WO2013035564A1 - 高分子化合物及び有機トランジスタ - Google Patents

高分子化合物及び有機トランジスタ Download PDF

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WO2013035564A1
WO2013035564A1 PCT/JP2012/071526 JP2012071526W WO2013035564A1 WO 2013035564 A1 WO2013035564 A1 WO 2013035564A1 JP 2012071526 W JP2012071526 W JP 2012071526W WO 2013035564 A1 WO2013035564 A1 WO 2013035564A1
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宏樹 寺井
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住友化学株式会社
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    • H10K10/40—Organic transistors
    • 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

Definitions

  • the present invention relates to a polymer compound and an organic transistor using the same.
  • organic transistors using organic semiconductor materials are expected to be lighter, have lower manufacturing costs and can be manufactured at lower temperatures than conventional transistors using inorganic semiconductor materials, they are actively researched and developed. Has been done.
  • the field effect mobility which is one of the performances of organic transistors, greatly depends on the field effect mobility of the organic semiconductor material contained in the active layer. Therefore, it is considered to use various organic semiconductor materials for the active layer of the organic transistor.
  • Chemistry of Materials, 2011, Vol. 23, pp. 2185-2200 proposes the following polymer compound having alkoxythiophene as a structural unit as an organic semiconductor material used for an organic transistor.
  • the organic transistor using the above polymer compound has not sufficiently high field effect mobility.
  • the present invention provides a polymer compound having a high field effect mobility and an organic transistor using the same.
  • the present invention is at least one selected from the group consisting of a structural unit represented by formula (1-1), a structural unit represented by formula (1-2), and a structural unit represented by formula (1-3).
  • a polymer compound comprising a seed structural unit and a structural unit represented by formula (2).
  • R 1 is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an aryl group, or a monovalent heterocyclic ring. Represents a group or a halogen atom. When a plurality of R 1 are present, they may be the same or different.
  • R 2 represents an optionally substituted alkyl group having 2 or more carbon atoms.
  • E is, -O -, - S -, - Se- , or -N (R a) - represents a.
  • R a represents a hydrogen atom, an optionally substituted alkyl group, an aryl group, or a monovalent heterocyclic group.
  • Ring A represents an aromatic ring or a heterocyclic ring.
  • n 2 represents an integer of 0 or more, and n 3 represents an integer of 1 to 3. ]
  • Ar ⁇ 1 > represents an arylene group or a bivalent heterocyclic group each independently.
  • Ar 1 is different from the structural unit represented by the formula (1-1), the structural unit represented by the formula (1-2), and the structural unit represented by the formula (1-3).
  • a plurality of Ar 1 may be the same or different.
  • m 1 represents an integer of 3 to 10.
  • the present invention also provides an organic semiconductor material containing the polymer compound. Furthermore, this invention provides the organic-semiconductor element which has an organic layer containing the said organic-semiconductor material.
  • FIG. 1 is a schematic cross-sectional view showing an example of the organic transistor of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another example of the organic transistor of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing another example of the organic transistor of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing another example of the organic transistor of the present invention.
  • FIG. 5 is a schematic cross-sectional view showing another example of the organic transistor of the present invention.
  • FIG. 6 is a schematic cross-sectional view showing another example of the organic transistor of the present invention.
  • FIG. 7 is a schematic cross-sectional view showing another example of the organic transistor of the present invention.
  • FIG. 8 is a schematic cross-sectional view showing another example of the organic transistor of the present invention.
  • FIG. 9 is a schematic cross-sectional view showing another example of the organic transistor of the present invention.
  • 1 is a substrate
  • 2 and 2a are active layers
  • 3 is an insulating layer.
  • 4 represents a gate electrode
  • 5 represents a source electrode
  • 6 represents a drain electrode
  • 100, 110, 120, 130, 140, 150, 160, 170 and 180 represent organic transistors.
  • R 1 Represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an aryl group, a monovalent heterocyclic ring or a halogen atom.
  • the alkyl group may have one or more substituents, and the alkyl group excluding the substituents usually has 1 to 60 carbon atoms, and preferably 1 to 20 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • Specific examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-octadecyl group, Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 3,7,11-trimethyldodecyl group, 2-hexyldecyl group, 2-octyldodecyl group
  • cyclic alkyl groups such as a branched alkyl group such as cyclopentyl group and cyclohexyl group.
  • the alkyl group may have include an alkoxy group (normally 1 to 60 carbon atoms), an aryl group (normally 6 to 60 carbon atoms), a halogen atom, and the like.
  • Specific examples of the substituted alkyl group include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.
  • the alkoxy group may have one or more substituents, and the alkoxy group excluding the substituents usually has 1 to 60 carbon atoms, and preferably 1 to 20 carbon atoms.
  • the alkyl part of the alkoxy group may be linear, branched or cyclic.
  • alkoxy group examples include n-butoxy group, n-hexyloxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, and n-dodecyloxy group.
  • substituent that the alkoxy group may have include an aryl group (normally 6 to 60 carbon atoms), a halogen atom, and the like.
  • the alkylthio group may have one or more substituents, and the alkylthio group excluding the substituents usually has 1 to 60 carbon atoms, and preferably 1 to 20 carbon atoms.
  • the alkyl part of the alkylthio group may be linear, branched or cyclic.
  • alkylthio group examples include n-butylthio group, n-hexylthio group, 2-ethylhexylthio group, 3,7-dimethyloctylthio group and n-dodecylthio group.
  • substituent that the alkylthio group may have include an aryl group (normally 6 to 60 carbon atoms), a halogen atom, and the like.
  • An aryl group is an atomic group obtained by removing one hydrogen atom directly bonded to an aromatic ring from an aromatic hydrocarbon compound which may have a substituent, a group having a benzene ring, a group having a condensed ring, an independent group A group in which two or more selected from an aromatic ring and a condensed ring are directly bonded.
  • the carbon number of the aryl group excluding the substituent of the aromatic hydrocarbon compound is usually 6 to 60, and preferably 6 to 20.
  • aryl group for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, Examples include 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group and 4-phenylphenyl group.
  • substituent that the aromatic hydrocarbon compound may have include an alkyl group (carbon number is usually 1 to 60), an alkoxy group (carbon number is usually 1 to 60), an alkylthio group (carbon number is usually 1 to 60).
  • a monovalent heterocyclic group, a halogen atom, etc. are mentioned.
  • the aryl group containing these groups include 4-hexylphenyl group, 3,5-dimethoxyphenyl group, pentafluorophenyl group and the like.
  • the aromatic hydrocarbon compound has a substituent, the substituent is preferably an alkyl group.
  • the monovalent heterocyclic group is an atomic group obtained by removing one hydrogen atom directly bonded to a ring from an optionally substituted heterocyclic compound, a group having a condensed ring, an independent heterocyclic ring And a group in which two or more selected from fused rings are directly bonded.
  • the number of carbon atoms of the monovalent heterocyclic group excluding the substituent of the heterocyclic compound is usually 2 to 60, and preferably 3 to 20.
  • a monovalent aromatic heterocyclic group is preferable.
  • heterocyclic compound examples include an alkyl group (normally 1 to 60 carbon atoms), an alkoxy group (normally 1 to 60 carbon atoms), an alkylthio group (normally 1 to 60 carbon atoms). ), An aryl group (normally 6 to 60 carbon atoms), a halogen atom, and the like.
  • alkyl group normally 1 to 60 carbon atoms
  • alkoxy group normally 1 to 60 carbon atoms
  • alkylthio group normally 1 to 60 carbon atoms
  • An aryl group normally 6 to 60 carbon atoms
  • a halogen atom examples include a 5-octyl-2-thienyl group and a 5-phenyl-2-furyl group.
  • the substituent is preferably an alkyl group.
  • the halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the R 1 Is preferably a hydrogen atom, an alkoxy group or a halogen atom, more preferably a hydrogen atom or an alkoxy group, and even more preferably a hydrogen atom.
  • R 2 Represents an optionally substituted alkyl group having 2 or more carbon atoms.
  • the number of carbon atoms of the alkyl group, excluding the substituent, represented by the formula is usually 2 to 60, and preferably 2 to 24.
  • R 2 The alkyl group represented by may be linear, branched or cyclic.
  • alkyl group represented by the formula are linear alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-dodecyl group, and n-octadecyl group.
  • Isopropyl group isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 3,7,11-trimethyldodecyl group, 2-hexyldecyl group, 2-octyldodecyl group And branched alkyl groups such as a group, and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group.
  • the alkyl group represented by the formula (1) may have one or more substituents, and examples of the substituent that the alkyl group may have include an alkoxy group (normally 1 to 60 carbon atoms), an aryl group (carbon The number is usually 6 to 60), and halogen atoms and the like can be mentioned.
  • Specific examples of the substituted alkyl group include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.
  • the R 2 Is preferably an alkyl group having 8 or more carbon atoms, more preferably an alkyl group having 12 or more carbon atoms, and still more preferably an alkyl group having 16 or more carbon atoms. Also, from the viewpoint of increasing solubility in order to produce an organic semiconductor element by a printing method, R 2 Is preferably a branched alkyl group. E is -O-, -S-, -Se- or -N (R a )-. R a Represents a hydrogen atom, an optionally substituted alkyl group, an aryl group or a monovalent heterocyclic group.
  • R in the formula (1-1) 1 The same as the definitions and specific examples of the alkyl group, aryl group and monovalent heterocyclic group which may be substituted.
  • E is preferably -S-.
  • Specific examples of the structural unit represented by Formula (1-1) include structural units represented by Formula (1-1-1) to Formula (1-1-11). From the viewpoint of enhancing solubility in order to produce an organic semiconductor element by a printing method, the structural unit represented by formula (1-1) is represented by formula (1-1-1) or formula (1-1-2).
  • Formula (1-1-4) to Formula (1-1-11) are preferable, and Formula (1-1-1), Formula (1-1-2), and Formula (1-1-5) are preferable. It is more preferable that they are the formula (1-1-9) and the formula (1-1-11).
  • the structural unit represented by Formula (1-1) is preferably Formula (1-1-1) to Formula (1-1-6).
  • R 1 Each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an aryl group, a monovalent heterocyclic group or a halogen atom. .
  • R 1 When two or more exist, they may be the same or different. Definitions and specific examples of the optionally substituted alkyl group, the optionally substituted alkoxy group, the optionally substituted alkylthio group, the aryl group, the monovalent heterocyclic group, and the halogen atom are shown in the formula (1).
  • R in -1) 1 The same as the definition and specific examples of the alkyl group which may be substituted, the alkoxy group which may be substituted, the alkylthio group which may be substituted, the aryl group, the monovalent heterocyclic group and the halogen atom represented by It is.
  • N 2 Represents an integer of 0 or more.
  • R 2 Represents an optionally substituted alkyl group having 2 or more carbon atoms.
  • the definition, specific examples and preferred examples of the optionally substituted alkyl group having 2 or more carbon atoms are represented by R in the formula (1-1). 2 Are the same as the definitions, specific examples and preferred examples of the optionally substituted alkyl group having 2 or more carbon atoms.
  • E is -O-, -S-, -Se-, or -N (R a )-.
  • R a Represents a hydrogen atom, an optionally substituted alkyl group, an aryl group or a monovalent heterocyclic group.
  • R in the formula (1-1) 1 The same as the definitions and specific examples of the alkyl group, aryl group and monovalent heterocyclic group which may be substituted.
  • a preferable example of E is the same as the preferable example of E in the formula (1-1).
  • Ring A represents an aromatic ring or a heterocyclic ring. Ring A is condensed with a 5-membered ring containing E.
  • the carbon number of the aromatic ring represented by ring A is usually 6 to 60, and preferably 6 to 20.
  • the number of carbon atoms of the heterocyclic ring represented by ring A is usually 2 to 60, and preferably 3 to 20.
  • Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, and a pentacene ring.
  • Examples of the heterocyclic ring include a furan ring, a thiophene ring, a selenophene ring, a pyrrole ring, and a thienothiophene ring. And a benzothiophene ring.
  • the ring A is preferably a heterocyclic ring, more preferably a thiophene ring, a thienothiophene ring, or a benzothiophene ring.
  • Specific examples of the structural unit represented by Formula (1-2) include the structural units represented by Formula (1-2-1) to Formula (1-2-9).
  • the structural unit represented by the formula (1-2) includes the formula (1-2-1) to the formula (1-2-3).
  • Formula (1-2-1) is more preferable.
  • R 1 Each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an aryl group, a monovalent heterocyclic group or a halogen atom. . Multiple R 1 May be the same or different. Definitions and specific examples of the optionally substituted alkyl group, the optionally substituted alkoxy group, the optionally substituted alkylthio group, the aryl group, the monovalent heterocyclic group, and the halogen atom are shown in the formula (1).
  • R in -1) 1 The same as the definition and specific examples of the alkyl group that may be substituted, the alkoxy group that may be substituted, the alkylthio group that may be substituted, the aryl group, the monovalent heterocyclic group, and the halogen atom It is.
  • N 3 Represents an integer of 1 to 3.
  • E represents -O-, -S-, -Se-, or -N (R a )-.
  • R a Represents a hydrogen atom, an optionally substituted alkyl group, an aryl group or a monovalent heterocyclic group.
  • R in the formula (1-1) 1 The same as the definitions and specific examples of the alkyl group, aryl group and monovalent heterocyclic group which may be substituted.
  • a preferred example of E is the same as the preferred example of E in the formula (1-1).
  • Specific examples of the structural unit represented by Formula (1-3) include structural units represented by Formula (1-3-1) to Formula (1-3-6). From the viewpoint of enhancing solubility in order to produce an organic semiconductor element by a printing method, the structural unit represented by formula (1-3) is represented by formula (1-3-2) or formula (1-3-3). It is preferable that it is Formula (1-3-2).
  • the structural unit represented by Formula (1-3) is preferably Formula (1-3-1) to Formula (1-3-4).
  • the structural unit represented by the formula (1-1) is a polymer compound as a structural unit represented by the formula (1-A), the formula (1-B) or the formula (1-C) in which two units are connected. It is preferable that it is contained in. [Wherein R 1 , R 2 And E independently represent the same meaning as described above.
  • R 1 Each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylthio group, an aryl group, a monovalent heterocyclic group or a halogen atom. . Multiple R 1 May be the same or different. Definitions and specific examples of the optionally substituted alkyl group, the optionally substituted alkoxy group, the optionally substituted alkylthio group, the aryl group, the monovalent heterocyclic group, and the halogen atom are as defined in the above formula (1).
  • R in -1) 1 The same as the definition and specific examples of the alkyl group which may be substituted, the alkoxy group which may be substituted, the alkylthio group which may be substituted, the aryl group, the monovalent heterocyclic group and the halogen atom represented by It is.
  • R 2 Each independently represents an optionally substituted alkyl group having 2 or more carbon atoms. Multiple R 2 May be the same or different.
  • the definition, specific examples and preferred examples of the optionally substituted alkyl group having 2 or more carbon atoms are represented by R in the formula (1-1). 2 Are the same as the definition, specific examples and preferred examples of the alkyl group which may be substituted with 2 or more carbon atoms.
  • E is independently -O-, -S-, -Se- or -N (R a )-.
  • R a Represents a hydrogen atom, an optionally substituted alkyl group, an aryl group or a monovalent heterocyclic group.
  • Definitions and specific examples of the alkyl group, aryl group and monovalent heterocyclic group which may be substituted are as follows: R in the formula (1-1) 1 The same as the definitions and specific examples of the alkyl group, aryl group and monovalent heterocyclic group which may be substituted.
  • a preferable example of E is the same as the preferable example of E in the formula (1-1).
  • the structural unit represented by the formula (1-A) include structural units represented by the formula (1-A-1) to the formula (1-A-8). From the viewpoint of ease of synthesis, the structural unit represented by Formula (1-A) is preferably Formula (1-A-1) to Formula (1-A-3). Specific examples of the structural unit represented by the formula (1-B) include structural units represented by the formula (1-B-1) to the formula (1-B-8). From the viewpoint of ease of synthesis, the structural unit represented by Formula (1-B) is preferably Formula (1-B-1) to Formula (1-B-3). Specific examples of the structural unit represented by the formula (1-C) include structural units represented by the formula (1-C-1) to the formula (1-C-8).
  • the structural unit represented by Formula (1-C) is preferably Formula (1-C-1) to Formula (1-C-3).
  • Ar 1 Each independently represents an arylene group or a divalent heterocyclic group. Multiple Ar 1 May be the same or different.
  • M in formula (2) 1 Represents an integer of 3 to 10, m from the viewpoint of ease of synthesis. 1 Is preferably an integer of 3 to 7, more preferably an integer of 3 to 5, and even more preferably 3.
  • the arylene group is an atomic group obtained by removing two hydrogen atoms directly bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon compound which may have a substituent, and includes a group having a condensed ring.
  • a group in which two or more selected from an aromatic ring and a condensed ring which are independent divalent groups are directly bonded is not included in the arylene group defined here.
  • the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, and a halogen atom.
  • alkyl groups, alkoxy groups, alkylthio groups, aryl groups, monovalent heterocyclic groups and halogen atoms are as follows: R in the above formula (1-1) 1
  • the definition and specific examples of the alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group and halogen atom represented by the formula are the same.
  • the carbon number of the arylene group not containing a substituent is usually 6 to 60, and preferably 6 to 20.
  • arylene group examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthenediyl group, a tetracenediyl group, a pyrenediyl group, a pentacenediyl group, a perylenediyl group, and a fluorenediyl group.
  • the divalent heterocyclic group is an atomic group obtained by removing two hydrogen atoms directly bonded to a ring from a heterocyclic compound which may have a substituent, and includes a group having a condensed ring.
  • a group in which two or more selected from a heterocyclic ring and a condensed ring which are independent divalent groups are directly bonded is not included in the divalent heterocyclic ring defined herein.
  • the carbon number of the divalent heterocyclic group excluding the substituent of the heterocyclic compound is usually 2 to 60, and preferably 3 to 20.
  • the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a monovalent heterocyclic group, and a halogen atom.
  • alkyl groups, alkoxy groups, alkylthio groups, aryl groups, monovalent heterocyclic groups and halogen atoms are as follows: R in the above formula (1-1) 1
  • the definition and specific examples of the alkyl group, alkoxy group, alkylthio group, aryl group, monovalent heterocyclic group and halogen atom represented by the formula are the same.
  • Ar 1 At least one of these is preferably an arylene group having an electron-withdrawing substituent or a carbonyl group from the viewpoint of further increasing the field-effect mobility of the polymer compound of the present invention.
  • Ar 1 At least one of the electron withdrawing substituents, sp 2 It is preferably a divalent aromatic heterocyclic group having a nitrogen atom or a carbonyl group, and an electron-withdrawing substituent or sp 2 More preferably, it is a divalent aromatic heterocyclic group having a nitrogen atom and a carbonyl group.
  • Electron withdrawing substituent is Hammett's ⁇ p A substituent whose value is positive. Hammett ⁇ of the substituent p Values are given in, for example, Chemical Review, 1991, Vol. 91, p. 165-195. ⁇ not listed here p The value is obtained by calculation.
  • the acid dissociation equilibrium constant of the compound is calculated by the method described in Journal of Physical Chemistry A (1997), Vol. 101, pages 5593-5595, and Hammett's ⁇ p The value can be determined.
  • the Hammett ⁇ of the substituent p The value is preferably in the range of 0.01 to 1.00.
  • Specific examples of the substituent include a nitro group, a cyano group, a trifluoromethylcarbonyl group, a trifluoromethyl group, a perfluorohexyl group, an acetyl group, a chlorine atom, and a fluorine atom, and a cyano group and a trifluoromethyl group.
  • the divalent heterocyclic group is preferably a divalent aromatic heterocyclic group, such as an oxadiazole diyl group, a thiadiazole diyl group, a thiophene diyl group, a pyrrole diyl group, a furandyl group, a selenophene diyl group, or a pyridinediyl group.
  • Triazinediyl group Triazinediyl group, benzothiophenediyl group, benzopyrrolediyl group, benzofurandiyl group, quinolinediyl group, isoquinolinediyl group, thienothiophenediyl group, benzodithiophenediyl group, cyclopentadithiophenediyl group, and formula (Ar 1 -1) to formula (Ar 1 Group represented by -14) and the like.
  • the formula (Ar 1 -1) to formula (Ar 1 ⁇ 11) is more preferable, and the group represented by formula (Ar) 1 -1), formula (Ar 1 -2), formula (Ar 1 -3), formula (Ar 1 -6), formula (Ar 1 -7) is particularly preferred, and the group represented by the formula (Ar 1 The group represented by -6) is most preferable.
  • R 3 Each independently represents a hydrogen atom, an optionally substituted alkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom.
  • R 3 When two or more exist, they may be the same or different.
  • R 4 Each independently represents a hydrogen atom, an optionally substituted alkyl group, an aryl group or a monovalent heterocyclic group.
  • R 4 When two or more exist, they may be the same or different.
  • Y independently represents -S-, -O-, or -Se-. When a plurality of Y are present, they may be the same or different.
  • the R 3 Is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. .
  • the R 4 Is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.
  • Ar 1 At least one of these is preferably a monocyclic arylene group or a monocyclic divalent heterocyclic group from the viewpoint of further increasing the field-effect mobility of the polymer compound of the present invention.
  • the monocyclic arylene group or monocyclic divalent heterocyclic group has the formula (Ar 1 -1) to formula (Ar 1 It is preferable to combine with the group represented by -11) from the viewpoint of further increasing the electric field mobility of the polymer compound of the present invention.
  • Specific examples of the structural unit represented by Formula (2) include structural units represented by Formula (2-1) to Formula (2-25).
  • the structural unit represented by the formula (2) includes the formula (2-1) to the formula (2-6) and the formula (2-12) to Formula (2-16), Formula (2-23) to Formula (2-25) are preferable, Formula (2-1), Formula (2-3), Formula (2-5), Formula (2-6) Is more preferable.
  • the polymer compound of the present invention includes a structural unit represented by formula (1-1), a structural unit represented by formula (1-2), a structural unit represented by formula (1-3), and a formula (1 -A), a structural unit represented by formula (1-B), a structural unit represented by formula (1-C), and a structural unit other than the structural unit represented by formula (2) (Hereinafter may be referred to as “other structural units”).
  • Other structural units may be contained alone or in combination of two or more in the polymer compound.
  • R b And R c Each independently represents a hydrogen atom, an optionally substituted alkyl group, an aryl group, a monovalent heterocyclic group or a halogen atom.
  • R b And R c The definitions and specific examples of the optionally substituted alkyl group, aryl group, monovalent heterocyclic group and halogen atom represented by formula (1-1) are as follows: 1 The definition and specific examples of the alkyl group, aryl group, monovalent heterocyclic group and halogen atom which may be substituted may be the same.
  • the polymer compound of the present invention is preferably a conjugated polymer compound from the viewpoint of further increasing the field effect mobility of the polymer compound.
  • the polymer compound of the present invention is selected from the group consisting of a structural unit represented by formula (1-1), a structural unit represented by formula (1-2), and a structural unit represented by formula (1-3).
  • a polymer compound comprising at least one selected structural unit, a structural unit represented by the formula (2), and another structural unit. It is preferably a polymer compound composed of a structural unit represented by (1-1), a structural unit represented by formula (2), and another structural unit, represented by formula (1-A).
  • the total proportion of the structural unit represented by formula (1-3) and the structural unit represented by formula (2) is preferably 50 mol% or more, and 70 mol% or more. Is more preferable.
  • the structural unit represented by the formula (1-1), the structural unit represented by the formula (1-2), or the formula (1-3) It is preferable that it is a copolymer of the structural unit represented by the structural unit represented by Formula (2), and is represented by the structural unit represented by Formula (1-1), and Formula (2).
  • the polymer compound of the present invention includes a structural unit represented by the formula (1-A), a structural unit represented by the formula (1-B), or a structure represented by the formula (1-C).
  • Examples thereof include a polymer compound represented by the formula (3-1) to the formula (3-32), which is a copolymer of the unit and the structural unit represented by the formula (2).
  • the polymer compound of the present invention may be produced by any method, for example, the formula: X 11 -A 11 -X 12 And a compound represented by the formula: X 13 -A 12 -X 14 Can be synthesized by a polymerization method such as known aryl coupling using an appropriate catalyst by dissolving in an organic solvent as necessary, adding a base as necessary.
  • a 11 Represents a structural unit represented by the formula (1-1), (1-2), (1-3), (1-A), (1-B) or (1-C), and
  • a 12 Represents a structural unit represented by the formula (2).
  • X 11 , X 12 , X 13 And X 14 Each independently represents a polymerization reactive group.
  • Polymerization reactive groups include halogen atoms, boric acid ester residues, boric acid residues (-B (OH) 2 ), A trialkylstannyl group and the like.
  • the halogen atom that is the polymerization reactive group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • boric acid ester residue that is the polymerization reactive group examples include groups represented by the following formula.
  • examples of the trialkylstannyl group that is the polymerization reactive group include a trimethylstannyl group and a tributylstannyl group.
  • Polymerization methods such as aryl coupling include polymerization by Suzuki coupling reaction (Chemical Review, 1995, Vol. 95, pages 2457-2483), polymerization by Stille coupling reaction (European Polymer Journal, 2005). Year 41, 2923-2933).
  • the polymerization reactive group is a halogen atom, a boric acid ester residue, a boric acid residue or the like when a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction is used.
  • a bromine atom, an iodine atom, and a boric acid ester residue are preferable.
  • the ratio of the total moles of bromine and iodine atoms and the total moles of boric acid ester residues, which are the polymerization reactive groups is 0.00. It is preferably 7 to 1.3, and more preferably 0.8 to 1.2.
  • the polymerization reactive group is a halogen atom, a trialkylstannyl group or the like when a palladium catalyst such as Stille coupling reaction is used.
  • the ratio of the total number of moles of bromine atom and iodine atom and the total number of moles of trialkylstannyl group, which are the polymerization reactive groups is 0.00. It is preferably 7 to 1.3, and more preferably 0.8 to 1.2.
  • the organic solvent used for polymerization include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, and dioxane.
  • Bases used for polymerization include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide And organic bases such as tetraethylammonium hydroxide and tetrabutylammonium hydroxide.
  • inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide
  • organic bases such as tetraethylammonium hydroxide and tetrabutylammonium hydroxide.
  • the catalyst used for the polymerization examples include transition metal complexes such as tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, dichlorobistriphenylphosphine palladium, and a transition metal complex, if necessary. It is a catalyst comprising a ligand such as phenylphosphine, tri-t-butylphosphine, tricyclohexylphosphine. As these catalysts, those synthesized in advance may be used, or those prepared in the reaction system may be used as they are. Moreover, these catalysts may be used individually by 1 type, or may use 2 or more types together.
  • transition metal complexes such as tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, palladium acetate, dichlorobistriphenylphosphine
  • the polymerization reaction temperature is preferably 0 to 200 ° C, more preferably 0 to 150 ° C, and still more preferably 0 to 120 ° C.
  • the polymerization reaction time is usually 1 hour or longer, preferably 2 to 500 hours.
  • the post-treatment of the polymerization can be carried out by a known method, for example, by a method in which the reaction solution obtained by the polymerization is added to a lower alcohol such as methanol and the resulting precipitate is filtered and dried.
  • a lower alcohol such as methanol
  • the resulting precipitate is filtered and dried.
  • the purity of the polymer compound obtained by the above polymerization reaction is low, it may be purified by a method such as recrystallization, continuous extraction with a Soxhlet extractor, or column chromatography.
  • the molecular chain terminal is preferably a stable group such as an aryl group or a monovalent aromatic heterocyclic group.
  • the polymer compound of the present invention may be any type of copolymer, such as a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer.
  • the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (hereinafter referred to as “GPC”) of the polymer compound of the present invention is usually 1 ⁇ 10.
  • the number average molecular weight is 2 ⁇ 10 3 The above is preferable. From the viewpoint of increasing the solubility in a solvent and facilitating the preparation of a thin film, the number average molecular weight is 1 ⁇ 10 6 The following is preferable.
  • Organic semiconductor element include an organic transistor, an organic solar battery, and an organic electroluminescence element. The polymer compound of the present invention is particularly useful as a charge transport material for organic transistors.
  • the organic semiconductor material may contain one kind of the polymer compound of the present invention alone, or may contain two or more kinds.
  • the organic semiconductor material may further contain a low-molecular compound or a polymer compound having field effect mobility.
  • the polymer compound of the present invention is preferably contained in an amount of 30% by weight or more, more preferably 50% by weight or more. When the content of the polymer compound of the present invention is less than 30% by weight, it may be difficult to form a thin film.
  • Examples of the compound having field effect mobility include arylamine derivatives, stilbene derivatives, oligothiophene and derivatives thereof, low molecular compounds such as oxadiazole derivatives, fullerenes and derivatives thereof, poly (N-vinylcarbazole) and derivatives thereof, Examples thereof include polymer compounds such as polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and polyfluorene and derivatives thereof.
  • the organic semiconductor material may contain a polymer compound material as a polymer binder.
  • polymer binder examples include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof.
  • Derivatives, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like can be mentioned.
  • Organic transistor has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path The thing which has is mentioned.
  • Examples of the organic transistor having such a configuration include a field effect organic transistor and a static induction organic transistor.
  • a field effect organic transistor usually has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path.
  • the organic transistor having an active layer and an insulating layer disposed between the gate electrode.
  • an organic transistor in which a source electrode and a drain electrode are provided in contact with an active layer and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween is preferable.
  • the electrostatic induction organic transistor usually has a source electrode and a drain electrode, a current path between these electrodes, an active layer containing the polymer compound of the present invention, and a gate electrode that controls the amount of current passing through the current path And the gate electrode is provided in the active layer.
  • an organic transistor in which a source electrode, a drain electrode, and a gate electrode are provided in contact with the active layer is preferable.
  • the gate electrode may have a structure in which a current path flowing from the source electrode to the drain electrode can be formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. .
  • FIG. 1 is a schematic cross-sectional view showing an example of an organic transistor (field-effect organic transistor) of the present invention.
  • An organic transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1 at a predetermined interval, and a source electrode 5 and a drain electrode 6 so as to cover the substrate 1. Formed on the insulating layer 3 so as to cover the active layer 2 formed on the insulating layer 3, the insulating layer 3 formed on the active layer 2, and the insulating layer 3 on the region between the source electrode 5 and the drain electrode 6. The gate electrode 4 is provided.
  • FIG. 2 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing another example of the organic transistor (field effect type organic transistor) of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention.
  • FIG. 5 is a schematic sectional view showing another example of the organic transistor (electrostatic induction type organic transistor) of the present invention.
  • FIG. 5 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the source electrode 5, and a plurality of active transistors 2 with a predetermined interval on the active layer 2.
  • FIG. 6 is a schematic cross-sectional view showing another example of the organic transistor (field effect type organic transistor) of the present invention.
  • FIG. 7 is a schematic cross-sectional view showing another example of the organic transistor (field-effect organic transistor) of the present invention.
  • FIG. 7 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom.
  • An active layer 2 formed so as to cover the region of the insulating layer 3 formed on the active layer 2, a source electrode 5 formed on the active layer 2 so as to cover a part of the active layer 2, and one of the active layers 2
  • a source electrode 5 and a drain electrode 6 formed on the active layer 2 with a predetermined interval are provided so as to cover the portion.
  • FIG. 8 is a schematic cross-sectional view showing another example of the organic transistor (field-effect organic transistor) of the present invention.
  • FIG. 9 is a schematic cross-sectional view showing another example of the organic transistor (field effect organic transistor) of the present invention.
  • the organic transistor 180 shown in FIG. 9 includes a gate electrode 4, an insulating layer 3 formed on the gate electrode 4, a source electrode 5 and a drain electrode 6 formed on the insulating layer 3 with a predetermined interval,
  • the active layer 2 is formed on the insulating layer 3 so as to cover a part of the source electrode 5 and the drain electrode 6.
  • the active layer 2 and / or the active layer 2a is composed of a film containing the polymer compound of the present invention, and a current path (channel) between the source electrode 5 and the drain electrode 6 is formed.
  • the gate electrode 4 controls the amount of current passing through the current path (channel) by applying a voltage.
  • Such a field effect organic transistor can be manufactured by a known method, for example, a method described in JP-A-5-110069.
  • the electrostatic induction organic transistor can be produced by a known method such as the method described in US2004 / 004215.
  • the material of the substrate 1 may be any material that does not hinder the characteristics of the organic transistor.
  • the material of the insulating layer 3 may be any material having high electrical insulation, such as SiO x , SiN x , Ta 2 O 5 Polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass, photoresist, and the like can be used. From the viewpoint of lowering the voltage, it is preferable to use a material having a high dielectric constant.
  • a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the active layer 2. It is also possible to form the active layer 2 after the modification.
  • silane coupling agents include alkylchlorosilanes (octyltrichlorosilane (OTS), octadecyltrichlorosilane (ODTS), phenylethyltrichlorosilane, etc.), alkylalkoxysilanes, fluorinated alkylchlorosilanes, and fluorinated alkylalkoxysilanes.
  • silylamine compounds such as hexamethyldisilazane (HMDS).
  • HMDS hexamethyldisilazane
  • the surface of the insulating layer is treated with ozone UV treatment, O before treatment with the surface treatment agent. 2 Plasma treatment may be performed.
  • the gate electrode 4 includes metals such as gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum, low-resistance polysilicon, low-resistance amorphous silicon, tin oxide, indium oxide, indium / tin oxide.
  • a material such as (ITO) can be used. These materials may be used alone or in combination of two or more. Note that a highly doped silicon substrate can be used as the gate electrode 4.
  • a highly doped silicon substrate has not only the performance as a gate electrode but also the performance as a substrate.
  • the substrate 1 may be omitted in the organic transistor in which the substrate 1 and the gate electrode 4 are in contact with each other.
  • the source electrode 5 and the drain electrode 6 are preferably made of a low resistance material, and particularly preferably made of gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum or the like. These materials may be used alone or in combination of two or more.
  • a layer composed of another compound may be interposed between the source electrode 5 and the drain electrode 6 and the active layer 2.
  • Such layers include low molecular compounds having electron transport properties, low molecular compounds having hole transport properties, alkali metals, alkaline earth metals, rare earth metals, complexes of these metals with organic compounds, iodine, bromine, Halogens such as chlorine and iodine chloride, sulfur oxide compounds such as sulfuric acid, sulfuric anhydride, sulfur dioxide and sulfate, nitric oxide compounds such as nitric acid, nitrogen dioxide and nitrate, halogenated compounds such as perchloric acid and hypochlorous acid, Examples thereof include layers made of aromatic thiol compounds such as alkyl thiol compounds, aromatic thiols, and fluorinated alkyl aromatic thiols.
  • an organic transistor is interrupted
  • the protective film can also reduce the influence on the organic transistor in the formation process.
  • a method for forming a protective film an organic transistor, UV curable resin, thermosetting resin or inorganic SiON x Examples include a method of covering with a film or the like.
  • a field effect organic transistor which is a kind of organic transistor configured as described above, can be applied as a pixel drive switching element of an active matrix drive type liquid crystal display or an organic electroluminescence display.
  • the organic field effect transistor of embodiment mentioned above is equipped with the active compound which contains the high molecular compound of this invention as an active layer, and the charge transport property improved by it, the field effect mobility is provided. Is expensive. Therefore, it is useful for manufacturing a display having a sufficient response speed.
  • NMR analysis> The NMR measurement was performed by dissolving the compound in deuterated chloroform and using an NMR apparatus (Varian, INOVA300).
  • ⁇ Molecular weight analysis> The number average molecular weight and the weight average molecular weight of the polymer compound were determined using gel permeation chromatography (GPC, manufactured by Waters, trade name: Alliance GPC 2000). The polymer compound to be measured was dissolved in orthodichlorobenzene and injected into GPC. Orthodichlorobenzene was used for the mobile phase of GPC.
  • the reaction solution was poured into water, washed with water, and toluene was distilled off with an evaporator.
  • the obtained liquid was purified with a silica gel column using hexane as a developing solvent to obtain 3- (2-octyldodecyloxy) thiophene.
  • the yield was 15.2 g and the yield was 91%.
  • the result of 1 H-NMR analysis of 3- (2-octyldodecyloxy) thiophene is shown below.
  • the reaction solution was filtered through celite, and the filtrate was concentrated with an evaporator.
  • Toluene and water were added here, and extracted with toluene. Washed with hydrochloric acid followed by water.
  • the toluene solution was evaporated with an evaporator.
  • the obtained liquid was subjected to silica gel column purification using a 4/1 mixed solution of hexane and chloroform as a developing solvent to obtain 3,3′-bis (2-octyldodecyloxy) -2,2′-bithiophene.
  • the yield was 7.72 g, and the yield was 44%.
  • Example 1 Synthesis of polymer compound P1>
  • 0.300 g (0.224 mmol) of compound M1 0.0987 g (0.215 mmol) of compound M2, 50 mL of toluene, 3 of tris (dibenzylideneacetone) dipalladium 0.1 mg and 6.1 mg of triortho-tolylphosphine were added and refluxed for 5 hours.
  • 35 mg of bromobenzene was added and refluxed for 1 hour.
  • the reaction solution was added dropwise to acetone to obtain a precipitate.
  • the precipitate was collected by filtration.
  • Toluene, water, and sodium N, N-diethyldithiocarbamate trihydrate were added to the precipitate and refluxed for 3 hours. Thereafter, the toluene layer was extracted. After the toluene solution was washed with an acetic acid aqueous solution and water, the toluene solution was added dropwise to acetone to obtain a precipitate. The precipitate was Soxhlet washed using acetone as a solvent to obtain a polymer compound P1. The yield was 0.15 g, the polystyrene-equivalent number average molecular weight was 6.6 ⁇ 10 4 , and the weight average molecular weight was 1.3 ⁇ 10 5 .
  • Example 2 Synthesis of polymer compound P2> A polymer compound P2 was synthesized in the same manner as in Example 1 except that 0.0937 g (0.202 mmol) of the compound M3 was used instead of the compound M2. The yield was 0.13 g, the number average molecular weight in terms of polystyrene was 1.7 ⁇ 10 4 , and the weight average molecular weight was 2.4 ⁇ 10 5 .
  • Compound M3 was synthesized according to the method described in Chemistry A European Journal, 2010, Vol. 16, p. 3743.
  • Example 3 Synthesis of polymer compound P3> A polymer compound P3 was synthesized in the same manner as in Example 1 except that 0.138 g (0.220 mmol) of the compound M4 was used instead of the compound M2. The yield was 0.21 g, the number average molecular weight in terms of polystyrene was 3.1 ⁇ 10 4 , and the weight average molecular weight was 8.8 ⁇ 10 4 .
  • Compound M4 was synthesized according to the method described in Synthetic Metals, 2010, 160, 2422.
  • ⁇ Synthesis Example 4 Synthesis of Compound M5> Compound M5-1 was synthesized according to the method described in “Tetrahedron, 2010, 66, 1837”.
  • Example 4 Synthesis of polymer compound P4> A polymer compound P4 was synthesized in the same manner as in Example 1 except that 0.0872 g (0.179 mmol) of the compound M5 was used instead of the compound M2. The yield was 0.12 g, the polystyrene-equivalent number average molecular weight was 2.5 ⁇ 10 4 , and the weight average molecular weight was 1.5 ⁇ 10 5 .
  • ⁇ Synthesis Example 5 Synthesis of polymer compound PA> A polymer compound PA was synthesized in the same manner as in Example 1 except that 0.0653 g (0.222 mmol) of 4,7-dibromobenzo-2,1,3-thiadiazole was used in place of the compound M2.
  • Example 5 Production and evaluation of organic transistor 1> An organic transistor 1 having a structure shown in FIG. 9 was produced using a solution containing the polymer compound P1. The surface of the heavily doped n-type silicon substrate to be the gate electrode was thermally oxidized to form a silicon oxide film (hereinafter referred to as “thermal oxide film”). The thermal oxide film functions as an insulating layer. Next, a source electrode and a drain electrode were formed on the thermal oxide film by a photolithography process.
  • the source electrode and the drain electrode had a chromium (Cr) layer and a gold (Au) layer from the thermal oxide film side, and had a channel length of 20 ⁇ m and a channel width of 2 mm.
  • the substrate on which the thermal oxide film, the source electrode, and the drain electrode thus obtained were ultrasonically cleaned with acetone, and UV ozone treatment was performed with an ozone UV cleaner. Thereafter, the surface of the thermal oxide film was modified with ⁇ -phenethyltrichlorosilane, and the surfaces of the source electrode and the drain electrode were modified with pentafluorobenzenethiol.
  • the surface-treated thermal oxide film, the source electrode and the drain electrode are spin-coated with an orthodichlorobenzene solution of 0.5% by weight of the polymer compound P1 at a rotational speed of 1000 rpm, and an organic semiconductor layer (active layer) ) Was formed. Thereafter, the organic semiconductor layer was heated at 170 ° C. for 30 minutes to manufacture the organic transistor 1.
  • the transistor characteristics were measured by changing the gate voltage Vg and the source-drain voltage Vsd of the organic transistor 1 obtained.
  • the field effect mobility was 1.6 ⁇ 10 ⁇ 2 cm 2 / Vs. The results are shown in Table 2.
  • Example 6 Production and evaluation of organic transistor 2> Organic transistor 2 was produced in the same manner as in Example 5 except that polymer compound P2 was used instead of polymer compound P1. The transistor characteristics were measured by changing the gate voltage Vg and the source-drain voltage Vsd of the organic transistor 2 obtained. The field effect mobility was 1.4 ⁇ 10 ⁇ 2 cm 2 / Vs. The results are shown in Table 2.
  • Example 7 Production and evaluation of organic transistor 3> An organic transistor 3 was produced in the same manner as in Example 5 except that the polymer compound P3 was used instead of the polymer compound P1. The transistor characteristics were measured by changing the gate voltage Vg and the source-drain voltage Vsd of the organic transistor 3 obtained.
  • Example 8 Production and evaluation of organic transistor 4> An organic transistor 4 was produced in the same manner as in Example 5 except that the polymer compound P4 was used instead of the polymer compound P1. The gate voltage Vg and source-drain voltage Vsd of the obtained organic transistor 4 were changed, and transistor characteristics were measured. The field effect mobility was 2.7 ⁇ 10 ⁇ 1 cm 2 / Vs. The results are shown in Table 2.
  • ⁇ Comparative Example 1 Production and Evaluation of Organic Transistor C1> Organic transistor C1 was produced in the same manner as in Example 5 except that polymer compound PA was used instead of polymer compound P1. The transistor characteristics were measured by changing the gate voltage Vg and the source-drain voltage Vsd of the obtained organic transistor C1. The field effect mobility was 3.5 ⁇ 10 ⁇ 4 cm 2 / Vs. The results are shown in Table 2.
  • a polymer compound having sufficiently high field effect mobility can be provided.
  • an organic transistor including the polymer compound of the present invention in an active layer and having sufficiently high field effect mobility can be provided.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104119503A (zh) * 2013-04-25 2014-10-29 海洋王照明科技股份有限公司 含噻吩并噻吩-二噻吩并苯并三唑-苯并噻二唑类共轭聚合物及其制备方法与应用
CN104211915A (zh) * 2013-05-29 2014-12-17 海洋王照明科技股份有限公司 共轭聚合物及其制备方法与应用
JP2015521672A (ja) * 2012-07-02 2015-07-30 メルク パテント ゲーエムベーハー 共役ポリマー

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6105739B2 (ja) * 2012-10-31 2017-03-29 トヨタ モーター ヨーロッパ ナームロゼ フェンノートシャップ／ソシエテ アノニム 電気化学エネルギー蓄積用の有機活物質

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003221434A (ja) * 2002-01-11 2003-08-05 Xerox Corp ポリチオフェン類及びその調製法
JP2003261655A (ja) * 2002-01-11 2003-09-19 Xerox Corp ポリチオフェン類及びそれを用いたデバイス
JP2006037098A (ja) * 2004-07-08 2006-02-09 Samsung Electronics Co Ltd ポリ（オリゴチオフェン−アリーレン）誘導体、有機半導体共重合体、半導体多層構造、およびポリ（オリゴチオフェン−アリーレン）誘導体の製造方法
WO2010117449A2 (en) * 2009-04-06 2010-10-14 University Of Kentucky Research Foundation Semiconducting compounds and devices incorporating same
WO2011005370A2 (en) * 2009-05-26 2011-01-13 University Of Florida Research Foundation, Inc. Earth-toned photovoltaic devices
JP2011060998A (ja) * 2009-09-10 2011-03-24 Konica Minolta Holdings Inc 有機光電変換素子、その製造方法、有機光電変換素子を用いた太陽電池及び光センサアレイ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003221434A (ja) * 2002-01-11 2003-08-05 Xerox Corp ポリチオフェン類及びその調製法
JP2003261655A (ja) * 2002-01-11 2003-09-19 Xerox Corp ポリチオフェン類及びそれを用いたデバイス
JP2006037098A (ja) * 2004-07-08 2006-02-09 Samsung Electronics Co Ltd ポリ（オリゴチオフェン−アリーレン）誘導体、有機半導体共重合体、半導体多層構造、およびポリ（オリゴチオフェン−アリーレン）誘導体の製造方法
WO2010117449A2 (en) * 2009-04-06 2010-10-14 University Of Kentucky Research Foundation Semiconducting compounds and devices incorporating same
WO2011005370A2 (en) * 2009-05-26 2011-01-13 University Of Florida Research Foundation, Inc. Earth-toned photovoltaic devices
JP2011060998A (ja) * 2009-09-10 2011-03-24 Konica Minolta Holdings Inc 有機光電変換素子、その製造方法、有機光電変換素子を用いた太陽電池及び光センサアレイ

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015521672A (ja) * 2012-07-02 2015-07-30 メルク パテント ゲーエムベーハー 共役ポリマー
US9695190B2 (en) 2012-07-02 2017-07-04 Merck Patent Gmbh Conjugated polymers
CN104119503A (zh) * 2013-04-25 2014-10-29 海洋王照明科技股份有限公司 含噻吩并噻吩-二噻吩并苯并三唑-苯并噻二唑类共轭聚合物及其制备方法与应用
CN104211915A (zh) * 2013-05-29 2014-12-17 海洋王照明科技股份有限公司 共轭聚合物及其制备方法与应用

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