WO2012165128A1 - Composé de masse moléculaire élevée et élément organique de conversion photoélectrique - Google Patents

Composé de masse moléculaire élevée et élément organique de conversion photoélectrique Download PDF

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WO2012165128A1
WO2012165128A1 PCT/JP2012/062249 JP2012062249W WO2012165128A1 WO 2012165128 A1 WO2012165128 A1 WO 2012165128A1 JP 2012062249 W JP2012062249 W JP 2012062249W WO 2012165128 A1 WO2012165128 A1 WO 2012165128A1
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substituted
fluorine atom
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上谷　保則
吉村　研
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 using the same.
  • Organic semiconductor materials are expected to be applied to organic photoelectric conversion elements such as organic solar cells and optical sensors.
  • the functional layer can be manufactured by an inexpensive coating method.
  • organic semiconductor materials that are various polymer compounds for the organic photoelectric conversion element has been studied.
  • an organic semiconductor material for example, 9,9-dioctylfluorene-2,7-diboronic acid ester and 5,5 ′′ ′′-dibromo-3 ′′, 4 ′′ -dihexyl- ⁇ -pentathiophene are polymerized.
  • a polymer compound has been proposed (WO2005 / 092947). However, the polymer compound does not sufficiently absorb light having a long wavelength.
  • the present invention provides a polymer compound having a high absorbance of light having a long wavelength. That is, this invention provides the high molecular compound containing the repeating unit represented by Formula (A), and the repeating unit represented by Formula (B).
  • X 1 and X 2 are the same or different and represent a nitrogen atom or ⁇ CH—.
  • R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom or a substituent.
  • W 1 represents a monovalent organic group having a fluorine atom, a cyano group, or a halogen atom.
  • W 2 represents a monovalent organic group having a fluorine atom, a cyano group, a halogen atom or a hydrogen atom.
  • Q and R are the same or different and are a hydrogen atom, a fluorine atom, an alkyl group which may be substituted with a fluorine atom, an alkoxy group which may be substituted with a fluorine atom, an aryl group which may be substituted, hetero Represents an aryl group or a group represented by formula (2).
  • Plural Qs may be the same or different.
  • a plurality of R may be the same or different. (In the formula, m1 represents an integer of 0 to 6, m2 represents an integer of 0 to 6.
  • R ′ represents an alkyl group which may be substituted with a fluorine atom, or an aryl group which may be substituted. Or represents a heteroaryl group.
  • this invention provides the high molecular compound containing the repeating unit represented by Formula (1).
  • X 1 , X 2 , Y 1 , W 1 , W 2 , Q and R have the same meaning as described above.
  • the present invention is further represented by formula (3).
  • a polymer compound containing a repeating unit is provided.
  • Q and R have the same meaning as described above.
  • the present invention also provides an organic photoelectric conversion element having a pair of electrodes and a functional layer provided between the electrodes, wherein the functional layer includes an electron-accepting compound and the polymer compound.
  • FIG. 1 is a diagram showing an absorption spectrum of a polymer compound 1 described later.
  • FIG. 2 is a diagram showing an absorption spectrum of polymer compound 2 described later.
  • the polymer compound of the present invention includes a repeating unit represented by the above formula (A) and a repeating unit represented by the formula (B).
  • R 1 ⁇ R 3 Specific examples of the substituent represented by the formula: halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), alkyl group, optionally substituted alkoxy group, optionally substituted alkylthio group, substituted Aryl group which may be substituted, aryloxy group which may be substituted, arylthio group which may be substituted, arylalkyl group which may be substituted, arylalkoxy group which may be substituted, substituted Arylalkylthio group, acyl group, acyloxy group, amide group, imide group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, heterocyclic group,
  • the alkyl group may be linear, branched, or cyclic.
  • the alkyl group usually has 1 to 30 carbon atoms.
  • Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl.
  • 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.
  • the alkyl part of the alkoxy group may be linear, branched or cyclic.
  • the alkoxy group may have a substituent.
  • the alkoxy group usually has 1 to 20 carbon atoms, and examples of the substituent of the alkoxy group include a halogen atom and an alkoxy group (for example, 1 to 20 carbon atoms).
  • Specific examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyl group.
  • the alkyl part of the alkylthio group may be linear, branched or cyclic.
  • the alkylthio group may have a substituent.
  • the alkylthio group usually has 1 to 20 carbon atoms, and examples of the substituent of the alkylthio group include a halogen atom.
  • substituent of the alkylthio group include a halogen atom.
  • Specific examples of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, and a cyclohexylthio group.
  • the aryl group means a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and usually has 6 to 60 carbon atoms.
  • the aryl group may have a substituent, and examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms).
  • a preferred embodiment is a C1-C8 alkoxyphenyl group, and a more preferred embodiment is a C1-C6 alkoxyphenyl group.
  • C1 to C8 alkoxy and C1 to C6 alkoxy include those of C1 to C8 and C1 to C6 among the alkoxys exemplified for the above alkoxy group.
  • the aryloxy group usually has 6 to 60 carbon atoms and may have a substituent in the aryl moiety. Examples of the substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms).
  • Specific examples of the aryloxy group which may have a substituent include phenoxy group, C1-C12 alkoxyphenoxy group, C1-C12 alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group and pentafluorophenoxy.
  • the arylthio group usually has 6 to 60 carbon atoms and may have a substituent in the aryl moiety.
  • substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms).
  • Specific examples of the arylthio group which may have a substituent include a phenylthio group, a C1-C12 alkoxyphenylthio group, a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group and a pentafluorophenylthio group.
  • the arylalkyl group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent.
  • substituent include a halogen atom and an alkoxy group (for example, 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 alkoxyphenyl-C1-C12 alkyl group, a C1-C12 alkylphenyl-C1-C12 alkyl group, Examples include 1-naphthyl-C1-C12 alkyl group and 2-naphthyl-C1-C12 alkyl group.
  • the arylalkoxy group usually has 7 to 60 carbon atoms and may have a substituent in the aryl moiety.
  • substituent include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms).
  • Specific examples of the arylalkoxy group which may have a substituent include a phenyl-C1 to C12 alkoxy group, a C1 to C12 alkoxyphenyl-C1 to C12 alkoxy group, a C1 to C12 alkylphenyl-C1 to C12 alkoxy group, Examples include 1-naphthyl-C1 to C12 alkoxy groups and 2-naphthyl-C1 to C12 alkoxy groups.
  • the arylalkylthio group usually has 7 to 60 carbon atoms, and the aryl moiety may have a substituent.
  • substituents include a halogen atom and an alkoxy group (for example, having 1 to 20 carbon atoms).
  • An acyl group means a group excluding a hydroxyl group in —COOH of a carboxylic acid, and usually has 2 to 20 carbon atoms.
  • acyl group examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a trifluoroacetyl group, an alkylcarbonyl group which may be substituted with a halogen having 2 to 20 carbon atoms, a benzoyl group, Examples thereof include a phenylcarbonyl group which may be substituted with a halogen such as a pentafluorobenzoyl group.
  • the acyloxy group means a group excluding a hydrogen atom in —COOH of a carboxylic acid, and usually has 2 to 20 carbon atoms.
  • acyloxy group examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.
  • An amide group means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from an amide, and the carbon number is usually 2 to 20.
  • the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group. , Ditrifluoroacetamide group and dipentafluorobenzamide group.
  • the imide group means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from imide (—CO—NH—CO—), and specific examples include a succinimide group and a phthalimide group.
  • a 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 include R 1 Are the same as the specific examples of the alkyl group and the aryl group which may be substituted.
  • the substituted amino group usually has 1 to 40 carbon atoms.
  • substituted 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 group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, Cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl
  • a substituted silyl group is one in which one, two, or three of the hydrogen atoms of the silyl group are substituted, generally one in which all three hydrogen atoms of the silyl group are substituted. And an aryl group which may be substituted.
  • Specific examples of the alkyl group and the optionally substituted aryl group include R 1 Are the same as the specific examples of the alkyl group and the aryl group which may be substituted.
  • substituted silyl group examples include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, Examples include a diphenylmethylsilyl group, a tert-butyldiphenylsilyl group, and a dimethylphenylsilyl group.
  • the substituted silyloxy group is a group in which an oxygen atom is bonded to the above substituted silyl group.
  • substituted silyloxy group examples include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylyl group.
  • examples thereof include a silyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group.
  • the substituted silylthio group is a group in which a sulfur atom is bonded to the above substituted silyl group.
  • substituted silylthio group examples include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, triisopropylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, and tri-p-xylyl.
  • examples thereof include a silylthio group, a tribenzylsilylthio group, a diphenylmethylsilylthio group, a tert-butyldiphenylsilylthio group, and a dimethylphenylsilylthio group.
  • the substituted silylamino group is one 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, triisopropylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylyl.
  • heterocyclic group optionally substituted furan, thiophene, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiazole, isothiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, prazolidine, furazane, Triazole, thiadiazole, oxadiazole, tetrazole, pyran, pyridine, piperidine, thiopyran, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, triazine, benzofuran, isobenzofuran, benzothiophene, indole, isoindole, indolizine, indoline, isoindoline , Chromene, chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzimid
  • Aromatic heterocyclic groups are preferred.
  • the heterocyclic oxy group include a group represented by the formula (11) in which an oxygen atom is bonded to the above heterocyclic group.
  • the heterocyclic thio group include a group represented by the formula (12) in which a sulfur atom is bonded to the above heterocyclic group.
  • the heterocyclic oxy group usually has 4 to 60 carbon atoms.
  • heterocyclic oxy group examples include thienyloxy group, C1-C12 alkylthienyloxy group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C1-C12 alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyl group. And a ruoxy group, an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group.
  • the heterocyclic thio group usually has 4 to 60 carbon atoms.
  • heterocyclic thio group examples 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, imidazolyl mercapto group, pyrazolyl mercapto group. , Triazolyl mercapto group, oxazolyl mercapto group, thiazole mercapto group and thiadiazole mercapto group.
  • the arylalkenyl group usually has 8 to 20 carbon atoms, and specific examples of the arylalkenyl group include a styryl group.
  • the arylalkynyl group usually has 8 to 20 carbon atoms, and specific examples of the arylalkynyl group include a phenylacetylenyl group.
  • Y 1 Is preferably a sulfur atom, an oxygen atom, or a selenium atom, more preferably a sulfur atom or an oxygen atom, and particularly preferably a sulfur atom.
  • W 1 Represents a monovalent organic group having a fluorine atom, a cyano group or a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom).
  • the monovalent organic group having a fluorine atom include a fluorine atom, Substituted alkyl group, alkoxy group substituted with fluorine atom, alkylthio group substituted with fluorine atom, aryl group substituted with fluorine atom, aryloxy group substituted with fluorine atom, arylthio substituted with fluorine atom Groups.
  • the alkyl group substituted with a fluorine atom is usually one in which one or more hydrogen atoms of an alkyl group having 1 to 30 carbon atoms are substituted with a fluorine atom.
  • Specific examples of the alkyl group include R 1 It is the same as the specific example of the alkyl group represented by these.
  • Specific examples of the alkyl group substituted with a fluorine atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a difluoroethyl group, a pentafluoromethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and a tridecafluorohexyl group.
  • the alkoxy group substituted with a fluorine atom is usually one in which one or more hydrogen atoms of an alkoxyl group having 1 to 20 carbon atoms are substituted with a fluorine atom.
  • Specific examples of the alkoxy group include R 1 It is the same as the specific example of the alkoxy group represented by these.
  • Specific examples of the alkoxy group substituted with a fluorine atom include a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a difluoroethoxy group, a pentafluoromethoxy group, a heptafluoropropoxy group, a nonafluorobutoxy group, and a tridecafluoro group.
  • the alkylthio group substituted with a fluorine atom is usually one in which one or more hydrogen atoms of an alkylthio group having 1 to 20 carbon atoms are substituted with a fluorine atom.
  • alkylthio group examples include R 1
  • the same as the specific examples of the alkylthio group represented by Specific examples of the alkylthio group substituted with a fluorine atom include a fluoromethylthio group, a difluoromethylthio group, a trifluoromethylthio group, a difluoroethylthio group, a pentafluoromethylthio group, a heptafluoropropylthio group, a nonafluorobutylthio group, A decafluorohexylthio group is mentioned.
  • the aryl group substituted with a fluorine atom is usually one in which one or more hydrogen atoms of a phenyl group or a naphthyl group are substituted with a fluorine atom.
  • Specific examples of the aryl group substituted with a fluorine atom include fluorophenyl Group, difluorophenyl group, trifluorophenyl group, pentafluorophenyl group, fluorobiphenyl group, nonafluorobiphenyl group, fluoronaphthyl group and heptafluoronaphthyl group.
  • the aryloxy group substituted with a fluorine atom is a group in which an oxygen atom is bonded to the above aryl group substituted with a fluorine atom.
  • Specific examples of the aryloxy group substituted with a fluorine atom include fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, fluorobiphenyloxy group, nonafluorobiphenyloxy group, fluoronaphthyloxy group, hepta A fluoronaphthyloxy group is mentioned.
  • the arylthio group substituted with a fluorine atom is a group in which a sulfur atom is bonded to the above aryl group substituted with a fluorine atom.
  • Specific examples of the arylthio group substituted with a fluorine atom include a fluorophenylthio group, a difluorophenylthio group, a trifluorophenylthio group, a pentafluorophenylthio group, a fluorobiphenylthio group, a nonafluorobiphenylthio group, and a fluoronaphthylthio group. Group and heptafluoronaphthylthio group.
  • W 1 Is preferably a halogen atom, more preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.
  • W 2 The definition and specific examples of the monovalent organic group having a fluorine atom represented by 1
  • the definition and specific examples of the monovalent organic group having a fluorine atom represented by W 2 Is preferably a halogen atom, more preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.
  • X 1 And X 2 are the same or different and each represents a nitrogen atom or ⁇ CH—, preferably X 1 And X 2 At least one of them is a nitrogen atom, more preferably X 1 And X 2 Is a nitrogen atom.
  • Examples of the repeating unit represented by the formula (A) include repeating units represented by the formulas (1001) to (1240). In formula (1001) to formula (1240), R 1 , R 2 And R 3 Represents the same meaning as described above.
  • 1001) Is a structural unit.
  • alkyl group represented by Q or R examples include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and octyl group. , Isooctyl group, decyl group, dodecyl group, pentadecyl group, and octadecyl group.
  • a hydrogen atom in the alkyl group may be substituted with a fluorine atom.
  • Examples of the alkyl group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
  • Examples of the alkoxy group represented by Q or R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group.
  • a hydrogen atom in the alkoxy group may be substituted with a fluorine atom.
  • Examples of the alkoxy group in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluorobutoxy group, a perfluorohexyloxy group, and a perfluorooctyloxy group.
  • the aryl group represented by Q or R is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon.
  • 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 number of carbon atoms of the aryl group is preferably 6 to 60, and more preferably 6 to 30.
  • the hydrogen atom in the aryl group may be substituted.
  • 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 halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group, and an alkoxy group. Specific examples of the alkyl group and alkoxy group are the same as the specific examples of the alkyl group and alkoxy group represented by R.
  • the heteroaryl group represented by Q or 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 halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group, and an alkoxy group.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom
  • alkyl group and alkoxy group Specific examples of the alkyl group and alkoxy group are the same as the 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 that may be substituted with a fluorine atom, an aryl group that may be substituted, or a heteroaryl group. Definitions and specific examples of the alkyl group which may be substituted with the fluorine atom represented by R ′, the aryl group which may be substituted and the heteroaryl group may be substituted with the fluorine atom represented by R. The definition and specific examples of the good alkyl group, the optionally substituted aryl group and the heteroaryl group are the same.
  • an alkyl group or alkoxy group which may be substituted with a fluorine atom from the viewpoint of solubility of the polymer compound in a solvent, an alkyl group or alkoxy
  • the group preferably has 1 to 20 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms.
  • Examples of the repeating unit represented by the formula (B) include the following repeating units.
  • 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).
  • X 1 , X 2 , Y 1 , W 1 , W 2 , Q and R have 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 polymer compound of the present invention preferably further contains a repeating unit represented by the formula (3).
  • Q and R have the same meaning as the above-mentioned.
  • Examples of the repeating unit represented by the formula (3) include the following repeating units.
  • the amount of the repeating unit represented by the formula (3) contained in the polymer compound of the present invention is such that the polymer is from the viewpoint of increasing the photoelectric conversion efficiency of the organic photoelectric conversion device having a functional layer containing the polymer compound.
  • the amount is preferably 10 to 80 mol%, more preferably 20 to 80 mol%, based on the total amount of repeating units contained in the compound.
  • the weight average molecular weight in terms of polystyrene of the polymer compound of the present invention is preferably 10 3 ⁇ 10 8 And more preferably 10 3 ⁇ 10 7 And more preferably 10 3 ⁇ 10 6 It is.
  • the ratio between the number of repeating units represented by formula (1) and the number of repeating units represented by formula (3) is preferably 10:90 to 90:10. More preferably, it is 20:80 to 80:20.
  • the ratio between the number of repeating units represented by formula (A) and the number of repeating units represented by formula (3) is preferably 10:90 to 90:10. More preferably, it is 20:80 to 80:20.
  • the ratio between the number of repeating units represented by formula (B) and the number of repeating units represented by formula (3) is preferably 10:90 to 90:10. More preferably, it is 20:80 to 80:20.
  • 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 includes a repeating unit represented by the formula (A), a repeating unit represented by the formula (B), a repeating unit represented by the formula (1), and a repeating represented by the formula (3).
  • 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 heteroarylene group include a flangyl group, a pyrrole diyl group, a pyridinediyl group, and the like.
  • 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 monomer can be synthesized with reference to, for example, a method disclosed in US2008 / 145571 and JP-A-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 adds a ligand as necessary to have a boronic acid residue or a boronic 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 containing the repeating unit represented by the formula (1) polymerizes, for example, a compound represented by the formula (4) and a compound represented by the formula (5). Can be manufactured.
  • the polymerization reaction include a Suzuki coupling reaction. (In formula (4), R and Q have the same meaning as described above. Z represents a boronic acid or boronic acid ester residue.
  • the boronic ester residue represented by Z represents a group in which one hydrogen atom has been removed from the boronic ester, and specific examples thereof include groups represented by the following formula.
  • Me represents a methyl group
  • Et represents an ethyl group.
  • the compound represented by formula (4) can be produced by reacting the compound represented by formula (6) with diboronic acid or diboronic acid ester in an organic solvent.
  • the diboronic acid or diboronic acid ester to be reacted with the compound represented by the formula (6) is preferably a diboronic acid ester from the viewpoint of reactivity.
  • the diboronic acid ester include the following structures (B-1) to (B-6).
  • the diboronic acid ester is preferably (B-1) or (B-3), particularly preferably (B-3).
  • the amount of diboronic acid or diboronic acid ester used is usually 2 molar equivalents (hereinafter, the molar equivalents are simply referred to as equivalents) to 10 equivalents with respect to the compound represented by formula (6), preferably 2 to 4 equivalents, more preferably 2 to 3 equivalents.
  • the reaction of the compound represented by formula (6) with diboronic acid or diboronic acid ester is usually carried out in an organic solvent.
  • organic solvent include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ether solvents, halogens.
  • aromatic hydrocarbon solvent include benzene, toluene, xylene, cumene and the like.
  • Examples of the aliphatic hydrocarbon solvent include hexane, octane, decane and the like.
  • ether solvent examples include diethyl ether, dibutyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane and the like.
  • halogenated hydrocarbon solvent examples include dichloromethane, chloroform, chlorobenzene, dichlorobenzene and the like.
  • aprotic polar solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and the like.
  • the solvent is preferably an aromatic hydrocarbon solvent or an ether solvent, and more preferably an ether solvent.
  • ether solvents tetrahydrofuran and 1,4-dioxane are preferable, and 1,4-dioxane is more preferable.
  • the reaction between the compound represented by formula (6) and diboronic acid or diboronic acid ester is preferably performed in the presence of a catalyst.
  • the catalyst include a palladium catalyst, a rhodium catalyst, a ruthenium catalyst, and a platinum catalyst, and among them, a palladium catalyst is preferable.
  • the palladium catalyst include a Pd (0) catalyst and a Pd (II) catalyst.
  • palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (triphenylphosphine) palladium, palladium acetate, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, dichlorobis (diphenyl) Phosphinoferrocene) palladium, and dichlorobis (diphenylphosphinoferrocene) palladium is preferred from the viewpoint of ease of reaction operation and reaction rate.
  • 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 (6), The amount is preferably 0.0003 mol to 0.2 mol.
  • a ligand can be used as necessary. Examples of the ligand include triphenylphosphine, tri (o-tolyl) phosphine, tri (o-methoxyphenyl) phosphine, tris (2-furyl) phosphine, 1,1′-bis (diphenylphosphino) ferrocene, and the like.
  • the ligand is preferably 1,1′-bis (diphenylphosphino) ferrocene.
  • 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 with respect to 1 mol of the palladium catalyst. ⁇ 10 moles.
  • the temperature at which the compound represented by formula (6) is reacted with diboronic acid or diboronic acid ester is usually about 50 to 160 ° C., preferably 60 to 120 ° C., although it depends on the solvent. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
  • reaction time may be analyzed by high performance liquid chromatography or the like and the end point may be when the target conversion rate is reached, but is usually about 0.1 to 200 hours. About 1 to 30 hours is efficient and preferable.
  • the compound represented by formula (6) is, for example, Macromolecules, 2009, Vol. 42, No. 17, p. 6564 to 6571 (Macromolecules, 42 (17), 6564 (2009)).
  • the polymer compound containing the repeating unit represented by the formula (3) can be produced by polymerizing the compound represented by the formula (7) and the compound represented by the formula (4). Examples of the polymerization reaction include a Suzuki coupling reaction. (In the formula, R has the same meaning as described above.
  • a plurality of R may be the same or different.
  • the compound represented by formula (7) can be produced, for example, by reacting the compound represented by formula (8) with a brominating agent.
  • a brominating agent include bromine and N-bromosuccinimide (NBS). NBS is preferable.
  • the reaction between the brominating agent and the compound represented by formula (7) is usually carried out in a solvent.
  • the solvent include chloroform, dichloromethane, carbon tetrachloride, tetrahydrofuran (THF), 1,4-dioxane, N, N-dimethylformamide (DMF) and the like.
  • the temperature at which the brominating agent and the compound represented by formula (7) are reacted is usually -50 ° C to 100 ° C, preferably -20 ° C to 40 ° C, particularly preferably -10 ° C to 20 ° C. It is.
  • the amount of the brominating agent to be reacted is usually 2 to 10 equivalents, preferably 2 to 4 equivalents, more preferably 2 to 3 equivalents, relative to the compound represented by the formula (7).
  • the reaction time of the brominating agent and the compound represented by the formula (7) is usually 1 minute to 10 hours, preferably 30 minutes to 5 hours.
  • the reaction normal post-treatment can be performed to obtain the compound represented by the formula (7).
  • 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 formula (8) can be produced, for example, by reacting the compound represented by formula (9) in the presence of an acid.
  • the acid used in the reaction for producing the compound represented by the formula (8) from the compound represented by the formula (9) 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 (8) from the compound represented by formula (9) 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 hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, Halogenated saturated hydrocarbon solvents such as chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, t
  • the reaction may be used alone or in combination.
  • normal post-treatment can be performed to obtain the compound represented by the formula (8).
  • 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 (9) can be produced, for example, by reacting the compound represented by the formula (10) with a Grignard reagent or an organolithium compound.
  • methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, propylmagnesium chloride, propylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, hexylmagnesium bromide, octylmagnesium 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 (9) from the compound represented by the formula (10) and the Grignard reagent or the organic lithium compound is preferably carried out in an inert gas atmosphere such as nitrogen or argon. 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, Examples include ether solvents such as tetrahydrofuran, tetrahydropyran, and dioxane. 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 (9).
  • the compound represented by the formula (10) can be produced, for example, by reacting the compound represented by the formula (11) 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 (10) from the compound represented by the formula (11) 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 obtained by mixing a carboxylic acid solvent with one or more solvents selected from the group consisting of carbon tetrachloride, chloroform, dichloromethane, benzene, and toluene. It is preferable to carry out the reaction.
  • the reaction temperature is preferably 0 ° C. or higher and 50 ° C. or lower.
  • the reaction normal post-treatment can be performed to obtain the compound represented by the formula (10).
  • 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 methods such as chromatographic fractionation and recrystallization.
  • a compound represented by Formula (7) the following compound is mentioned, for example. Since the polymer compound of the present invention has a high absorbance of light having a long wavelength such as 600 nm light and efficiently absorbs sunlight, an organic photoelectric conversion element manufactured using the polymer compound of the present invention has a short-circuit current. Density increases. Further, the polymer compound of the present invention has a large ionization potential and can obtain a large open-circuit voltage.
  • 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 and a fullerene derivative are 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. 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, more preferably 40 to 250 parts by weight with respect to 100 parts by weight of the polymer. The amount is preferably 80 to 120 parts by weight. From the viewpoint of increasing the short-circuit current density, the amount of the fullerene derivative in the functional layer is preferably 20 to 250 parts by weight and more preferably 40 to 120 parts by weight with respect to 100 parts by weight of the polymer.
  • the organic photoelectric conversion element In order for the organic photoelectric conversion element to have high photoelectric conversion efficiency, an absorption region in which the electron-accepting compound and the polymer compound represented by the formula (1) can efficiently absorb a spectrum of desired incident light is provided. It is important that the heterojunction interface contains many heterojunction interfaces in order to efficiently separate excitons, and that the heterojunction interface has a charge transporting property to quickly transport the charges generated by the heterojunction interface to the electrode. is there. From such a viewpoint, as the organic photoelectric conversion element, the above 1. And 2. From the standpoint of including a large number of heterojunction interfaces, the organic photoelectric conversion element is preferable. The organic photoelectric conversion element is more preferable.
  • 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.
  • the material for the substrate include glass, plastic, polymer film, and silicon.
  • the opposite electrode that is, the electrode far from the substrate
  • a material for the pair of electrodes a metal, a conductive polymer, or the like can be used.
  • the material of one of the pair of electrodes is preferably a material having a low work function.
  • 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 for the transparent or translucent electrode examples 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.
  • materials used for the charge transport layer as an additional layer that is, a hole transport layer or an 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 has a thickness of usually 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 said high molecular compound individually by 1 type, or may contain it in combination of 2 or more types.
  • 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.
  • the electron-donating compound that the organic thin film may contain in addition to the polymer compound having the repeating unit represented by the formula (1) include, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligos.
  • Thiophene and derivatives thereof polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof Derivatives, polythienylene vinylene and its derivatives.
  • Examples of the electron accepting compound include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone derivatives.
  • Diphenyldicyanoethylene and derivatives thereof diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, C 60 And phenanthroline derivatives such as carbon nanotubes and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
  • 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.
  • Fullerene and its derivatives 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 a group having an alkyl group, an aryl group, a heteroaryl group or an ester structure. Multiple R a May be the same or different.
  • R b Represents an alkyl group or an aryl group. Multiple R b May be the same or different.
  • R a And R b The definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R.
  • R a Examples of the group having an ester structure represented by the formula (V) include a group represented by the formula (V). (Wherein u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, R c Represents an alkyl group, an aryl group or a heteroaryl group.
  • the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by are the same as the definitions and specific examples of the alkyl group, aryl group and heteroaryl group represented by R.
  • C 60 Specific examples of the derivatives include the following.
  • C 70 Specific examples of the derivatives 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.
  • the solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, Halogenated saturated hydrocarbon solvents such as chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, tetrahydrofuran, tetrahydro Examples include ether
  • 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.
  • reaction solution was again cooled to ⁇ 78 ° C., and a hexane solution of n-BuLi (2.6 M, 62 mL, 161 mmol) was added dropwise over 15 minutes. After dropping, the reaction solution was stirred at ⁇ 25 ° C. for 2 hours, and further stirred at room temperature (25 ° C.) for 1 hour. Thereafter, the reaction solution was cooled to ⁇ 25 ° C., and a solution in which 60 g (236 mmol) of iodine was dissolved in 1000 mL of diethyl ether was added dropwise over 30 minutes.
  • the flask was cooled to room temperature (25 ° C.) and diluted with 100 mL of chloroform.
  • the obtained solution was poured into 300 mL of 5 wt% aqueous sodium sulfite solution and stirred for 1 hour.
  • the organic layer of the obtained mixture was separated with a separatory funnel, and the aqueous layer was extracted with chloroform three times.
  • the obtained extract was combined with the organic layer separated earlier and dried over sodium sulfate, and the solvent was distilled off with an evaporator.
  • the obtained yellow solid was dissolved in 90 mL of methanol heated to 55 ° C., and then cooled to 25 ° C.
  • reaction solution was cooled to room temperature and filtered using Celite as a filter aid.
  • the filtrate was neutralized with sodium hydrogen carbonate, and the precipitated solid was obtained by filtration.
  • the obtained solid is suspended in chloroform, insoluble matter is removed by filtration with a polytetrafluoroethylene filter having a pore size of 0.45 ⁇ m, and the solvent of the filtrate is distilled off with an evaporator to give a light brown solid compound 2.86 g of 12 was obtained.
  • polymer compound 1 The polymer was filtered and dried, the resulting polymer was redissolved in 8 mL of o-dichlorobenzene, passed through an alumina / silica gel column, the resulting solution was poured into methanol to precipitate the polymer, the polymer was filtered and dried, 26 mg of purified polymer was obtained.
  • this polymer is referred to as polymer compound 1.
  • Example 2 (Synthesis of polymer compound 2) 76.0 mg (0.098 mmol) of Compound 11 and 50.0 mg (0.098 mmol) of Compound 13, methyltrialkylammonium chloride (trade name Aliquat 336 (registered trademark), Aldrich) 50.0 mg) was added, dissolved in 10 mL of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Then, 0.43 mg of palladium acetate, 2.36 mg of tris (2-methoxyphenyl) phosphine (Tris (2-methoxyphenyl) phosphine), 1 mL of aqueous sodium carbonate (16.7 wt. Stir for 5 hours.
  • methyltrialkylammonium chloride trade name Aliquat 336 (registered trademark), Aldrich
  • the polymer compound 2 had a polystyrene-equivalent weight average molecular weight of 18,000 and a polystyrene-equivalent number average molecular weight of 5900.
  • the weight average molecular weight in terms of polystyrene of the polymer compound 3 was 1.1 ⁇ 10 5 .
  • Measurement Example 1 Measurement of absorbance of organic thin film
  • the polymer compound 1 was dissolved in o-dichlorobenzene at a concentration of 1.0% by weight to prepare a coating solution.
  • the obtained coating solution was applied onto a glass substrate by spin coating.
  • the coating operation was performed at 23 ° C.
  • 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
  • the polymer compound 2 was dissolved in o-dichlorobenzene at a concentration of 1.0% by weight to prepare a coating solution.
  • the obtained coating solution was applied onto a glass substrate by spin coating.
  • the coating operation was performed at 23 ° C.
  • 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.
  • Comparative Example 1 Measurement of absorbance of organic thin film
  • An organic thin film was prepared in the same manner as in Measurement Example 1 except that the high molecular compound 3 was used in place of the high molecular compound 1 and the concentration was 0.5% by weight, and the absorption spectrum of the organic thin film was measured. The measured spectrum is shown in FIG. Table 1 shows the absorbance at 600 nm, 700 nm, 800 nm, and 900 nm.
  • Example 2 (Measurement of ionization potential of organic thin film)
  • the ionization potential of the organic thin film prepared in Example 1 was measured using an atmospheric photoelectron spectrometer (AC-2 manufactured by Riken Keiki Co., Ltd.). The obtained ionization potential was 5.4 eV.
  • Example 3 (Measurement of ionization potential of organic thin film) With the organic thin film created in Measurement Example 2, the ionization potential was measured using an atmospheric photoelectron spectrometer (AC-2 manufactured by Riken Keiki Co., Ltd.). The obtained ionization potential was 5.3 eV.
  • Comparative Example 2 Measurement of ionization potential of organic thin film
  • the ionization potential was measured using an atmospheric photoelectron spectrometer (AC-2 manufactured by Riken Keiki Co., Ltd.). The obtained ionization potential was 5.2 eV.
  • the polymer compound of the present invention containing the repeating unit represented by the formula (A) and the repeating unit represented by the formula (B) has a high absorbance of long-wavelength light and is useful for an organic photoelectric conversion device.

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Abstract

L'invention concerne un composé de masse moléculaire élevée comprenant une unité répétitive représentée par la formule (A) et une unité répétitive représentée par la formule (B), qui présente une absorption élevée d'une lumière ayant une grande longueur d'onde et qui est utile pour un élément organique de conversion photoélectrique. [Dans la formule, X1, et X2 sont identiques ou différents l'un de l'autre et représentent indépendamment un atome d'azote ou =CH- ; Y1 représente un atome de soufre, un atome d'oxygène, un atome de sélénium, -N(R1)- ou -CR2=CR3-; R1, R2 et R3 sont identiques ou différents les uns des autres et représentent indépendamment un atome d'hydrogène ou un substituant ; W1 représente un groupe organique monovalent ayant un atome de fluor, un groupe cyano ou un atome d'halogène ; W2 représente un groupe organique monovalent ayant un atome de fluor, un groupe cyano, un atome d'halogène ou un atome d'hydrogène ; et Q et R sont identiques ou différents l'un de l'autre et représentent indépendamment 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 qui peut être substitué, un groupe hétéroaryle ou un groupe représenté par la formule (2)].
PCT/JP2012/062249 2011-05-27 2012-05-08 Composé de masse moléculaire élevée et élément organique de conversion photoélectrique WO2012165128A1 (fr)

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CN105683193B (zh) * 2013-10-28 2018-09-18 株式会社Lg化学 单分子和包含其的太阳能电池
JP2015151450A (ja) * 2014-02-13 2015-08-24 国立大学法人山形大学 ９，９’−ビフルオレニリデンを骨格に含む重合体及びこれを用いた有機薄膜太陽電池
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