solution was obtained.
  • the obtained toluene solution was bubbled with nitrogen for 30 minutes.
  • polymer A The polystyrene equivalent weight average molecular weight of the polymer A measured by GPC was 41100, and the polystyrene equivalent number average molecular weight was 21,000.
  • the light absorption terminal wavelength of the polymer A was 1030 nm.
  • Example 2 (Production and evaluation of organic thin-film solar cells) A glass substrate on which an ITO film having a thickness of 100 nm was formed by a sputtering method was subjected to ultrasonic cleaning using a surfactant solution, water, acetone and 2-propanol in this order. Next, polymer A and phenyl C71-butyric acid methyl ester (C70PCBM) (phenyl C71-butyric acid methyl ester, manufactured by Solenne) were dissolved in a mixed solvent of chloroform and o-dichlorobenzene to produce ink 1. .
  • C70PCBM phenyl C71-butyric acid methyl ester, manufactured by Solenne
  • ink 1 the weight ratio of C70PCBM to the weight of polymer A was 2, and the volume ratio of chloroform to the volume of o-dichlorobenzene was 9.
  • the total weight of the polymer A and the C70PCBM was 1% by weight with respect to the weight of the ink 1.
  • the ink 1 was applied onto a substrate by spin coating to produce an organic film containing the polymer A.
  • the organic film functions as an active layer.
  • the thickness of the organic film was about 80 nm.
  • the thus prepared organic film had a light absorption terminal wavelength of 1030 nm.
  • calcium was vapor-deposited with a thickness of 10 nm on the organic film by a vacuum vapor deposition machine, and then aluminum was vapor-deposited with a thickness of 30 nm to produce an organic thin film solar cell.
  • the shape of the obtained organic thin film solar cell was a rectangle of 3 mm ⁇ 4 mm.
  • the resulting organic thin-film solar cell is irradiated with a certain amount of light through a 2 mm x 3 mm metal mask using a solar simulator (trade name PEC-L11, manufactured by Peccell Technologies, Inc., irradiance 100 mW / cm 2 ).
  • the current and voltage to be measured were measured to obtain photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor.
  • Jsc short circuit current density
  • Voc open end voltage
  • ff fill factor (curve factor)
  • photoelectric conversion efficiency ⁇
  • the obtained organic thin film solar cell was measured for Jsc, Voc, ff, and ⁇ in the same manner as in Example 2.
  • Jsc was 18.73 mA / cm 2
  • Voc was 0.42 V
  • ff was 0.58
  • ⁇ was 4.56%.
  • the polymer A was dissolved in orthodichlorobenzene to prepare a solution having a concentration of the polymer A of 0.5% by weight, and the solution was filtered through a membrane filter to prepare a coating solution.
  • the coating solution was applied onto the silane-treated n-type silicon substrate by spin coating to form a coating film of polymer A having a thickness of about 60 nm. Thereafter, the coating film was heated in a nitrogen atmosphere at 170 ° C. for 30 minutes to form an organic semiconductor thin film of polymer A.
  • the organic semiconductor film functions as an active layer.
  • a metal mask is disposed on the organic semiconductor thin film, and molybdenum trioxide and gold are sequentially stacked on the organic semiconductor thin film by a vacuum deposition method, and a source electrode and a drain electrode having a stacked structure of molybdenum trioxide and gold are formed.
  • An organic transistor was manufactured by manufacturing.
  • the electrical characteristics of the organic transistor were measured using a semiconductor characteristic evaluation system (semiconductor parameter analyzer 4200-SCS, manufactured by KEITHLEY). When the negative gate voltage applied to the gate electrode is increased, the negative drain current is also increased. Therefore, it was confirmed that the organic transistor was a p-type organic transistor.
  • the saturation field effect mobility ⁇ (cm 2 V ⁇ 1 sec ⁇ 1 ) of the carrier in the organic transistor was calculated using the following formula (a) representing the drain current Id in the saturation region of the electrical characteristics of the organic transistor.
  • polymer B The polystyrene equivalent weight average molecular weight of the polymer B measured by GPC was 38600, and the polystyrene equivalent number average molecular weight was 18,900.
  • the light absorption terminal wavelength of the polymer B was 1010 nm.
  • Synthesis example 3 (Synthesis of polymer C) Compound 6 was synthesized according to the method described in JP-T-2009-506519. In a 200 mL flask in which the gas in the flask was replaced with argon, 561 mg (1.00 mmol) of Compound 6 and Compound 7 (4,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxabolan- 2-yl) -2,1,3-benzothiadiazole) (Aldrich) 388.1 mg (1.00 mmol), methyltrialkylammonium chloride (trade name Aliquat 336 (registered trademark), Aldrich) 202 mg was added, Dissolved in 20 ml of toluene.
  • the obtained toluene solution was bubbled with argon for 30 minutes. Thereafter, 2.25 mg of palladium acetate, 12.3 mg of tris (2-methoxyphenyl) phosphine, and 6.5 mL of a 16.7 wt% aqueous sodium carbonate solution were added to the reaction solution, followed by stirring at 100 ° C. for 5 hours. Thereafter, 50 mg of phenylboric acid was added to the reaction solution, and further reacted at 70 ° C. for 2 hours. Thereafter, 2 g of sodium diethyldithiocarbamate and 20 mL of water were added to the reaction solution, followed by stirring under reflux for 2 hours.
  • the organic layer was washed twice with 20 ml of water, then twice with 20 mL of a 3% by weight aqueous acetic acid solution, and further washed twice with 20 mL of water.
  • the obtained solution was poured into methanol to precipitate a polymer.
  • the polymer was filtered and dried, and the resulting polymer was dissolved in 30 mL of o-dichlorobenzene and passed through an alumina / silica gel column.
  • the obtained solution was poured into methanol to precipitate a polymer.
  • the polymer was filtered and dried to obtain 280 mg of a purified polymer.
  • this polymer is referred to as polymer C.
  • the weight average molecular weight was 30,000, and the number average molecular weight was 14,000.
  • Example 2 (Production and evaluation of organic thin-film solar cells)
  • the polymer C was used instead of the polymer A, and the photoelectric conversion efficiency, the short-circuit current density, the open-end voltage, and the fill factor were obtained.
  • Table 1 summarizes the photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor of each organic thin-film solar cell of Examples 2 and 3 and Comparative Examples 1 and 2.

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Abstract

L'objet de la présente invention est un composé de poids moléculaire élevé qui permet d'augmenter la densité de courant de court-circuit quand il est utilisé dans une couche organique contenue dans un élément de conversion photoélectrique. Plus spécifiquement, l'objet de la présente invention est un composé de poids moléculaire élevé contenant un motif de répétition représenté par la formule (1), un motif de répétition représenté par la formule (2) et un motif de répétition représenté par la formule (3).
PCT/JP2012/060355 2011-04-25 2012-04-17 Composé de poids moléculaire élevé et élément électronique le contenant Ceased WO2012147564A1 (fr)

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WO2016076213A1 (fr) * 2014-11-13 2016-05-19 住友化学株式会社 Composition d'encre et élément de conversion photoélectrique produit à l'aide de celle-ci
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CN107431125A (zh) * 2015-03-16 2017-12-01 富士胶片株式会社 有机半导体元件及其制造方法、化合物、有机半导体组合物和有机半导体膜及其制造方法
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