WO2011078246A1 - Composé polymère, et couche mince et composition d'encre contenant chacune celui-ci - Google Patents

Composé polymère, et couche mince et composition d'encre contenant chacune celui-ci Download PDF

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WO2011078246A1
WO2011078246A1 PCT/JP2010/073181 JP2010073181W WO2011078246A1 WO 2011078246 A1 WO2011078246 A1 WO 2011078246A1 JP 2010073181 W JP2010073181 W JP 2010073181W WO 2011078246 A1 WO2011078246 A1 WO 2011078246A1
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polymer compound
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和男 瀧宮
格 尾坂
健司 小廣
健一郎 大家
邦仁 三宅
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住友化学株式会社
国立大学法人広島大学
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    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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Definitions

  • the present invention relates to a polymer compound, a thin film and an ink composition containing the polymer compound, an organic transistor including the thin film, a planar light source including the organic transistor, and a display device.
  • Organic transistors are suitable for uses such as electronic paper and flexible displays because they have low cost and are flexible and bendable, and have attracted attention in recent years.
  • An organic transistor includes a layer having a charge transport property (meaning holes and electrons, hereinafter the same) composed of an organic substance, and an organic semiconductor material is mainly used as the organic substance.
  • an organic semiconductor material a high molecular compound capable of forming a layer (that is, an organic semiconductor layer, generally also referred to as an active layer) by a coating method in a state dissolved in a solvent has been studied, For example, a polymer compound having only a thiophene skeleton has been proposed (Non-Patent Document 1).
  • the characteristics of the organic transistor mainly depend on the charge mobility in the organic semiconductor layer, and the higher the charge mobility, the better the field effect mobility of the organic transistor and the better the characteristics.
  • the use of organic transistors has been diversified, and higher charge mobility is required than ever before.
  • the conventional polymer compound as described above it tends to be difficult to obtain sufficient high mobility as recently required.
  • an object of the present invention is to provide a polymer compound capable of obtaining high charge mobility.
  • Another object of the present invention is to provide a thin film and an ink composition containing the polymer compound, an organic transistor including the thin film, a planar light source including the organic transistor, and a display device.
  • the present invention provides a polymer compound having at least one repeating unit selected from the group consisting of a repeating unit represented by formula (1) and a repeating unit represented by formula (2).
  • I will provide a.
  • [X 11 and X 12 in Formula (1) and X 21 and X 22 in Formula (2) are the same or different and each represent a chalcogen atom
  • R 13 , R 14 , R 15 and R 16 in Formula (1) Are the same or different and each represents a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, substituted silyl group, unsubstituted or substituted
  • the polymer compound of the present invention has a repeating unit represented by the formula (1) or (2), and thus can exhibit high charge mobility when applied as an organic semiconductor layer. .
  • a plurality of aromatic rings are condensed, and the structure of the condensed structure is highly symmetric, so that the main chains of the polymer compound are easy to overlap (easy to pack). From this, it is considered that high conjugation is obtained.
  • the polymer compound of the present invention since the polymer compound of the present invention has the specific repeating unit described above, it tends to be highly soluble in a solvent, and it is relatively easy to form an organic semiconductor layer by a coating method as a solution state. It is.
  • X 11 and X 12 and X 21 and X 22 are preferably an oxygen atom, a sulfur atom or a selenium atom. According to the polymer compound having such a structure, higher charge mobility can be obtained. In particular, X 11 and X 12 and X 21 and X 22 are preferably sulfur atoms. Such a polymer compound has an advantage that high charge mobility is easily obtained, synthesis is easy, and environmental load is small.
  • the combination of R 13 and R 15 and the combination of R 14 and R 16 in the formula (1) are combinations of the same groups, and the combination of R 23 and R 25 in the formula (2)
  • the combination of R 24 and R 26 is preferably a combination of the same groups. In this way, by making specific groups the same group, the polymer compound has a repeating unit with higher symmetry and becomes easy to pack, so that higher charge mobility can be obtained.
  • More preferable structures include structures in which R 13 , R 14 , R 15 and R 16 in formula (1) and R 23 , R 24 , R 25 and R 26 in formula (2) are hydrogen atoms. It is done. As a result, higher charge mobility can be obtained.
  • the polymer compound of the present invention further has a repeating unit represented by the formula (3) in addition to at least one repeating unit represented by the formulas (1) and (2). And preferred. By further including such a repeating unit, it is possible to obtain even better charge mobility.
  • Y represents an arylene group, a divalent heterocyclic group, a divalent group having a metal complex structure or an ethynylene group, each of which may have a substituent.
  • two or more Y exists they may be the same or different.
  • Y in the repeating unit represented by the formula (3) is a 5-membered divalent heterocyclic group having 4 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a polycyclic divalent heterocyclic group. Is preferable. By doing so, even better charge mobility can be obtained.
  • Y in the repeating unit represented by the formula (3) is preferably a group represented by the formula (4).
  • T represents a divalent heterocyclic group which may have a substituent
  • n represents an integer of 2 to 8.
  • two or more T exists they may be the same or different.
  • Y in the repeating unit represented by the formula (3) is preferably a group represented by the formula (5).
  • Ar 1 and Ar 2 are the same or different and each have an aromatic hydrocarbon ring which may have a substituent, a heterocyclic ring which may have a substituent, or a substituent. It is a condensed ring of an aromatic hydrocarbon ring which may be substituted and a heterocyclic ring which may have a substituent.
  • R 51 and R 52 are the same or different and each is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, substituted silyl group, An unsubstituted or substituted carboxyl group, a monovalent heterocyclic group which may have a substituent, a cyano group or a fluorine atom is shown. ]
  • the repeating unit represented by the formula (3) preferably includes at least one kind of aromatic group having an electron accepting property (hereinafter referred to as “electron accepting group”).
  • electron accepting group an electron accepting property
  • the value of the energy level of the highest occupied trajectory possessed by the repeating unit represented by the formula (1) and the highest occupied trajectory possessed by the repeating unit represented by the formula (2) is 4.4 eV or less. In particular, excellent charge mobility tends to be obtained.
  • the present invention also provides a thin film containing the polymer compound of the present invention. Moreover, this invention provides an organic transistor provided with the organic-semiconductor layer which consists of this thin film. Since the thin film of the present invention contains the polymer compound of the present invention, it can exhibit high charge mobility. Therefore, the organic transistor of the present invention including the organic semiconductor layer made of such a thin film has high electric field effect mobility because the charge mobility of the organic semiconductor layer is high.
  • the present invention also provides an ink composition containing the polymer compound of the present invention and a solvent.
  • Such an ink composition is extremely effective for forming an organic semiconductor layer or the like by a coating method because the polymer compound is uniformly dispersed or dissolved in a solvent.
  • this invention provides the planar light source provided with the organic transistor of the said invention, and a display apparatus provided with the said organic transistor of this invention. Since these planar light sources and display devices include the organic transistor of the present invention that provides excellent field effect mobility, they can exhibit excellent characteristics.
  • the present invention also includes an anode, a cathode, and an organic semiconductor layer provided between the anode and the cathode, and the organic semiconductor layer includes an electron donating compound and an electron accepting compound, and the electron donating compound And a photoelectric conversion element in which at least one of the electron-accepting compounds is the polymer compound of the present invention, and a solar cell module and an image sensor including the photoelectric conversion element. These also exhibit excellent characteristics because the organic semiconductor layer has high charge mobility.
  • the polymer compound of the present invention having the specific structure described above can obtain high charge mobility when used in an organic semiconductor layer. And when the high molecular compound of this invention is used, formation of such an organic-semiconductor layer is comparatively easy. Furthermore, according to the present invention, an ink composition containing such a polymer compound and advantageous for forming a thin film, and a thin film having a high charge mobility, which is preferably obtained by such an ink composition, are provided. Can do.
  • the present invention includes an organic semiconductor layer made of a thin film containing the polymer compound of the present invention, and has an organic transistor capable of obtaining excellent field-effect mobility, and has high characteristics.
  • a planar light source and a display device can be provided.
  • Such an organic transistor of the present invention is, for example, a liquid crystal display or electronic paper drive circuit, a curved or flat light source switch circuit for illumination, a segment type display element, a dot matrix flat panel display, etc. Useful for drive circuits.
  • the polymer compound of the present invention can also be used as a material for an organic semiconductor layer of a photoelectric conversion element.
  • the photoelectric conversion element of the present invention includes an anode, a cathode, and an organic semiconductor layer provided between the anode and the cathode, and the organic semiconductor layer includes an electron donating compound and an electron accepting compound, At least one of the functional compound and the electron accepting compound is the polymer compound of the present invention.
  • a photoelectric conversion element provided with such an organic semiconductor layer is useful, for example, as a solar cell module or an image sensor.
  • 1 is a schematic cross-sectional view of an organic transistor according to a first embodiment. It is a schematic cross section of the organic transistor which concerns on 2nd Embodiment. It is a schematic cross section of the organic transistor which concerns on 3rd Embodiment. It is a schematic cross section of the organic transistor which concerns on 4th Embodiment. It is a schematic cross section of the organic transistor which concerns on 5th Embodiment. It is a schematic cross section of the organic transistor which concerns on 6th Embodiment. It is a schematic cross section of the organic transistor which concerns on 7th Embodiment. It is a schematic cross section of the planar light source according to the embodiment. It is a schematic cross section of the organic transistor produced in the Example. It is a schematic cross section of the photoelectric conversion element which concerns on embodiment.
  • “repeating unit” means a monomer unit forming a skeleton of a polymer compound, and is a structural unit present in at least one polymer compound.
  • the “n-valent heterocyclic group” (n is 1 or 2) is formed by removing n hydrogen atoms from a heterocyclic compound (particularly a heterocyclic compound having aromaticity). , A group whose part forms a bond with another atom.
  • a “heterocyclic compound” is an organic compound having a cyclic structure in which the elements constituting the ring are not only carbon atoms but also hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, and the like. An atom containing an atom in the ring.
  • the polymer compound of the present invention has at least one repeating unit selected from the group consisting of the repeating unit represented by the above formula (1) and the repeating unit represented by the formula (2).
  • the polymer compound may be a homopolymer having only one of the repeating units represented by formulas (1) and (2) as a repeating unit. ) And (2), or a copolymer having a combination of one of the formulas (1) and (2) and other types.
  • X 11 and X 12 in formula (1) and X 21 and X 22 in formula (2) are the same or different and are chalcogen atoms.
  • a chalcogen atom is an element belonging to Group 16 of the periodic table, and examples include an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and a polonium atom. Since high charge mobility can be obtained, the chalcogen atom is preferably an oxygen atom, a sulfur atom, and a selenium atom, and more preferably an oxygen atom and a sulfur atom, and a sulfur atom is particularly preferable in consideration of environmental load. preferable.
  • R 13 , R 14 , R 15 and R 16 (hereinafter referred to as “R 13 to R 16 ”) in the formula (1) are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group.
  • R 23 to R 26 in Formula (2) are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, A substituted silyl group, an unsubstituted or substituted carboxyl group, a monovalent heterocyclic group which may have a substituent, a cyano group or a fluorine atom is shown.
  • the alkyl group may be linear, branched or cyclic, and preferably has 1 to 36 carbon atoms, more preferably 6 to 30 carbon atoms, and still more preferably 8 to 24 carbon atoms.
  • Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2 -Ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, undecyl, dodecyl, tetradecyl, hexadodecyl, octadodecyl trifluoromethyl, pentafluoroethyl, perfluorobutyl,
  • the alkoxy group may be linear, branched or cyclic, and preferably has 1 to 36 carbon atoms, more preferably 6 to 30 carbon atoms.
  • Specific examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyl Oxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, undecyloxy group, dodecyloxy group, tetradecyloxy group, hexadecyloxy group, octadecyloxy group, trifluoromethoxy Group, pentafluoroethoxy group, perfluorobutoxy group, perfluor
  • An undecyloxy group, a dodecyloxy group, a tetradecyloxy group, a hexadecyloxy group, and an octadecyloxy group are preferable.
  • the alkylthio group may be linear, branched or cyclic, and preferably has 1 to 36 carbon atoms, more preferably 6 to 30 carbon atoms.
  • Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2 -Ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, undecylthio group, dodecylthio group, tetradecylthio group, hexadecylthio group, octadecyl
  • hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, 3,7-dimethyloctylthio group, undecylthio group Group, dodecylthio group, tetradecylthio group, hexadecylthio group and octadecylthio group are preferred.
  • An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, having a condensed ring, or having two or more independent benzene rings or condensed rings bonded directly or via a vinylene group including.
  • the aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 48, still more preferably 6 to 20, and particularly preferably 6 to 10. This carbon number does not include the carbon number of the substituent.
  • the aryl group includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-tetracenyl group, a 2-tetracenyl group, a 5-tetracenyl group, 1- Pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-perenyl group, 3-perylenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 1-biphenylenyl group, 2-biphenylenyl group, 2- Phenanthrenyl group, 9-phenanthrenyl group, 6-chrycenyl group, 1-coronenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, 4- (anthrac
  • the hydrogen atoms in these groups are alkyl groups, alkoxy groups, alkyloxycarbonyl groups, acyl groups, N, N-dialkylamino groups, N, N-diarylamino groups, cyano groups, nitro groups, chlorine atoms, fluorine atoms, etc. May be substituted.
  • the aryloxy group preferably has 6 to 60 carbon atoms, more preferably 7 to 48 carbon atoms.
  • Examples of the aryloxy group include a phenoxy group, a C 1 -C 18 alkoxyphenoxy group (“C 1 -C 18 alkoxy” indicates that the alkoxy moiety has 1 to 18 carbon atoms, and the same applies hereinafter)
  • a C 1 -C 18 alkylphenoxy group (“C 1 -C 18 alkyl” indicates that the alkyl moiety has 1 to 18 carbon atoms, the same shall apply hereinafter), a 1-naphthyloxy group, 2-naphthyl Examples thereof include an oxy group and a pentafluorophenyloxy group.
  • a C 1 -C 18 alkoxyphenoxy group and a C 1 -C 18 alkylphenoxy group are preferred because the balance between the solubility of the polymer compound in an organic solvent and the heat resistance becomes good.
  • C 1 -C 18 alkoxyphenoxy groups include methoxyphenoxy group, ethoxyphenoxy group, propyloxyphenoxy group, isopropyloxyphenoxy group, butoxyphenoxy group, isobutoxyphenoxy group, tert-butoxyphenoxy group, pentyloxyphenoxy group, hexyl Oxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3,7-dimethyloctyloxyphenoxy group, undecyloxyphenoxy group Group, dodecyloxyphenoxy group, tetradecyloxyphenoxy group, hexadecyloxyphenoxy group, octadecyloxyphenoxy group It is.
  • Examples of the C 1 -C 18 alkylphenoxy group include methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, butylphenoxy group.
  • the arylthio group preferably has 3 to 60 carbon atoms.
  • the arylthio group include a phenylthio group, a C 1 -C 18 alkoxyphenylthio group, a C 1 -C 18 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.
  • a C 1 -C 18 alkoxyphenylthio group and a C 1 -C 18 alkylphenylthio group are preferred because the balance between the solubility of the polymer compound in an organic solvent and the heat resistance is improved.
  • the arylalkyl group preferably has 7 to 60 carbon atoms, more preferably 7 to 48 carbon atoms.
  • Examples of the arylalkyl group include a phenyl-C 1 -C 18 alkyl group, a C 1 -C 18 alkoxyphenyl-C 1 -C 18 alkyl group, a C 1 -C 18 alkylphenyl-C 1 -C 18 alkyl group, Examples thereof include 1 -naphthyl-C 1 -C 18 alkyl group and 2-naphthyl-C 1 -C 18 alkyl group.
  • the arylalkoxy group preferably has 7 to 60 carbon atoms, more preferably 7 to 48 carbon atoms.
  • arylalkoxy groups include phenyl-C 1 -C 18 alkoxy such as phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, phenyloctyloxy group, etc.
  • C 1 -C 18 alkoxyphenyl-C 1 -C 18 alkoxy group C 1 -C 18 alkylphenyl-C 1 -C 18 alkoxy group, 1-naphthyl-C 1 -C 18 alkoxy group, 2-naphthyl- And C 1 -C 18 alkoxy groups.
  • a C 1 -C 18 alkoxyphenyl-C 1 -C 18 alkoxy group, a C 1 -C 18 alkylphenyl-C 1 - C18 alkoxy groups are preferred.
  • the arylalkylthio group preferably has 7 to 60 carbon atoms, more preferably 7 to 48 carbon atoms.
  • Examples of the arylalkylthio group include phenyl-C 1 -C 18 alkylthio group, C 1 -C 18 alkoxyphenyl-C 1 -C 18 alkylthio group, C 1 -C 18 alkylphenyl-C 1 -C 18 alkylthio group, Examples thereof include a 1 -naphthyl-C 1 -C 18 alkylthio group and a 2-naphthyl-C 1 -C 18 alkylthio group.
  • Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group.
  • the substituted silyl group preferably has 1 to 60 carbon atoms, more preferably 3 to 48 carbon atoms. Note that the alkyl group, aryl group, arylalkyl group, or monovalent heterocyclic group may have a substituent.
  • substituted silyl groups include trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, dimethylisopropylpropyl, diethylisopropylsilyl, tert-butylsilyldimethylsilyl, pentyldimethylsilyl, hexyldimethylsilyl.
  • substituted carboxyl group examples include an alkyl group, an aryl group, an arylalkyl group or a carboxyl group substituted with a monovalent heterocyclic group, preferably having 2 to 60 carbon atoms, more preferably 2 carbon atoms. 48.
  • substituted carboxyl groups include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group Cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, undecyloxycarbonyl group, Dodecyloxycarbonyl group, tetradecyloxycarbonyl group, hexadecyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethoxycarbonyl , Pentafluoro
  • the monovalent heterocyclic group preferably has 4 to 60 carbon atoms, more preferably 4 to 20 carbon atoms.
  • the carbon number of the monovalent heterocyclic group does not include the carbon number of the substituent.
  • Examples of the monovalent heterocyclic group include thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group, pyrimidyl group, and triazinyl group.
  • a thienyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrimidyl group, and a triazinyl group are preferable, and a thienyl group, a pyridyl group, a pyrimidyl group, and a triazinyl group are more preferable.
  • the monovalent heterocyclic group may have a substituent such as an alkyl group or an alkoxy group.
  • the substituents of the condensed ring structure in the formulas (1) and (2) are each a repeating unit. It is preferable that the structure is linearly symmetric with respect to any one axis or is replaced with a point-symmetrical structure with respect to the center of gravity.
  • the combination of R 13 and R 15 and the combination of R 14 and R 16 in the formula (1) are combinations of the same groups, and R 23 in the formula (2) and
  • the combination with R 25 and the combination of R 24 and R 26 are each preferably a combination of the same groups.
  • the “combination of the same groups with each other” means that the groups are of the same type, for example, alkyl groups or alkoxy groups.
  • the combination of the same groups is preferably the same when the substituent structure is the same, such as chain length or branching, because the packing of the polymer compound is extremely improved.
  • R 13 to R 16 in the formula (1) and R 23 in the formula (2) are preferably a hydrogen atom.
  • the repeating units represented by the formulas (1) and (2) are preferably the repeating units represented by the formulas (1a) and (2a), respectively.
  • X 11 , X 12 , X 21 and X 22 are synonymous with the groups represented by the same symbols in the above formulas (1) and (2).
  • a suitable repeating unit to be combined with at least one repeating unit of the repeating units represented by the formulas (1) and (2) is represented by the formula (3). Repeating units. By further including such a repeating unit, higher charge mobility tends to be easily obtained.
  • Y represents an arylene group, a divalent heterocyclic group, a divalent group having a metal complex structure, or an ethynylene group (a group represented by —C ⁇ C—), It may have a substituent.
  • Y is preferably a repeating unit represented by the formula (3) and the repeating unit represented by the formula (1) and the formula (2) is a repeating unit represented by the formula (1) and the formula (2).
  • a copolymer is formed with at least one of the above, in the skeleton that is the main chain of the polymer compound, multiple bonds and single bonds are alternately repeated by bonds between carbons or bonds between carbons and heteroatoms. It is a group selected so that a continuous ⁇ -conjugated system is formed. Examples of such a ⁇ -conjugated system include structures shown within a dotted line in the following exemplary formula (E1).
  • the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and includes those having an independent benzene ring or condensed ring.
  • the arylene group preferably has 6 to 60 carbon atoms, more preferably 6 to 48 carbon atoms, still more preferably 6 to 30 carbon atoms, and particularly preferably 6 to 18 carbon atoms.
  • arylene group examples include unsubstituted or substituted phenylene groups such as 1,4-phenylene group, 1,3-phenylene group and 1,2-phenylene group; 1,4-naphthalenediyl group and 1,5-naphthalenediyl group 1,6-naphthalenediyl group such as 2,6-naphthalenediyl group; 1,4-anthracenediyl group, 1,5-anthracenediyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group Unsubstituted or substituted anthracenediyl group such as 2,7-phenanthrenediyl group, etc .; 1,7-naphthacenediyl group, 2,8-naphthacenediyl group, 5,12 -Unsubstituted or substituted naphthacenediyl group such as naphthacenediyl group; 2,7-fluorenediyl group,
  • an unsubstituted or substituted phenylene group an unsubstituted or substituted fluorenediyl group is preferable, an unsubstituted or substituted fluorenediyl group is more preferable, and a substituted fluorenediyl group is preferably used. Particularly preferred.
  • Examples of such an arylene group include groups represented by formulas (8a) to (8f).
  • R 83 , R 84 and R 86 are the same or different and each is a hydrogen atom, a halogen atom or a monovalent group, and R 85 is a halogen atom or a monovalent group. is there.
  • U is an integer of 0 or more.
  • Examples of the monovalent group include the same monovalent groups as those exemplified as R 13 to R 16 in the formula (1).
  • groups represented by the same reference numerals may be the same or different.
  • R 83 , R 84 , R 85 and R 86 or groups represented by the same symbol are bonded to the same carbon atom or adjacent carbon atoms, this relationship is established.
  • Some groups may be bonded together to form a ring.
  • the ring formed in this case may be a single ring or a condensed ring, and may be a hydrocarbon ring or a heterocyclic ring. Moreover, these rings may have a substituent.
  • the ring to be formed is preferably a monocyclic hydrocarbon ring or a monocyclic heterocycle containing an oxygen atom or a sulfur atom as a hetero atom.
  • the divalent heterocyclic group generally has 4 to 60 carbon atoms, preferably 4 to 48, more preferably 4 to 30, still more preferably 4 to 22, and particularly preferably 4 carbon atoms. ⁇ 12, particularly preferably 4. This carbon number does not include the carbon number of the substituent.
  • divalent heterocyclic group examples include an unsubstituted or substituted thiophenediyl group such as a 2,5-thiophenediyl group; an unsubstituted or substituted furandyl group such as a 2,5-furandiyl group; -Unsubstituted or substituted pyridinediyl group such as pyridinediyl group and 2,6-pyridinediyl group; unsubstituted or substituted quinolinediyl group such as 2,6-quinolinediyl group; 1,4-isoquinolinediyl group and 1,5 -Unsubstituted or substituted isoquinoline diyl group such as isoquinoline diyl group; unsubstituted or substituted quinoxaline diyl group such as 5,8-quinoxaline diyl group; and 4,7-benzo [1,2,5] thiadiazole diyl group Unsubstituted or substituted benzo [1,2,5] thiadiazoled
  • Benzothiazolediyl group unsubstituted or substituted carbazolediyl group such as 2,7-carbazolediyl group and 3,6-carbazolediyl group; unsubstituted or substituted phenoxazinediyl group such as 3,7-phenoxazinediyl group
  • An unsubstituted or substituted phenothiazinediyl group such as a 3,7-phenothiazinediyl group
  • dibenzosiloldiyl group such as a 2,7-dibenzosiloldiyl group.
  • the divalent heterocyclic group is preferably an unsubstituted or substituted thiophenediyl group such as a 2,5-thiophenediyl group; an unsubstituted or substituted furandyl group such as a 2,5-furandiyl group; An unsubstituted or substituted pyridinediyl group such as a 2,5-pyridinediyl group, a 2,6-pyridinediyl group; an unsubstituted or substituted quinolinediyl group such as a 2,6-quinolinediyl group; a 1,4-isoquinolinediyl group More preferred is an unsubstituted or substituted thiophenediyl group such as a 2,5-thiophenediyl group.
  • Examples of such a divalent heterocyclic group include groups represented by formulas (7a) to (7p).
  • R 73 , R 74 , R 75 , R 76 and v are R 83 , R 84 , R 85 , R 86 and u in the above formulas (8a) to (8f), respectively.
  • Is synonymous with Z is a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, or a silicon atom.
  • the divalent group having a metal complex structure is a group composed of the remaining atomic groups formed by removing two hydrogen atoms from an organic ligand of a metal complex having an organic ligand and a central metal.
  • the metal complex include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, a triplet light-emitting complex, and the like.
  • the central metal of the metal complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
  • the carbon number of the organic ligand is preferably 4 to 60.
  • organic ligands include 8-quinolinol and its derivatives, benzoquinolinol and its derivatives, 2-phenyl-pyridine and its derivatives, 2-phenyl-benzothiazole and its derivatives, 2-phenyl-benzoxazole and its derivatives Derivatives, porphyrins and their derivatives, etc. are mentioned.
  • Examples of the divalent group having such a metal complex structure include groups represented by formulas (100) to (106).
  • R in the formulas (100) to (106) is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group , Arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, non A substituted or substituted carboxyl group or a cyano group is represented. Moreover, the carbon atom which these groups have may be substituted with the nitrogen atom, the oxygen atom, or the sulfur atom, and also the hydrogen atom may be substituted with the fluorine atom. A plurality of R may be the same or different.
  • Y in the repeating unit represented by the formula (3) is preferably a group represented by the formula (4).
  • the polymer compound can exhibit extremely high charge mobility.
  • T represents a divalent heterocyclic group which may have a substituent, and n represents an integer of 2 to 8.
  • a plurality of T may be the same or different.
  • the group represented by the formula (4) is more preferably a group represented by the formula (4a).
  • the polymer compound can exhibit higher charge mobility.
  • R 41 , R 42 , R 43 and R 44 are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, or a substituent.
  • a silyl group, an unsubstituted or substituted carboxyl group, a monovalent heterocyclic group, a cyano group or a fluorine atom is shown.
  • the groups represented by R 41 to R 44 are the same as the groups represented by R 13 to R 16 described above, but are preferably alkyl groups.
  • Y in Formula (3) is preferable even if it is group represented by Formula (5).
  • Ar 1 and Ar 2 are the same or different and each have an aromatic hydrocarbon ring which may have a substituent, a heterocyclic ring which may have a substituent, or a substituent. It is a condensed ring of an aromatic hydrocarbon ring which may be substituted and a heterocyclic ring which may have a substituent.
  • R 51 and R 52 are the same or different and each is a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, substituted silyl group, An unsubstituted or substituted carboxyl group, a monovalent heterocyclic group which may have a substituent, a cyano group or a fluorine atom is shown. ]
  • the group represented by the formula (5) is preferably a group represented by the formula (5a).
  • R 53 and R 54 are the same or different and each represents a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, substituted silyl group, unsubstituted or A substituted carboxyl group, a monovalent heterocyclic group, a cyano group or a fluorine atom is shown.
  • R 53 and R 54 are the same or different and each represents a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, substituted silyl group, unsubstituted or A substituted carboxyl group, a monovalent heterocyclic group, a cyano group or a fluorine atom is shown.
  • R 51 to R 54 are the same as the groups represented by R 13 to R 16 described above.
  • Ar 1 and Ar 2 are preferably benzene rings which may have a substituent.
  • the polymer compound may have a plurality of types in which the groups represented by Y in the formula are different from each other as the repeating unit represented by the formula (3).
  • Y is an unsubstituted or substituted bithiophenediyl group (represented by the formula (4a)) as the repeating unit represented by the formula (3).
  • the polymer compound of the present invention is a homopolymer (that is, a homopolymer) or a copolymer having at least one of the repeating units represented by the formulas (1) and (2). is there.
  • the repeating unit represented by the formula (3) is preferably used as a repeating unit combined with at least one of the repeating units represented by the formulas (1) and (2). is doing.
  • the electron acceptability in a predetermined group is estimated by the value of the energy level of the lowest unoccupied molecular orbital (LUMO), and the value of the energy level of this LUMO is calculated by quantum chemical calculation Gaussian.
  • the density functional method is used as the calculation method
  • B3LYP is used as the density functional
  • 3-21G * is used as the basis function
  • the program used is Gaussian 09 Rev.
  • the case where the LUMO energy level value calculated as A02 is ⁇ 1.4 eV or less is called electron acceptability.
  • the value of the LUMO energy level of the electron accepting group in formula (3) is preferably 4.4 eV or less.
  • the polymer compound includes a plurality of types of repeating units represented by the formulas (1) and (2) and a plurality of types of electron-accepting groups, they are represented by the formulas (1) and (2).
  • the difference between the lowest value of the HOMO energy levels calculated as described above for the repeating unit and the highest value of the LUMO energy levels of the electron-accepting group is 4.4 eV or less. It is preferable to do so.
  • Examples of such electron-accepting groups include groups represented by formulas (9a) to (9j).
  • R 93 , R 94 and R 96 have the same meanings as R 83 , R 84 and R 86 in formulas (8a) to (8f), respectively.
  • At least one of Y in the repeating unit represented by the formula (3) is an electron-accepting group such as a group represented by the formula (6).
  • X 61 represents a chalcogen atom, —N (R 63 ) — or —CR 64 ⁇ CR 65 —.
  • R 61 , R 62 , R 63 , R 64 and R 65 are the same or different and each represents a hydrogen atom or a substituent.
  • R 61 and R 62 are substituents, groups having 1 to 30 carbon atoms are preferred.
  • substituents include methyl groups, ethyl groups, butyl groups, hexyl groups, octyl groups, dodecyl groups and other alkyl groups, methoxy groups, ethoxy groups, butoxy groups, hexyloxy groups, octyloxy groups, dodecyloxy groups.
  • aryl groups such as phenyl and naphthyl.
  • R 61 and R 62 may be connected to each other to form a cyclic structure.
  • Specific examples of the group represented by the formula (6) in which R 61 and R 62 are linked to form a cyclic structure include the following.
  • R 66 and R 67 are the same or different and each represents a hydrogen atom or a substituent.
  • substituent represented by R 66 and R 67 include the same groups as the substituents represented by R 61 and R 62 described above, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. It is.
  • X 61 is preferably a sulfur atom.
  • group represented by Formula (6a) is especially preferable.
  • the value of the LUMO energy level calculated by the above quantum chemical calculation Gaussian in such a repeating unit is ⁇ 2.32 eV.
  • N in the following formulas (110) to (160) represents the number of repeating units (degree of polymerization), preferably 4 to 3000, and more preferably 6 to 850.
  • N in the following formulas (110) to (160) represents the number of repeating units (degree of polymerization), preferably 4 to 3000, and more preferably 6 to 850.
  • n 4 to 3000 (preferably 6 to 850) are also suitable polymer compounds.
  • the polymer compound is a copolymer
  • good charge injection properties and solubility can be obtained, so the total number of repeating units represented by formulas (1) and (2) with respect to the total number of moles of all repeating units.
  • the number of moles is preferably 20 to 80%, more preferably 30 to 70%, and still more preferably 40 to 60%.
  • the total number of repeating units other than these is the total number of repeating units represented by formulas (1) and (2).
  • the number is preferably 10% or less, more preferably 5% or less, further preferably 1% or less, and particularly preferably 0.05% or less.
  • any copolymer may be used, such as a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer. There may be. However, since good charge injection property, charge transfer property, main chain packing and solubility are obtained, at least one repeating unit represented by formulas (1) and (2) in the structure of the polymer compound. And a repeating unit represented by the formula (3) is preferably included.
  • a high molecular compound is a repeating unit represented by any 1 type of the repeating unit represented by Formula (1) and (2), and a repeating unit represented by Formula (3). Is preferably a structure in which the repeating units represented by formula (1) and the repeating unit represented by formula (3) are alternately bonded.
  • the total number of repeating units constituting the “alternately bonded structure” It is preferably 90% or more, more preferably 99% or more, further preferably 99.5% or more, and particularly preferably 99.9% or more, based on the unit, on a molar basis.
  • the polymer compound is a compound having a plurality of repeating units, and at least one of them is a repeating unit represented by the formula (1) or (2).
  • the polymer compound gel permeation chromatography (hereinafter, "GPC" hereinafter.)
  • the number average molecular weight in terms of polystyrene by (Mn) is preferable to be 1 ⁇ 10 3 ⁇ 1 ⁇ 10 8, 1 ⁇ 10 4 More preferably, it is ⁇ 1 ⁇ 10 6 .
  • the weight average molecular weight (Mw) in terms of polystyrene by GPC of this polymer compound is preferably 1 ⁇ 10 3 to 1 ⁇ 10 8 .
  • a good film formability can be obtained, and high mobility can be obtained when used for device fabrication. Therefore, the weight average molecular weight is more preferably 1 ⁇ 10 4 to 5 ⁇ 10 6. more preferable to be 4 ⁇ 5 ⁇ 10 5, and particularly preferably 1 ⁇ 10 4 ⁇ 5 ⁇ 10 5.
  • the terminal group is preferably a stable group.
  • Such a terminal group is preferably one having a conjugated bond to the main chain, such as a structure bonded to an aryl group or a heterocyclic group via a carbon-carbon bond.
  • substituents described in Chemical formula 10 of JP-A-9-45478 can be exemplified as terminal groups.
  • Such a high molecular compound is useful as it is as a light emitting material, a hole transport material, an electron transport material, or the like, but when used, it may be used in combination with other high molecular weight compounds. You may use as such a composition.
  • the polymer compound is obtained by condensing the raw material compounds corresponding to the repeating units represented by the formulas (1) and (2) such as the compound represented by the formula (21) and the compound represented by the formula (22). It can be produced by polymerization. Further, when the polymer compound is a copolymer, these compounds may be subjected to condensation polymerization in combination with a raw material compound corresponding to the repeating unit to be combined. For example, when the repeating unit represented by the formula (3) is introduced, it is preferable to use the raw material compound represented by the formula (23) in combination.
  • Z 11 , Z 12 , Z 21 , Z 22 , Z 31 and Z 32 are the same or different polymerization active groups.
  • the polymerization active group include a halogen atom, a sulfonate group represented by the formula (a-1), a methoxy group, a boric acid ester residue, a boric acid residue (a group represented by —B (OH) 2 ), Examples thereof include a group represented by the formula (a-2), a group represented by the formula (a-3), and a group represented by the formula (a-4).
  • groups represented by the same reference numerals may be the same or different from each other.
  • R T represents an alkyl group which may have a substituent, or an aryl group which may have a substituent, and X A represents a halogen atom.
  • X A represents a halogen atom.
  • plural R T in may each be the same or different.
  • Examples of the alkyl group and aryl group represented by R T include the same groups as those exemplified as R 13 to R 16 in the above formula (1).
  • the halogen atom represented by X A a chlorine atom, a bromine atom, an iodine atom.
  • the halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom.
  • the sulfonate group represented by the formula (a-1) include a methane sulfonate group, a trifluoromethane sulfonate group, a phenyl sulfonate group, and a 4-methylphenyl sulfonate group.
  • boric acid ester residue examples are represented by the formula (a-5), (a-6), (a-7), (a-8), (a-9) or (a-10). Groups.
  • examples of the group represented by the formula (a-4) include a trimethylstannanyl group, a triethylstannanyl group, and a tributylstannanyl group.
  • the synthesis of the raw material compounds represented by these formulas is easy and easy to handle, so that a halogen atom, a borate ester residue, boric acid Residues are preferred.
  • the raw material compounds represented by the formulas (21) to (23) those synthesized and isolated in advance may be used, or those prepared in the reaction system may be used as they are.
  • Examples of the method for subjecting the raw material compound to condensation polymerization include a method in which the raw material compound is reacted using an appropriate catalyst or an appropriate base as necessary.
  • the catalyst include palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium complexes such as palladium acetate, nickel [tetrakis (triphenylphosphine)], [1,3-bis And transition metal complexes such as (diphenylphosphino) propane] dichloronickel and nickel complexes such as [bis (1,4-cyclooctadiene)] nickel.
  • transition metal complexes can be combined with a ligand such as triphenylphosphine, tri (tert-butylphosphine), tricyclohexylphosphine, diphenylphosphinopropane, bipyridyl, or the like to form a catalyst.
  • a ligand such as triphenylphosphine, tri (tert-butylphosphine), tricyclohexylphosphine, diphenylphosphinopropane, bipyridyl, or the like to form a catalyst.
  • a catalyst synthesized in advance may be used, or a catalyst prepared in a reaction system may be used as it is.
  • a catalyst may be used individually by 1 type and may use 2 or more types together.
  • a catalyst When a catalyst is used, it is preferably 0.00001 to 3 molar equivalents, more preferably 0.00005 to 0.5 molar equivalents, and further 0.0001 to 0.2 molar equivalents relative to the total number of moles of raw material compounds. preferable.
  • Examples of the base that promotes the condensation reaction include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, and tripotassium phosphate, tetrabutylammonium fluoride, tetrabutylammonium chloride, and bromide.
  • examples include organic bases such as tetrabutylammonium and tetrabutylammonium hydroxide.
  • the amount thereof is preferably 0.5 to 20 molar equivalents and more preferably 1 to 10 molar equivalents relative to the total number of moles of the raw material compounds.
  • the condensation polymerization may be performed in the absence of a solvent or in the presence of a solvent, but is preferably performed in the presence of an organic solvent.
  • organic solvent for example, toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide can be used, although it varies depending on the type of raw material compound and reaction. . Since side reactions can be suppressed, it is desirable to use an organic solvent that has been subjected to deoxygenation treatment. These organic solvents may be used individually by 1 type, and may use 2 or more types together.
  • the amount used is preferably such that the total concentration of the raw material compounds is 0.1 to 90% by weight, more preferably 1 to 50% by weight. More preferably, the amount is 30% by weight.
  • the reaction temperature for the condensation polymerization is preferably ⁇ 100 ° C. to 200 ° C., more preferably ⁇ 80 ° C. to 150 ° C., and further preferably 0 ° C. to 120 ° C.
  • a suitable reaction time is 1 hour or more, more preferably 2 to 500 hours, although it depends on conditions such as reaction temperature.
  • condensation polymerization examples include a method of polymerizing by a Suzuki reaction (Chem. Rev., Vol. 95, p. 2457 (1995)), a method of polymerizing by a Grignard reaction (Kyoritsu Shuppan, series of functional polymer materials) Volume 2, Polymer Synthesis and Reaction (2), pages 432 to 433), Method of Polymerization by Yamamoto Polymerization Method (Progressive Polymer Science (Prog. Polym. Sci.), Volume 17, pages 1153-1205, 1992 Year).
  • a known post-treatment can be performed after the condensation polymerization.
  • a method may be mentioned in which a reaction solution obtained by condensation polymerization is added to a lower alcohol such as methanol and the resulting precipitate is filtered and dried.
  • the polymer compound of the present invention can be obtained.
  • the purity of the polymer compound is low, it can be purified by usual methods such as recrystallization, continuous extraction with a Soxhlet extractor, column chromatography and the like. That's fine.
  • the polymer compound is the former raw material compound. It is preferable to carry out the following reaction, since it is preferable to alternately have a repeating unit consisting of and a repeating unit consisting of the latter raw material compound.
  • a combination of a compound in which the polymerization active group in formulas (21) and (22) is a halogen atom and a compound in which the polymerization active group in formula (23) is a boric acid residue or a boric acid ester residue Alternatively, a combination of a compound in which the polymerization active group in formulas (21) and (22) is a boric acid residue or a borate ester residue and a compound in which the polymerization active group in formula (23) is a halogen atom
  • a method of polymerizing by using Suzuki polymerization is preferable.
  • composition The above-described polymer compound of the present invention can be used as a light-emitting material or a charge transport material as a composition containing a combination of other components.
  • a composition include those containing a polymer compound and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material.
  • suitable hole transport materials and electron transport materials those exemplified in the description of the thin film described later can be applied.
  • the content ratio of the polymer compound and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material may be determined according to the use of the composition.
  • the polymer compound is preferably 20 to 99 parts by weight and more preferably 40 to 95 parts by weight with respect to 100 parts by weight of the total composition.
  • the number average molecular weight (Mn) in terms of polystyrene by GPC of the composition containing the polymer compound is preferably 1 ⁇ 10 3 to 1 ⁇ 10 8 and more preferably 5 ⁇ 10 3 to 1 ⁇ 10 6. preferable.
  • the weight average molecular weight (Mw) in terms of polystyrene is preferably 1 ⁇ 10 3 to 1 ⁇ 10 8 , good film formability can be obtained, and high efficiency can be obtained when used for device fabrication. Therefore, it is more preferably 1 ⁇ 10 4 to 5 ⁇ 10 6 .
  • the average molecular weight of the composition containing the polymer compound refers to a value obtained by analyzing this composition by GPC.
  • the composition of the present invention can also be a solution containing a solvent such as an organic solvent (hereinafter referred to as “ink composition”), as will be described later.
  • a solvent such as an organic solvent
  • a suitable form of the ink composition will be described.
  • the ink composition containing the polymer compound of the present invention contains a polymer compound and a solvent.
  • the ink composition may contain a composition containing the polymer compound as described above and a solvent.
  • This ink composition is mainly in the form of a solution and is useful for forming a thin film by a printing method or the like.
  • Components other than the polymer compound and solvent contained in the ink composition include hole transport materials, electron transport materials, light emitting materials, stabilizers, thickeners (high molecular weight compounds and poor solvents for increasing viscosity), viscosity A low molecular weight compound for lowering the pH, a surfactant (for lowering the surface tension), an antioxidant and the like.
  • the ink composition may contain only one kind of the polymer compound of the present invention, or may contain two or more kinds in combination. Further, it may contain a high molecular weight compound other than the polymer compound of the present invention as long as the characteristics are not impaired when used for the production of an element.
  • the ratio of the polymer compound of the present invention in the ink composition is preferably 1 to 99.9 parts by weight and more preferably 60 to 99.5 parts by weight with respect to 100 parts by weight of the total amount of the ink composition. 80 to 99.0 parts by weight is even more preferable.
  • the coating method can be performed satisfactorily, and a thin film or the like that can exhibit the excellent characteristics of the polymer compound can be easily formed.
  • the viscosity of the ink composition may be adjusted depending on the type of printing method to be used.For example, when the ink composition such as an ink jet printing method is applied to a method that passes through a discharge device, clogging or flight bending at the time of discharge is caused. In order to prevent this, it is preferably in the range of 1 to 20 mPa ⁇ s at 25 ° C.
  • the solvent used in the ink composition is preferably one that can dissolve or uniformly disperse the solid components in the ink composition.
  • Solvents include chloro solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, ether solvents such as tetrahydrofuran, dioxane, anisole, toluene, xylene, etc.
  • Aromatic hydrocarbon solvents cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, Ketone solvents such as cyclohexanone, benzophenone and acetophenone, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol Polyethyl alcohol and its derivatives such as monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, g
  • aromatic hydrocarbon solvents ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, n-hexylbenzene, cyclohexylbenzene, 1-methylnaphthalene, Tetralin, anisole, ethoxybenzene, cyclohexane, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, decalin,
  • the solvent film formability and device characteristics are improved, so that two or more types are preferably used in combination, more preferably two to three types are used in combination, and two types are particularly preferably used in combination. .
  • one of the solvents When combining two types of solvents, one of the solvents may be in a solid state at 25 ° C.
  • the boiling point of at least one kind of solvent is preferably 180 ° C. or higher, and more preferably 200 ° C. or higher.
  • both of the two types of solvents are those capable of dissolving 1% by weight or more of the aromatic polymer at 60 ° C., and in particular, one of the two types of solvents.
  • the type of solvent is preferably one that dissolves 1% by weight or more of the aromatic polymer at 25 ° C.
  • the solvent having the highest boiling point among the combined solvents should be 40 to 90% by weight of the total solvent weight. It is preferably 50 to 90% by weight, more preferably 65 to 85% by weight.
  • the ink composition contains a high molecular weight compound as a thickener
  • this compound is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport when a device is formed.
  • thickeners include high molecular weight polystyrene and high molecular weight polymethyl methacrylate. These high molecular weight compounds preferably have a polystyrene equivalent weight average molecular weight of 500,000 or more, more preferably 1,000,000 or more.
  • the poor solvent with respect to solid content in the component of an ink composition can also be used.
  • the viscosity can be increased moderately by adding a small amount of such a poor solvent.
  • the type and amount of the solvent may be selected as long as the solid content in the ink composition does not precipitate.
  • the amount of the poor solvent is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, with respect to 100 parts by weight of the entire ink composition. .
  • the antioxidant is for improving the storage stability of the ink composition.
  • the antioxidant is not particularly limited as long as it is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport when a device is formed.
  • a phenolic antioxidant or a phosphorus antioxidant Is exemplified.
  • the ink composition may contain water, metal or a salt thereof in the range of 1 to 1000 ppm on a weight basis.
  • the metal include lithium, sodium, calcium, potassium, iron, copper, nickel, aluminum, zinc, chromium, manganese, cobalt, platinum, and iridium.
  • the ink composition may contain silicon, phosphorus, fluorine, chlorine, bromine and the like in a range of 1 to 1000 ppm on a weight basis.
  • the thin film containing the polymer compound of the present invention can be applied as, for example, a light-emitting thin film, a conductive thin film, or an organic semiconductor thin film.
  • the thin film is a light-emitting thin film
  • high luminance and light emission voltage can be obtained, so that the quantum yield of light emission is preferably 30% or more, more preferably 50% or more, and 60% or more. Is more preferable, and 70% or more is particularly preferable.
  • the surface resistance is preferably 1 k ⁇ / ⁇ or less, more preferably 100 ⁇ / ⁇ or less, and even more preferably 10 ⁇ / ⁇ or less.
  • the conductive thin film is doped with a Lewis acid, an ionic compound, or the like, higher electrical conductivity can be obtained.
  • the larger one of the electron mobility and the hole mobility is preferably 10 ⁇ 5 cm 2 / Vs or more, and more preferably 10 ⁇ 3 cm 2 / Vs or more. Preferably, it is more preferably 10 ⁇ 1 cm 2 / Vs or more.
  • An organic transistor as described later can be formed using such an organic semiconductor thin film.
  • the thickness is preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, still more preferably 3 nm to 500 nm, and particularly preferably 5 nm to 200 nm.
  • the organic semiconductor thin film may contain one kind of the polymer compound of the present invention alone, or may contain two or more kinds in combination.
  • a low molecular compound or polymer compound having electron transport property or hole transport property other than the polymer compound may be mixed.
  • hole transport material known materials can be used, such as pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triaryldiamine derivatives, oligothiophenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilanes and derivatives thereof, side chains or main chains.
  • pyrazoline derivatives such as pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triaryldiamine derivatives, oligothiophenes and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilanes and derivatives thereof, side chains or main chains.
  • examples thereof include polysiloxane derivatives having an aromatic amine, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyarylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.
  • known materials can be used, such as oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodi. methane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and its derivatives, polyfluorene and its derivatives, such as C 60 Examples include fullerenes and derivatives thereof.
  • the thin film of this embodiment may contain the charge generation material in order to generate an electric charge with the light absorbed by the said thin film depending on a use.
  • the charge generation material known materials can be used, azo compounds and derivatives thereof, diazo compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, polycyclic quinone series compounds and their derivatives, squarylium compounds and their derivatives, azulenium compounds and their derivatives, thiapyrylium compounds and their derivatives, fullerenes and derivatives thereof such as C 60 is illustrated.
  • the thin film of this embodiment may contain other materials necessary for expressing various functions.
  • examples of such materials include sensitizers for sensitizing the function of generating charges by absorbed light, stabilizers for increasing stability, and UV absorbers for absorbing UV light.
  • a polymer compound other than the polymer compound of the present invention may be included as a polymer binder.
  • the polymer binder those not extremely disturbing the electron transport property or hole transport property are preferable, and those having no strong absorption against visible light are preferably used.
  • Such polymer binders 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.
  • Examples include derivatives, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
  • Examples of the method for producing a thin film of the present embodiment include a method of using the polymer compound of the present invention as it is, or a method of forming a film using the above-described composition (for example, an ink composition).
  • a thin film can be formed by vacuum deposition.
  • Thin film formation methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing.
  • Method, offset printing method, inkjet printing method, capillary coating method, nozzle coating method, dispenser printing method, etc., screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing method are preferable, flexographic printing method A printing method, an inkjet method, and a dispenser printing method are more preferable.
  • a solution for example, an ink composition
  • a solvent to be used in addition to the polymer compound of the present invention, components to be mixed (electron transport material, hole transport material, polymer binder, etc.) are dissolved. It is preferable to use those to be used.
  • those used in the ink composition described above can be applied, and unsaturated hydrocarbons such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, etc.
  • unsaturated hydrocarbons such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, etc.
  • Solvent halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, trichlorobenzene And halogenated unsaturated hydrocarbon solvents such as tetrahydrofuran, and ether solvents such as tetrahydrofuran and tetrahydropyran.
  • the polymer compound of the present invention depends on its structure and molecular weight, it can often be dissolved in these solvents in an amount of 0.1% by weight or more.
  • the glass transition temperature of the polymer compound of the present invention contained in this solution tends to be high, and thus it can be baked at a temperature of 100 ° C. or higher during the film formation process. In addition, even when baked at a temperature of 130 ° C., the characteristics are less likely to be deteriorated when used for device fabrication, so that a thin film can be easily formed. Furthermore, depending on the type of the polymer compound, baking may be performed at a temperature of 160 ° C. or higher.
  • the process of orientating a high molecular compound may be included in the manufacturing process.
  • the main chain molecules or the side chain molecules are arranged in one direction, and therefore the charge mobility is further increased.
  • a method of aligning the polymer compound a method known as a liquid crystal alignment method can be used.
  • the rubbing method, the photo-alignment method, the sharing method (shear stress application method) and the pulling coating method are simple, useful and easy to use as the alignment method, and the rubbing method and the sharing method are preferable.
  • the thin film of the present invention Since the thin film of the present invention has a charge transport property, it can control the transport of electrons or holes injected from the electrode or the charge generated by light absorption, such as organic transistors, solar cell modules, and optical sensors. It can be used for the organic thin film element. In addition, when using the thin film of this invention for these organic thin film elements, it is preferable to orientate and use by the orientation process mentioned above from higher electron transport property or hole transport property being obtained. Hereinafter, suitable examples of the organic thin film element will be described.
  • Organic transistor First, a preferred embodiment of an organic transistor including an organic semiconductor layer containing the polymer compound of the present invention will be described.
  • An organic transistor includes a source electrode and a drain electrode, an organic semiconductor layer containing the polymer compound as a current path between them, and a gate electrode that controls the amount of current passing through the current path.
  • An electric induction type is exemplified.
  • a field-effect organic transistor includes a source electrode and a drain electrode, an organic semiconductor layer serving as a current path between them, a gate electrode that controls the amount of current passing through the current path, and a gap between the organic semiconductor layer and the gate electrode. It is preferable to provide an insulating layer to be disposed.
  • the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer, and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween.
  • the static induction organic transistor has a source electrode and a drain electrode, an organic semiconductor layer serving as a current path between them, and a gate electrode for controlling the amount of current passing through the current path, and the gate electrode is in the organic semiconductor layer.
  • the source electrode, the drain electrode, and the gate electrode provided in the organic semiconductor layer are preferably provided in contact with the organic semiconductor layer.
  • the structure of the gate electrode may be a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. An electrode is mentioned.
  • FIG. 1 is a schematic cross-sectional view of an organic transistor (field effect organic transistor) according to the first embodiment.
  • the organic transistor 100 shown in FIG. 1 is formed on the substrate 1 so as to cover the substrate 1, the source electrode 5 and the drain electrode 6 formed on the substrate 1 with a predetermined interval, and the source electrode 5 and the drain electrode 6.
  • a gate electrode 4 is a schematic cross-sectional view of an organic transistor (field effect organic transistor) according to the first embodiment.
  • the organic transistor 100 shown in FIG. 1 is formed on the substrate 1 so as to cover the substrate 1, the source electrode 5 and the drain electrode 6 formed on the substrate 1 with a predetermined interval, and the source electrode 5 and the drain electrode 6.
  • Formed on the insulating layer 3 so as to cover the region of the insulating layer 3 formed on the organic semiconductor layer 2,
  • FIG. 2 is a schematic cross-sectional view of an organic transistor (field effect organic transistor) according to the second embodiment.
  • An organic transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an organic semiconductor layer 2 formed on the substrate 1 so as to cover the source electrode 5, The drain electrode 6 formed on the organic semiconductor layer 2 with a predetermined interval, the insulating layer 3 formed on the organic semiconductor layer 2 and the drain electrode 6, and the insulation between the source electrode 5 and the drain electrode 6 And a gate electrode 4 formed on the insulating layer 3 so as to cover the region of the layer 3.
  • FIG. 3 is a schematic cross-sectional view of an organic transistor (field effect organic transistor) according to a third embodiment.
  • 3 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.
  • FIG. 4 is a schematic cross-sectional view of an organic transistor (field effect organic transistor) according to a fourth embodiment.
  • An organic transistor 130 shown in FIG. 4 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.
  • FIG. 5 is a schematic cross-sectional view of an organic transistor (static induction organic transistor) according to a fifth embodiment.
  • the organic transistor 140 shown in FIG. 5 includes a substrate 1, a source electrode 5 formed on the substrate 1, an organic semiconductor layer 2 formed on the source electrode 5, and a plurality of organic transistors 140 with a predetermined interval on the organic semiconductor layer 2.
  • a drain electrode 6 formed on the organic semiconductor layer 2a is a schematic cross-sectional view of an organic transistor (static induction organic transistor) according to a fifth embodiment.
  • the organic transistor 140 shown in FIG. 5 includes a substrate 1, a source electrode 5 formed on the substrate 1, an organic semiconductor layer 2 formed on the source electrode 5, and a plurality of organic transistors 140 with a predetermined interval on the organic semiconductor layer 2.
  • FIG. 6 is a schematic cross-sectional view of an organic transistor (field effect organic transistor) according to a sixth embodiment.
  • An organic transistor 150 shown in FIG. 6 includes a substrate 1, an organic semiconductor layer 2 formed on the substrate 1, a source electrode 5 and a drain electrode 6 formed on the organic semiconductor layer 2 with a predetermined interval, and a source electrode. 5 and the drain electrode 6 so as to partially cover the insulating layer 3 formed on the organic semiconductor layer 2, the region of the insulating layer 3 where the source electrode 5 is formed below, and the drain electrode 6 are formed below.
  • a gate electrode 4 formed on the insulating layer 3 so as to partially cover the region of the insulating layer 3.
  • FIG. 7 is a schematic cross-sectional view of an organic transistor (field effect organic transistor) according to a seventh embodiment.
  • the organic transistor 160 shown in 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 below.
  • the organic semiconductor layer 2 formed so as to cover the region of the insulating layer 3 formed on the organic semiconductor layer 2 and the organic semiconductor layer 2 so as to partially cover the region of the organic semiconductor layer 2 where the gate electrode 4 is formed below.
  • the drain formed on the organic semiconductor layer 2 with a predetermined distance from the source electrode 5 so as to partially cover the region of the organic semiconductor layer 2 on which the source electrode 5 and the gate electrode 4 are formed below.
  • the electrode 6 is provided.
  • the organic semiconductor layer 2 and / or the organic semiconductor layer 2a serve as a current path (channel) between the source electrode 5 and the drain electrode 6.
  • the gate electrode 4 controls the amount of current passing through the current path (channel) in the organic semiconductor layer 2 and / or the organic semiconductor layer 2a by applying a voltage.
  • a field effect organic transistor can be produced by a known method, for example, a method described in JP-A-5-110069.
  • the electrostatic induction organic transistor can be manufactured by a known method, for example, a method described in JP-A-2004-006476.
  • the substrate 1 does not have to obstruct the characteristics as an organic transistor, and a glass substrate, a flexible film substrate, or a plastic substrate can also be used.
  • the organic semiconductor layer 2 is composed of a thin film (organic semiconductor thin film) containing the polymer compound of the present invention described above.
  • This organic semiconductor layer 2 may be composed of only this polymer compound, or may be composed of materials other than the polymer compound. Moreover, only 1 type of the high molecular compound of this invention may be included, and 2 or more types may be included.
  • the organic semiconductor layer 2 may further contain an electron transport material and / or a hole transport material in addition to the polymer compound of the present invention in order to enhance the electron transport property or the hole transport property.
  • As the hole transport material and the electron transport material those which can be contained in the above-described thin film can be applied.
  • the organic semiconductor layer 2 may contain a polymer binder in order to obtain high mechanical properties. As the polymer binder, those which can be contained in the above-described thin film can be applied.
  • the thickness of the organic semiconductor layer 2 is preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, still more preferably 3 nm to 500 nm, and particularly preferably 5 nm to 200 nm.
  • the organic semiconductor layer 2 can be formed by applying the thin film forming method as described above. That is, in the manufacture of an organic transistor, a thin film (organic semiconductor thin film) is formed on the surface on which the organic semiconductor layer 2 is to be formed (for example, the substrate 1 or the insulating layer 3) by the above-described thin film forming method, thereby The semiconductor layer 2 is formed. Moreover, when forming the organic-semiconductor layer 2, when the process of orienting the high molecular compound contained in a thin film is performed, since the mobility of an electric charge improves, it is preferable.
  • any material having high electrical insulation may be used, and a known material can be used.
  • the constituent material of the insulating layer 3 include SiO x , SiN x , Ta 2 O 5 , polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass, and photoresist. Since the voltage can be lowered, it is preferable to use a material having a high dielectric constant for the insulating layer 3.
  • the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the organic semiconductor layer 2. It is also possible to form the organic semiconductor layer 2 after the surface modification.
  • a surface treatment agent such as a silane coupling agent
  • silane coupling agents include alkylchlorosilanes (octyltrichlorosilane (OTS), octadecyltrichlorosilane (ODTS), phenylethyltrichlorosilane, etc.), alkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxysilanes, Examples thereof include silylamine compounds such as hexamethyldisilazane (HMDS).
  • HMDS hexamethyldisilazane
  • the surface of the insulating layer 3 can be treated with ozone UV or O 2 plasma before the treatment with the surface treatment agent.
  • the surface energy of the silicon oxide film or the like used as the insulating layer 3 can be controlled. Further, the surface treatment improves the orientation of the polymer compound constituting the organic semiconductor layer 2 on the insulating layer 3, thereby obtaining high charge mobility.
  • the gate electrode 4 examples include metals such as gold, platinum, silver, copper, chromium, palladium, aluminum, indium, molybdenum, low resistance polysilicon, and low resistance amorphous silicon, tin oxide, indium oxide, indium / tin oxide.
  • a material such as (ITO) can be used. These materials can be used alone or in combination of two or more.
  • a highly doped silicon substrate can be used as the gate electrode 4.
  • a highly doped silicon substrate has not only a property as a gate electrode but also a property 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 gate electrode 4 can also serve as the substrate 1.
  • the source electrode 5 and the drain electrode 6 are made of a low resistance material, for example, gold, platinum, silver, copper, chromium, palladium, aluminum, indium, or molybdenum.
  • a low resistance material for example, gold, platinum, silver, copper, chromium, palladium, aluminum, indium, or molybdenum.
  • gold and platinum are preferable because the charge injection property is good, and gold is more preferable because the processability is also good.
  • These materials may be used alone or in combination of two or more.
  • an organic transistor is not limited to said embodiment.
  • a layer made of a compound different from the above-described polymer compound of the present invention may be interposed between the source electrode 5 and the drain electrode 6 and the organic semiconductor layer 2. Thereby, the contact resistance between the source electrode 5 and the drain electrode 6 and the organic semiconductor layer 2 is reduced, and the carrier mobility of the organic transistor may be further increased.
  • Such layers include low molecular compounds having electron or hole transport properties as described above; alkali metals, alkaline earth metals, rare earth metals, complexes of these metals with organic compounds, etc .; iodine, bromine, chlorine, Halogens such as iodine chloride; sulfur oxide compounds such as sulfuric acid, sulfuric anhydride, sulfur dioxide, and sulfates; nitric oxide compounds such as nitric acid, nitrogen dioxide, and nitrates; halogenated compounds such as perchloric acid and hypochlorous acid; alkylthiols Examples thereof include a layer made of an aromatic thiol compound such as a compound, an aromatic thiol, and a fluorinated alkyl aromatic thiol.
  • the organic transistor after manufacturing the organic transistor as described above, it is preferable to form a protective film on the organic transistor in order to protect the element. Thereby, an organic transistor is interrupted
  • Examples of the method for forming the protective film include a method of covering the organic transistor with a UV curable resin, a thermosetting resin, an inorganic SiON x film, or the like.
  • a method of covering the organic transistor with a UV curable resin, a thermosetting resin, an inorganic SiON x film, or the like.
  • the planar light source and the display device include at least two organic transistors, that is, a driving transistor and a switching transistor.
  • the planar light source and display device of the present embodiment uses the above-described organic transistor of the present invention as at least one of the organic transistors.
  • FIG. 8 is a schematic cross-sectional view of a planar light source according to a preferred embodiment.
  • An organic transistor T is configured by the organic semiconductor layer 2 formed on the insulating layer 3 so as to partially cover the organic semiconductor layer 2 and the protective film 11 formed on the organic semiconductor layer 2 so as to cover the entire organic semiconductor layer 2. Yes.
  • a lower electrode (anode) 13, a light emitting element 14, and an upper electrode (cathode) 15 are sequentially stacked on the organic transistor T via the interlayer insulating film 12.
  • the lower electrode 13 and the drain electrode 6 are electrically connected through a via hole provided in 12.
  • a bank portion 16 is provided around the lower electrode 13 and the light emitting element 14.
  • a substrate 18 is disposed above the upper electrode 15, and a gap between the upper electrode 15 and the substrate 18 is sealed with a sealing member 17.
  • the organic transistor T functions as a drive transistor. Further, in the planar light source 200 shown in FIG. 8, the switching transistor is omitted.
  • the organic transistor of the present invention described above is used as the organic transistor T.
  • the structural member in a well-known planar light source can be used.
  • substrate 18, a transparent thing is used.
  • planar light source 200 shown in FIG. 8 functions as a planar light source by using a white light emitting material for the light emitting element 14, but uses a red light emitting material, a blue light emitting material, and a green light emitting material for the light emitting element 14. By controlling the driving of each light emitting element, a color display device can be obtained.
  • a method of installing a mask provided with a patterned window on the surface of the planar light emitting element, non-light emission of a light emitting layer constituting the light emitting element There are a method of forming a portion to be extremely thick and making substantially no light emission, and a method of forming an anode or a cathode, or both electrodes in a pattern.
  • both the anode and the cathode may be formed in stripes and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of light emitting materials having different emission colors or a method using a color filter or a fluorescence conversion filter.
  • the dot matrix element can be passively driven or can be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.
  • the polymer compound of the present invention is also useful as a material applied to an organic semiconductor layer for a photoelectric conversion element.
  • a pair of electrodes at least one of which is transparent or translucent, an electron donating compound (p-type organic semiconductor) and an electron-accepting compound (n-type organic semiconductor, etc.) Examples include a bulk hetero organic semiconductor layer or a p / n stacked organic semiconductor layer formed from an organic composition.
  • the polymer compound of the present invention described above is contained in these organic semiconductor layers as at least one of an electron donating compound and an electron accepting compound.
  • the photoelectric conversion device having such a configuration, the light energy incident from the transparent or translucent electrode is absorbed by the electron-accepting compound and / or the electron-donating compound, and the electron and the hole are subjected to Coulomb coupling. Create a child.
  • the excitons generated thereby move and reach the heterojunction interface where the electron accepting compound and the electron donating compound are adjacent to each other, the value of the energy level of each HOMO and the value of the energy level of the LUMO at the interface.
  • the electron and hole are separated from each other, and a charge that can move independently is generated. Then, each generated charge moves to each electrode, and can be taken out as electric energy (current) to the outside. Since the photoelectric conversion element having the organic semiconductor layer containing the polymer compound of the present invention described above has high mobility of the polymer compound, excellent photoelectric conversion efficiency can be obtained.
  • FIG. 10 is a schematic cross-sectional view showing a photoelectric conversion element according to a preferred embodiment.
  • a photoelectric conversion element 300 shown in FIG. 10 is formed on the substrate 1, the anode 7a formed on the substrate 1, the organic semiconductor layer 2 made of an organic thin film formed on the anode 7a, and the organic semiconductor layer 2.
  • the organic semiconductor layer 2 includes an electron donating compound and an electron accepting compound, and at least one of them is the above-described polymer compound of the present invention.
  • anode 7a the organic semiconductor layer 2, and the electron-donating compound and electron-accepting compound, the cathode 7b, and other components formed as necessary, which constitute the photoelectric conversion element 300, will be described in detail. To do.
  • the photoelectric conversion element usually has a configuration in which each layer is formed on a substrate.
  • the substrate 1 may be any substrate that can form electrodes and does not change chemically when forming an organic layer. Examples of the material of the substrate 1 include glass, plastic, polymer film, silicon, and the like.
  • the opposite electrode that is, the electrode far from the substrate
  • At least one of the electrodes is made of a transparent or translucent electrode material.
  • the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film. Specifically, it is manufactured using indium oxide, zinc oxide, tin oxide, and conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA that are composites thereof. A film, gold, platinum, silver, copper or the like is used. Of these, ITO, indium / zinc / oxide, and tin oxide are preferable.
  • Electrodes When either one of the electrodes (the anode 7a and the cathode 7b) is transparent or translucent, the other may not be transparent.
  • a metal, a conductive polymer, or the like can be used as a material for such an electrode.
  • electrode materials include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, And two or more alloys thereof, or one or more metals selected from the group consisting of one or more of the metals and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin.
  • the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
  • Examples of methods for producing these electrodes include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
  • the transparent or translucent electrode may be an anode or a cathode.
  • the organic semiconductor layer 2 included in the photoelectric conversion element 300 includes the above-described polymer compound of the present invention as at least one of an electron donating compound and an electron accepting compound.
  • the electron-donating compound and the electron-accepting compound are relatively determined from the value of the energy level of HOMO or LUMO of these compounds.
  • the electron donating compound the polymer compound of the present invention, and other low molecular compounds and polymer compounds can be applied.
  • the electron donating compound other than the polymer compound of the present invention include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, side Polysiloxane derivatives having aromatic amines in the chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polymer compounds having thiophene as a partial skeleton, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and And derivatives thereof.
  • the electron donating compound the above-described polymer compound of the present invention is particularly suitable.
  • Examples of the electron-donating compound other than the polymer compound of the present invention include polythiophene (including polythiophene and derivatives thereof) which may have a substituent, a structure containing a dimer or pentamer of thiophene, or a derivative of thiophene.
  • a polymer compound having a structure containing a ⁇ 5-mer and a polymer compound having thiophene as a partial skeleton are preferable. Of these, polythiophene and its derivatives are more preferable.
  • the polythiophene derivative refers to a polymer compound having a thiophenediyl group having a substituent.
  • Polythiophene and its derivatives are preferably homopolymers.
  • the homopolymer means a polymer in which only a plurality of groups selected from the group consisting of a thiophenediyl group and a substituted thiophenediyl group are bonded.
  • the thiophene diyl group is preferably a thiophene-2,5-diyl group, and the thiophene diyl group having a substituent is preferably an alkylthiophene-2, 5-diyl group.
  • homopolymer polythiophene and derivatives thereof include poly (3-hexylthiophene-2,5-diyl) (P3HT), poly (3-octylthiophene-2,5-diyl), poly (3-dodecyl) Thiophene-2,5-diyl) and poly (3-octadecylthiophene-2,5-diyl).
  • P3HT poly (3-hexylthiophene-2,5-diyl)
  • poly3HT poly (3-octylthiophene-2,5-diyl)
  • poly (3-dodecyl) Thiophene-2,5-diyl) poly (3-octadecylthiophene-2,5-diyl
  • polythiophenes and derivatives thereof that are homopolymers polythiophene homopolymers composed of thiophene diyl groups substituted with alkyl groups having 6 to
  • n the number of repetitions.
  • R 111 and R 112 are the same or different and each represents a hydrogen atom or a substituent.
  • a plurality of R 111 and R 112 may be the same or different.
  • the substituent represented by R 111 and R 112 an alkoxy group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms are preferable.
  • the polymer compound represented by the formula (11) is preferably a polymer compound in which R 111 is an alkyl group and R 112 is a hydrogen atom.
  • a polymer compound is represented, for example, by the formula (11-1).
  • n represents the number of repetitions.
  • the electron-accepting compound in addition to the polymer compound of the present invention described above, for example, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof Tetracyanoanthraquinodimethane and derivatives thereof, 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 derivatives, fullerene and derivatives thereof such as C 60, phenanthrene derivatives such as bathocuproin, metal oxides such as titanium oxide, and carbon nanotube.
  • oxadiazole derivatives anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone
  • the electron-accepting compound preferably, in addition to the polymer compound of the present invention, a compound having a benzothiadiazole structure, a polymer compound having a benzothiadiazole structure in a repeating unit, a compound having a quinoxaline structure, and a quinoxaline structure in a repeating unit.
  • a compound having a benzothiadiazole structure preferably, in addition to the polymer compound of the present invention, a compound having a benzothiadiazole structure, a polymer compound having a benzothiadiazole structure in a repeating unit, a compound having a quinoxaline structure, and a quinoxaline structure in a repeating unit.
  • examples thereof include high molecular compounds, titanium oxide, carbon nanotubes, fullerenes and fullerene derivatives.
  • fullerenes, fullerene derivatives, compounds having a benzothiadiazole structure, polymer compounds having a benzothiadiazole structure in a repeating unit, compounds having a quinoxaline structure, and polymers having a quinoxaline structure in a repeating unit are more preferable. More preferred are a compound having a benzothiadiazole structure, a polymer compound having a benzothiadiazole structure in a repeating unit, a compound having a quinoxaline structure, and a polymer compound having a quinoxaline structure in a repeating unit. Particularly preferred are a polymer compound containing a benzothiadiazole structure in the repeating unit and a polymer compound containing a quinoxaline structure in the repeating unit.
  • Examples of the polymer compound having a benzothiadiazole structure in the repeating unit include the polymer compound represented by the formula (11) exemplified as the electron donating compound, and represented by the formula (11-1). High molecular compounds are preferred. That is, depending on the combination with the compound applied as the electron donating compound, the polymer compound represented by the formula (11) can be applied as the electron accepting compound.
  • examples of an n-type semiconductor suitable as an electron-accepting compound include fullerene and fullerene derivatives.
  • the fullerene derivative refers to a compound in which at least a part of fullerene is modified.
  • Examples of fullerene, C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene, include C 84 fullerene, the fullerene derivative, derivatives of the fullerene and the like.
  • C 60 fullerene derivative examples include compounds represented by the following formulae.
  • Examples of the C 70 fullerene derivative include compounds represented by the following formulae.
  • Examples of other fullerene derivatives include [6,6] phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6] -Phenyl C61 butyric acid methyl ester), [6,6] phenyl-C71 butyric acid methyl ester. (C70PCBM, [6,6] -Phenyl C71 butyric acidmethyl ester), [6,6] Phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6] -Phenyl C85 butyric acid methyl ester), [6,6] thienyl -C61 butyric acid methyl ester ([6,6] -Thienyl C61 butyric acidmethyl ester).
  • the content ratio of the electron accepting compound is preferably 10 to 1000 parts by weight, and more preferably 20 to 500 parts by weight with respect to 100 parts by weight of the electron donating compound.
  • the thickness of the organic semiconductor layer 2 is preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, further preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.
  • Examples of the combination of the electron donating compound and the electron accepting compound contained in the organic semiconductor layer 2 include a combination of the polymer compound (electron donating compound) of the present invention and a fullerene derivative (electron accepting compound), an electron A combination in which both the donating compound and the electron accepting compound are the polymer compounds of the present invention is suitable.
  • the polymer compounds that are the electron-donating compound and the electron-accepting compound are combined so that HOMO suitable as the electron-donating compound and LUMO suitable as the electron-accepting compound can be obtained.
  • the organic semiconductor layer 2 may contain components other than those described above in order to develop various functions.
  • Components other than the above include, for example, ultraviolet absorbers, antioxidants, sensitizers for sensitizing the function of generating charges by absorbed light, and light stabilizers for increasing stability from ultraviolet rays. Can be mentioned.
  • Components other than the electron-donating compound and the electron-accepting compound that constitute the organic semiconductor layer 2 are each 5 parts by weight or less, particularly 0.01% with respect to 100 parts by weight of the total amount of the electron-donating compound and the electron-accepting compound. Mixing at a ratio of ⁇ 3 parts by weight is effective because high charge mobility can be obtained while obtaining the effect of each component.
  • the organic semiconductor layer 2 may contain a polymer compound other than an electron donating compound and an electron accepting compound as a polymer binder in order to improve mechanical properties.
  • a polymer binder those that do not inhibit the electron transport property or hole transport property and those that do not strongly absorb visible light are preferably used.
  • Polymer binders 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, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.
  • the organic semiconductor layer 2 having the above-described configuration is formed using a solution containing an electron-donating compound, an electron-accepting compound, and other components blended as necessary. It can be formed by doing.
  • the organic semiconductor layer 2 can be formed by applying this solution on the anode 7a or the cathode 7b.
  • the solvent in film formation using a solution may be any solvent that dissolves the above-described electron-donating compound and electron-accepting compound, and a plurality of solvents may be mixed.
  • the solvent include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, Halogenated saturated hydrocarbon solvents such as dichloroethane, dichloropropane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, and halogenated unsaturated carbonization such as chlorobenzene, dichlorobenzene and trichlor
  • the organic semiconductor layer 2 is formed by spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing.
  • Application methods such as gravure printing, flexographic printing, offset printing, ink jet printing, dispenser printing, nozzle coating, and capillary coating can be used. Of these, spin coating, flexographic printing, gravure printing, ink jet printing, and dispenser printing are preferred.
  • the photoelectric conversion element 300 includes an additional intermediate layer (buffer layer) other than the organic semiconductor layer 2 in order to improve the photoelectric conversion efficiency.
  • buffer layer buffer layer
  • Charge transport layer etc.
  • Such an intermediate layer can be formed, for example, between the anode 7 a and the organic semiconductor layer 2 or between the cathode 7 b and the organic semiconductor layer 2.
  • the intermediate layer examples include alkali metal or alkaline earth metal halides or oxides such as lithium fluoride.
  • the intermediate layer also includes fine particles of inorganic semiconductor such as titanium oxide, a mixture of PEDOT (poly (3,4-ethylenedioxythiophene)) and PSS (poly (4-styrenesulfonate)) (PEDOT: PSS), etc. May be used.
  • the photoelectric conversion element 300 as described above irradiates light such as sunlight from the transparent or translucent electrode (anode 7a or cathode 7b) side, thereby generating a photovoltaic power between these electrodes, and organic It can be operated as a thin film solar cell element.
  • a solar cell module can also be configured by integrating a plurality of these organic thin-film solar cell elements.
  • the photoelectric conversion element 300 has a photocurrent generated by making light incident from a transparent or translucent electrode in a state where a voltage is applied between the electrodes (the anode 7a and the cathode 7b) or in a state where no voltage is applied. Since it flows, it can be operated as an organic light sensor. By integrating a plurality of such organic photosensors, it can be used as an organic image sensor.
  • the organic thin-film solar cell using the photoelectric conversion element of the present invention can have a module structure basically similar to that of a conventional solar cell module. That is, as a solar cell module, a cell (for example, the photoelectric conversion element of the above-described embodiment) is formed on a support substrate such as metal or ceramic, and the top is covered with a filling resin or protective glass, and is opposite to the support substrate. One having a structure for taking in light from the side is mentioned. Further, by using a transparent material such as tempered glass for the support substrate and forming a cell thereon, it is possible to adopt a structure for taking in light from the transparent support substrate side.
  • a transparent material such as tempered glass for the support substrate and forming a cell thereon
  • a module structure called a super straight type, a substrate type, or a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known.
  • the organic thin film solar cell to which the photoelectric conversion element of the present invention is applied can also select these module structures according to the purpose of use, the place of use, the environment of use, and the like.
  • cells are arranged at regular intervals between support substrates that are transparent on one side or both sides and treated with antireflection, and adjacent cells are metal leads. Or it has the structure which takes out generated electric power outside by having the structure where the current collection electrode is arrange
  • plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filling resin depending on the purpose in order to protect the cell and improve the current collection efficiency.
  • EVA ethylene vinyl acetate
  • the protective function can be achieved by configuring the surface protective layer with a transparent plastic film or curing the filling resin. It is also possible to eliminate the support substrate on one side.
  • the periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material. May be.
  • a sealing material if a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.
  • a solar cell using a flexible support such as a polymer film
  • cells are sequentially formed while feeding a roll-shaped support, cut into a desired size, and then the periphery is made of a flexible and moisture-proof material.
  • the main body of the solar cell can be manufactured by sealing.
  • a module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 may be used.
  • a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.
  • the molecular weight of the polymer compound (polymer) is GPC (trade name: LC-10Avp) manufactured by Shimadzu Corporation (hereinafter referred to as “LC-10Avp”) or GPC (trade name: GPC Laboratory).
  • LC-10Avp LC-10Avp
  • GPC GPC Laboratory
  • PL-GPC2000 PL-GPC2000
  • the polymer When measuring with LC-10Avp, the polymer was dissolved in tetrahydrofuran (THF) to a concentration of about 0.5% by weight, and 50 ⁇ L was injected into GPC. Tetrahydrofuran was used as the GPC mobile phase, and flowed at a flow rate of 0.6 mL / min.
  • THF tetrahydrofuran
  • Tetrahydrofuran was used as the GPC mobile phase, and flowed at a flow rate of 0.6 mL / min.
  • TSKgel SuperHM-H manufactured by Tosoh
  • TSKgel SuperH2000 manufactured by Tosoh
  • a differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.
  • the polymer when measured with PL-GPC2000, the polymer was dissolved in o-dichlorobenzene so as to have a concentration of about 1% by weight.
  • o-dichlorobenzene As the mobile phase of GPC, o-dichlorobenzene was used and allowed to flow at a measurement temperature of 140 ° C. at a flow rate of 1 mL / min.
  • the column three PLGEL 10 ⁇ m MIXED-B (PL Laboratory) were connected in series.
  • the obtained reaction solution was poured into a mixed solution of methanol (200 ml) and hydrochloric acid (5 ml) and stirred for 3 hours.
  • the deposited precipitate was collected by filtration, washed with methanol and hexane in order, and then extracted with chloroform.
  • the obtained chloroform solution was concentrated, this solution was poured into methanol, and the deposited precipitate was collected by filtration to obtain a polymer compound (polymer compound P1) (44 mg) represented by the following formula P1 as a red solid. It was.
  • the polymer compound P1 had a polystyrene-equivalent number average molecular weight of 8.3 ⁇ 10 3 and a weight average molecular weight of 1.5 ⁇ 10 4 .
  • This reaction is as shown in the following reaction formula. In the formula, n represents the number of repeating units.
  • the organic transistor shown in FIG. 9 was produced using the polymer compound P1, and the transistor characteristics were measured. That is, first, the surface of the heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 200 nm silicon oxide film 32. After thoroughly washing the substrate, the substrate surface was silane treated with hexamethylene disilazane (HMDS).
  • HMDS hexamethylene disilazane
  • the polymer compound P1 was dissolved in chloroform to prepare a 3 g / L solution, which was filtered through a membrane filter.
  • a thin film (organic semiconductor layer 35) containing a polymer compound P1 of about 30 nm was formed on the surface-treated substrate by spin coating. This thin film was heated at 150 ° C. for 30 minutes in a nitrogen atmosphere. Then, a source electrode 33 and a drain electrode 34 having a channel length of 50 ⁇ m and a channel width of 1.5 mm were produced on the obtained thin film by vacuum deposition, thereby obtaining an organic transistor.
  • polymer compound P2 (302 mg) represented by the following formula P2.
  • n represents the number of repeating units.
  • the polymer compound P2 had a polystyrene-equivalent number average molecular weight of 8.5 ⁇ 10 3 and a weight average molecular weight of 4.3 ⁇ 10 4 .
  • An organic transistor shown in FIG. 9 was prepared using the polymer compound P2, and the transistor characteristics were measured. That is, first, the surface of the heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 200 nm silicon oxide film 32. The substrate was ultrasonically cleaned with acetone for 10 minutes and then irradiated with ozone UV for 20 minutes. Thereafter, silane treatment was performed on the substrate surface by spin coating using ⁇ -phenethyltrichlorosilane ( ⁇ -PTS).
  • ⁇ -PTS ⁇ -phenethyltrichlorosilane
  • the polymer compound P2 was dissolved in toluene as a solvent to prepare a solution having a total concentration of 0.5% by weight, and this was filtered through a membrane filter.
  • the obtained solution was applied on the surface-treated substrate by a spin coating method to form a thin film (organic semiconductor layer 35) of a polymer compound P2 having a thickness of about 60 nm.
  • a source electrode 33 and a drain electrode 34 (having a laminated structure of MoO 3 and gold in order from the thin film side) by a vacuum deposition method using a metal mask with a channel length of 20 ⁇ m and a channel width of 2 mm. Electrode) to produce an organic transistor.
  • the reaction solution was poured into a mixed solution of methanol (200 ml) and hydrochloric acid (5 ml) and stirred for 3 hours.
  • the deposited precipitate was collected by filtration, washed with methanol, hexane, and chloroform, and extracted with chlorobenzene.
  • the chlorobenzene solution was concentrated, this solution was poured into methanol, and the deposited precipitate was collected by filtration to obtain a polymer compound (polymer compound P3) (31 mg) represented by the following formula P3 as a red solid.
  • the polymer compound P3 had a polystyrene-equivalent number average molecular weight of 4.4 ⁇ 10 4 and a weight average molecular weight of 7.7 ⁇ 10 4 .
  • This reaction is as shown in the following reaction formula. In the formula, n represents the number of repeating units.
  • the reaction solution was poured into a mixed solution of methanol (200 ml) and hydrochloric acid (5 ml) and stirred for 3 hours.
  • the deposited precipitate was collected by filtration, washed with methanol, hexane and chloroform, and extracted with chlorobenzene.
  • the chlorobenzene solution was concentrated, this solution was poured into methanol, and the deposited precipitate was collected by filtration to obtain a polymer compound (polymer compound P4) (76 mg) represented by the following formula P4 as an orange solid.
  • the polymer compound P4 had a polystyrene-equivalent number average molecular weight of 2.8 ⁇ 10 4 and a weight average molecular weight of 4.9 ⁇ 10 4 .
  • This reaction is as shown in the following reaction formula. In the formula, n represents the number of repeating units.
  • the reaction solution was poured into a mixed solution of methanol (200 ml) and hydrochloric acid (5 ml) and stirred for 3 hours.
  • the deposited precipitate was collected by filtration, washed with methanol, hexane and chloroform, and extracted with chlorobenzene.
  • the chlorobenzene solution was concentrated, this solution was poured into methanol, and the deposited precipitate was collected by filtration to obtain a polymer compound (polymer compound P5) (5 mg) represented by the following formula P5 as an orange solid.
  • the polymer compound P5 had a polystyrene-equivalent number average molecular weight of 4.7 ⁇ 10 4 and a weight average molecular weight of 9.4 ⁇ 10 4 .
  • This reaction is as shown in the following reaction formula. In the formula, n represents the number of repeating units.
  • the reaction solution was poured into a mixed solution of methanol (200 ml) and hydrochloric acid (5 ml) and stirred for 3 hours.
  • the deposited precipitate was collected by filtration, heated and washed with methanol and hexane, and extracted with chloroform.
  • the chloroform solution was concentrated, this solution was poured into methanol, and the deposited precipitate was collected by filtration to obtain a polymer compound (polymer compound P6) (106 mg) represented by the following formula P6 as a black-brown solid.
  • the polymer compound P6 had a polystyrene-equivalent number average molecular weight of 1.5 ⁇ 10 4 and a weight average molecular weight of 2.4 ⁇ 10 4 .
  • This reaction is as shown in the following reaction formula. In the formula, n represents the number of repeating units.
  • the shape of the obtained organic thin film solar cell was a circle having a diameter of 2 mm.
  • the obtained organic thin-film solar cell is irradiated with constant light using a solar simulator (trade name HAL302: AM1.5G filter, irradiance 100 mW / cm 2 , manufactured by Asahi Spectroscopic Co., Ltd.), and the generated current and voltage are measured.
  • the photoelectric conversion efficiency, the short circuit current density, the open circuit voltage, and the fill factor were obtained.
  • the reaction solution was poured into a mixed solution of methanol (200 ml) and hydrochloric acid (5 ml) and stirred for 3 hours.
  • the deposited precipitate was collected by filtration, heated and washed with methanol and hexane, and extracted with chloroform.
  • the chloroform solution was concentrated, this solution was poured into methanol, and the deposited precipitate was collected by filtration to obtain a polymer compound (polymer compound P7) (224 mg) represented by the following formula P7 as a black-brown solid.
  • the number average molecular weight in terms of polystyrene of the polymer compound P7 was 1.9 ⁇ 10 4 , and the weight average molecular weight was 6.7 ⁇ 10 4 .
  • This reaction is as shown in the following reaction formula. In the formula, n represents the number of repeating units.
  • the polymer was filtered and dried to obtain 460 mg of a polymer compound represented by the following formula P10 (polymer compound P10).
  • the polymer compound P10 measured by GPC had a polystyrene equivalent weight average molecular weight of 3.2 ⁇ 10 4 and a number average molecular weight of 1.2 ⁇ 10 4 .
  • This reaction is as shown in the following reaction formula. In the formula, n represents the number of repeating units.
  • the transistor characteristics were measured by changing the gate voltage Vg from 10 to ⁇ 60 V and the source-drain voltage Vsd from 0 to ⁇ 60 V.
  • the drain current value was 0.54 ⁇ A, which was lower than that in Example 1. From this result, the field effect mobility was calculated to be 2.0 ⁇ 10 ⁇ 4 cm 2 / Vs.
  • Organic-semiconductor layer 100 ... Organic transistor which concerns on 1st Embodiment, 110 ... Organic transistor which concerns on 2nd Embodiment, 120 ... 3rd Embodiment

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Abstract

La présente invention concerne un composé polymère qui est capable de produire une mobilité de charge élevée. La présente invention concerne spécifiquement un composé polymère qui a au moins un motif de répétition choisi dans le groupe constitué de motifs de répétition représentés par les formules (1) et (2). (X11 et X12 dans la formule (1) et X21 et X22 dans la formule (2) représentent chacun un atome d'oxygène ou un atome de chalcogène ; et R13 à R16 dans la formule (1) et R23 à R26 dans la formule (2) représentent chacun un atome d'hydrogène, un groupe alkyle, un groupe alcoxy, un groupe alkylthio, un groupe aryloxy, un groupe arylthio, un groupe arylalkyle, un groupe arylalcoxy, un groupe arylalkylthio, un groupe silyle substitué, un groupe carboxyle non substitué ou substitué, un groupe hétérocyclique monovalent facultativement substitué, un groupe cyano ou un atome de fluor).
PCT/JP2010/073181 2009-12-25 2010-12-22 Composé polymère, et couche mince et composition d'encre contenant chacune celui-ci WO2011078246A1 (fr)

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JP2013207259A (ja) * 2012-03-29 2013-10-07 Sumitomo Chemical Co Ltd 光電変換素子
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