WO2012090912A1 - Composé et couche mince le contenant - Google Patents

Composé et couche mince le contenant Download PDF

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WO2012090912A1
WO2012090912A1 PCT/JP2011/080022 JP2011080022W WO2012090912A1 WO 2012090912 A1 WO2012090912 A1 WO 2012090912A1 JP 2011080022 W JP2011080022 W JP 2011080022W WO 2012090912 A1 WO2012090912 A1 WO 2012090912A1
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compound
group
formula
substituent
structural unit
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信一 山手
宏樹 寺井
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
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    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/36—Oligomers, i.e. comprising up to 10 repeat units
    • C08G2261/364—Oligomers, i.e. comprising up to 10 repeat units containing hetero atoms
    • C—CHEMISTRY; METALLURGY
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    • C08G2261/40—Polymerisation processes
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    • C08G2261/411—Suzuki reactions
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/92—TFT applications

Definitions

  • the present invention relates to a compound and a thin film containing the compound.
  • an organic semiconductor element such as an organic transistor
  • a high-temperature process and a vacuum process necessary for manufacturing an inorganic semiconductor element such as a silicon-based transistor can be omitted, and energy required for manufacturing can be reduced.
  • the organic semiconductor element can be made into a film-like element having flexibility, and has attracted attention as a next-generation element.
  • a compound having a ⁇ -conjugated structure exhibits conductivity and semiconductivity, and has attracted attention as an organic semiconductor compound used for an organic semiconductor element.
  • P3HT poly-3-hexylthiophene
  • Non-Patent Document 1 describes an organic transistor in which an organic semiconductor layer is formed by spin-coating a chloroform solution of poly-3-hexylthiophene (P3HT) on a silicon wafer.
  • P3HT poly-3-hexylthiophene
  • the organic transistor has insufficient transistor characteristics, and a novel organic semiconductor compound useful for inclusion in the organic semiconductor layer of the organic transistor is demanded.
  • Non-Patent Document 2 describes polyanthracene and a copolymer of anthracene and benzene as a compound having a ⁇ -conjugated structure. Many of the anthracene moieties are light-emitting, and a polymer having an anthracene moiety as part of the ⁇ -conjugated structure is a material that is highly likely to exhibit electroluminescence.
  • Non-Patent Document 2 proposes a precursor that can be heated to be changed into polyanthracene and a copolymer of anthracene and benzene, and is soluble in a solvent.
  • the precursor has a structure in which maleic anhydride is added to Diels Alder to the anthracene portion of polyanthracene or anthracene-benzene copolymer.
  • the present invention solves the above-described conventional problems, and an object of the present invention is to provide a compound having a ⁇ -conjugated structure useful for inclusion in an organic semiconductor layer of an organic transistor, a thin film containing the compound, and the ⁇
  • the object is to provide a compound which is a precursor for obtaining a compound containing a conjugated structure.
  • the present invention has the formula (1)
  • R 1 and R 2 each independently represents a substituent.
  • R 3 and R 4 each independently represents a hydrogen atom or a substituent.
  • n and m each independently represents an integer of 0 to 3.
  • Y represents a divalent group.
  • R 1 s they may be the same or different.
  • R 2 they may be the same or different.
  • R 5 represents a substituent. s represents an integer of 1 to 4. p represents an integer of 0 to 4. q represents an integer of 0 to 4. When there are a plurality of R 5 , they may be the same or different. ] A structural unit represented by formula (5)
  • An arylene group having 8 or more ring carbon atoms which may be present or a heteroarylene group which may have a substituent is represented.
  • Ar 1 is not a group represented by the formula (1).
  • Two R A each independently represents a hydrogen atom or a substituent.
  • R B represents a hydrogen atom or a substituent.
  • r and rr represent the number of structural units (—Ar 3 —NAr 6 —) and the number of structural units (—Ar 5 —NAr 7 —), respectively, and are each independently 0 or 1.
  • Ar 2 , Ar 3 , Ar 4 and Ar 5 each independently represent an arylene group which may have a substituent or a heteroarylene group which may have a substituent.
  • Ar 6 , Ar 7 and Ar 8 each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
  • the left benzene ring has two C atoms on the right side (one of which is bonded to R 3 and the other is bonded to R 4 ).
  • any one of the benzene ring carbon atoms other than the two bonded benzene ring carbon atoms in place of the hydrogen atom, bonded to n R 1 groups and one adjacent structural unit (not shown) Yes.
  • each of s R 5 groups replaces a hydrogen atom, and is a group of ring carbon atoms other than two ring carbon atoms bonded to an adjacent structural unit (not shown). It is bound to any s ring carbon atoms.
  • Other expressions similar to Expression (1) and Expression (2) are interpreted in the same manner.
  • the compound has two or more structural units represented by the formula (1).
  • the structural units represented by the formula (1) may be the same as or different from each other.
  • the said compound is further Formula (7).
  • the divalent group represented by Y is a group represented by any of formulas (Y-1) to (Y-8)
  • R 10 to R 20 each independently represents a hydrogen atom or a substituent.
  • X 1 represents a hydrogen atom or a halogen atom. When there are a plurality of X 1 , they may be the same or different.
  • Ys in these structural units may be the same or different from each other.
  • the compound is a polymer compound having a weight average molecular weight of 3000 or more.
  • the said compound is further Formula (8).
  • the present invention also provides a solution containing any one of the above compounds and a solvent.
  • the present invention also provides a thin film containing any one of the above compounds.
  • the present invention is a laminate having a substrate and a thin film, The thin film is coated on the substrate to form a coating film containing a compound containing a structural unit represented by the formula (1),
  • the structural unit represented by the formula (1) contained in at least a part of the entire compound including the structural unit represented by the formula (1) contained in the coating film is represented by the formula
  • Provided is a laminate that is a film obtained by converting into the structural unit represented by (8).
  • the present invention is a method for producing a laminate having a thin film and a substrate, Applying the solution onto a substrate to form a coating film containing a compound containing a structural unit represented by formula (1);
  • the structural unit represented by the formula (1) contained in at least a part of the entire compound including the structural unit represented by the formula (1) contained in the coating film is represented by the formula
  • membrane is provided.
  • a compound having a ⁇ -conjugated structure useful for inclusion in an organic semiconductor layer of an organic transistor, a thin film containing the compound, and a compound that is a precursor for obtaining a compound containing the ⁇ -conjugated structure are provided.
  • FIG. 10 is a cross-sectional view showing the structure of an organic transistor manufactured as Reference Example 3.
  • FIG. 5 is a cross-sectional view showing the structure of organic transistors manufactured as Reference Examples 4 to 11.
  • the compound of the present invention contains a structural unit represented by the formula (1).
  • R 1 and R 2 each independently represent a substituent.
  • substituents a halogen atom and a group having 1 to 30 carbon atoms are preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom and a chlorine atom are preferable.
  • Examples of the group having 1 to 30 carbon atoms include alkyl groups such as ethyl group, butyl group, hexyl group, octyl group, dodecyl group, methoxy group, ethoxy group, butoxy group, hexyloxy group, octyloxy group, dodecyloxy group.
  • An alkoxy group such as a group, a heteroaryl group such as a thienyl group, an aryl group such as a phenyl group and a naphthyl group, and a cyano group.
  • the hydrogen atom in the group having 1 to 30 carbon atoms may be substituted with a halogen atom. When a hydrogen atom in a group having 1 to 30 carbon atoms is substituted with a halogen atom, it is preferably substituted with a fluorine atom among the halogen atoms.
  • n and m each independently represents an integer of 0 to 3. n and m are preferably 0. When there are a plurality of R 1 s , they may be the same or different. When there are a plurality of R 2 , they may be the same or different.
  • R 3 and R 4 represent a hydrogen atom or a substituent.
  • substituent represented by R 3 or R 4 include the same groups as the examples of the substituent represented by R 1 . From the viewpoint of ease of synthesis of the compound, R 3 and R 4 are preferably hydrogen atoms.
  • Y represents a divalent group.
  • divalent groups a group that can be removed by applying energy such as heat or light is preferable.
  • Examples of the divalent group represented by Y include the following groups.
  • R 10 to R 20 are the same or different and each represents a hydrogen atom or a substituent. Of these, a hydrogen atom or a group having 1 to 30 carbon atoms is preferable.
  • R 10 to R 19 are substituents
  • substituents include alkyl groups such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, a methoxy group, an ethoxy group, and a butoxy group.
  • an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, an alkyl group having 1 to 12 carbon atoms is further preferable, and an alkyl group having 1 to 6 carbon atoms is particularly preferable. preferable.
  • R 20 is a substituent
  • substituents include alkyl groups such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, a methoxy group, an ethoxy group, a butoxy group, and a hexyloxy group.
  • alkoxy group such as octyloxy group and dodecyloxy group
  • an aryl group such as phenyl group and naphthyl group
  • vinyl group and a group containing an ester structure a group containing an ester structure.
  • X 1 represents a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable.
  • groups represented by the formulas (Y-1) to (Y-8) are preferable, and the formulas (Y-3) to (Y-7) are preferable, and the formulas (Y-3) to (Y-7) A group represented by (Y-5) is more preferable.
  • preferred Y is represented by the formula (Y-3) or (Y-4), wherein R 16 , R 17 , R 18 and R 19 are each an alkoxy group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms. It becomes group which becomes the alkoxy group.
  • the compound of the present invention has a structural unit having a ⁇ -conjugated structure in addition to the structural unit represented by the formula (1).
  • Specific examples of the structural unit having a ⁇ -conjugated structure include a structural unit represented by the following formula (2), a structural unit represented by the formula (3), a structural unit represented by the formula (4), a formula ( 5) and at least one structural unit selected from the group consisting of the structural unit represented by formula (6) is included.
  • R 5 represents a substituent.
  • Examples of the substituent represented by R 5 include the same groups as the examples of the substituent represented by R 1 .
  • s represents an integer of 1 to 4.
  • p represents an integer of 0 to 4.
  • p is preferably 0.
  • q represents an integer of 0 to 4. q is preferably 0.
  • Ar 1 is not a group represented by the formula (1).
  • Two R A each independently represents a hydrogen atom or a substituent.
  • R B represents a hydrogen atom or a substituent. Examples of the substituent represented by R A or R B include the same groups as the examples of the substituent represented by R 1 .
  • the arylene group includes a group obtained by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon, a group obtained by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon, and two or more aromatic hydrocarbons directly bonded Or a group obtained by removing two hydrogen atoms from a compound bonded via a vinylene group.
  • the arylene group is a group obtained by removing two hydrogen atoms from a monocyclic aromatic hydrocarbon
  • the arylene group preferably has 8 to 60 carbon atoms, more preferably 8 to 48 carbon atoms. 8 to 30 is more preferable, and 8 to 14 is particularly preferable. This carbon number does not include the carbon number of the substituent.
  • the arylene group is a group obtained by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon
  • the arylene group preferably has 10 to 60 carbon atoms, and more preferably 10 to 48 carbon atoms. It is more preferably 10-30, and particularly preferably 10-14. This carbon number does not include the carbon number of the substituent.
  • arylene group is a group obtained by removing two hydrogen atoms from a polycyclic aromatic hydrocarbon
  • examples of the arylene group which may have a substituent include the following groups.
  • each R independently represents a hydrogen atom or a substituent.
  • R is a substituent, alkyl group such as methyl group, ethyl group, butyl group, 2-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, hexadecyl group, methoxy group, ethoxy group, butoxy Groups, hexyloxy groups, octyloxy groups, alkoxy groups such as dodecyloxy groups, aryl groups such as phenyl and naphthyl, heteroaryl groups such as thienyl, halogen atoms, and cyano groups.
  • R is an alkyl group
  • an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.
  • R is an alkoxy group
  • an alkoxy group having 1 to 20 carbon atoms is preferable, an alkoxy group having 1 to 12 carbon atoms is more preferable, and an alkoxy group having 1 to 8 carbon atoms is more preferable.
  • the arylene group is a group obtained by removing two hydrogen atoms from a compound in which two or more aromatic hydrocarbons are directly bonded or bonded via a vinylene group
  • benzene is preferable as the aromatic hydrocarbon.
  • the arylene group is a group obtained by removing two hydrogen atoms from a compound in which two or more benzenes are directly bonded or bonded via a vinylene group
  • examples of the arylene group which may have a substituent include The following groups are mentioned.
  • R represents the same meaning as described above.
  • the heteroarylene group includes a group obtained by removing two hydrogen atoms from a monocyclic aromatic heterocyclic compound, a group obtained by removing two hydrogen atoms from a polycyclic aromatic heterocyclic compound, and at least one aromatic Examples thereof include a group in which two hydrogen atoms are removed from a compound in which two or more aromatic compounds including a heterocyclic compound are bonded directly or via a vinylene group.
  • the heteroarylene group is a group obtained by removing two hydrogen atoms from a monocyclic aromatic heterocyclic compound or a group obtained by removing two hydrogen atoms from a polycyclic aromatic heterocyclic compound
  • the number of carbon atoms is preferably 3 to 60, and more preferably 3 to 20. This carbon number does not include the carbon number of the substituent.
  • the heteroarylene group is a group obtained by removing two hydrogen atoms from a monocyclic aromatic heterocyclic compound or a group obtained by removing two hydrogen atoms from a polycyclic aromatic heterocyclic compound
  • the heteroarylene group has a substituent.
  • Examples of the heteroarylene group which may be included include the following groups.
  • R represents the same meaning as described above.
  • heteroarylene group is a group obtained by removing two hydrogen atoms from a compound in which two or more aromatic compounds including at least one aromatic heterocyclic compound are bonded directly or via a vinylene group
  • heteroarylene group which may have a group include the following groups.
  • R represents the same meaning as described above.
  • X 2 represents —CH ⁇ or a nitrogen atom. If X 2 there is a plurality, they may be the same or different.
  • Ar 1 is preferably an arylene group having 8 or more ring carbon atoms which may have a substituent or a heteroarylene group which may have a substituent.
  • Ar 2 , Ar 3 , Ar 4 and Ar 5 each independently represent an arylene group which may have a substituent or a heteroarylene group which may have a substituent.
  • Examples of the arylene group and heteroarylene group include the same groups as the examples of the phenylene group, the arylene group represented by Ar 1 , and the heteroarylene group.
  • Ar 2 , Ar 3 , Ar 4 and Ar 5 are preferably a phenylene group which may have a substituent.
  • Ar 6 , Ar 7 and Ar 8 each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
  • aryl groups include phenyl, naphthyl, and anthryl groups.
  • heteroaryl groups include thienyl groups.
  • Ar 6 , Ar 7 and Ar 8 are each independently preferably a phenyl group which may have a substituent, and more preferably a phenyl group which may have an alkyl group.
  • r and rr each represent the number of structural units (—Ar 3 —NAr 6 —) and the number of structural units (—Ar 5 —NAr 7 —), and each independently represents 0 or 1 is there.
  • Ar 5, Ar 6, carbon atoms in the group represented by Ar 7 or Ar 8 are the nitrogen to which the group represented by Ar 5, Ar 6, Ar 7 or Ar 8 are attached Directly bonded to the carbon atom in the group represented by Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 7 or Ar 8 bonded to the atom, or —O—, —S—, —C Bonded via ( ⁇ O) —, —C ( ⁇ O) —O—, —N (R C ) —, —C ( ⁇ O) —N (R c ) — or —C (R c ) 2 — And may form a 5- to 7-membered ring.
  • R C represents an alkyl group, an aryl group, a heteroaryl group or an aralkyl group.
  • Examples of the structural unit represented by the formula (6) include the following groups.
  • R represents the same meaning as described above.
  • the compound of the present invention may contain only one type or two or more types of structural units represented by the formulas (2) to (6).
  • the compound of the present invention may further contain one or more structural units represented by the formula (7).
  • the compound of the present invention may further contain one or more structural units represented by the formula (8).
  • n, m, R 1 , R 2 , R 3 and R 4 represent the same meaning as those in formula (1).
  • the compound of the present invention preferably contains two or more structural units represented by the formula (1).
  • the structural unit represented by the formula (1) may be the same as or different from each other.
  • the molecular weight of the compound of the present invention is not particularly limited, and any molecular weight can be used, but a polymer compound is preferable.
  • the polymer compound in the present invention refers to a polymer having a polystyrene equivalent weight average molecular weight of 3 ⁇ 10 3 or more.
  • polymer compounds having a weight average molecular weight of 3 ⁇ 10 3 to 1 ⁇ 10 7 are preferably used.
  • the weight average molecular weight is 3 ⁇ 10 3 or more, generation of defects is suppressed in film formation at the time of device fabrication, and when it is 1 ⁇ 10 7 or less, solubility in a solvent and applicability at the time of device creation are increased. .
  • the weight average molecular weight is more preferably 8 ⁇ 10 3 to 5 ⁇ 10 6 , and particularly preferably 1 ⁇ 10 4 to 1 ⁇ 10 6 . From the viewpoint of suppressing the occurrence of defects in film formation during device fabrication, 10,000 or more are preferable.
  • the number average molecular weight in terms of polystyrene is preferably 1 ⁇ 10 3 to 1 ⁇ 10 8 , more preferably 2 ⁇ 10 3 to 1 ⁇ 10 7 .
  • the number average molecular weight in terms of polystyrene is 1 ⁇ 10 3 or more, a tough thin film is easily obtained.
  • it is 10 8 or less, the solubility of the polymer compound is high and the production of the thin film is easy.
  • weight average molecular weight in this invention points out the weight average molecular weight computed using the polystyrene standard using gel permeation chromatography (GPC).
  • the compound of the present invention is a polymer compound, from the viewpoint of solubility in a solvent, when the total amount of all repeating units possessed by the polymer compound is 100, it is represented by the formula (1) containing as a repeating unit.
  • the amount of the structural unit is preferably 20 to 99, and more preferably 30 to 60.
  • the properties when the obtained polymer compound is used in an organic element may be deteriorated. It is preferably protected with a stable group that does not.
  • the stable group is preferably a group having a conjugated bond continuous with the conjugated structure of the molecular chain main chain.
  • the solubility in a solvent is high because of the ease of element production.
  • it preferably has a solubility capable of producing a solution of 0.01 wt% or more, more preferably has a solubility capable of producing a solution of 0.1 wt% or more, and a solution of 0.4 wt% or more. More preferably, it has a solubility that can be produced.
  • the production method of the compound is not particularly limited, but a method using a reductive coupling reaction using a Ni catalyst, a method using a Stille coupling reaction, Examples thereof include a method using a Suzuki coupling reaction. In view of the ease of synthesis of the compound, a method using a Suzuki coupling reaction is preferred.
  • E 1 represents a structural unit represented by the formula (1).
  • Q 1 and Q 2 are the same or different and represent a boronic acid residue or a boric acid ester residue.
  • One or more compounds represented by the formula T 1 -E 2 -T 2 (200) [Wherein E 2 represents a structural unit represented by formula (2) to formula (8).
  • T 1 and T 2 are the same or different and each represents a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an arylalkyl sulfonate group.
  • the manufacturing method which has a process with which 1 or more types of compounds represented by these are made to react in presence of a palladium catalyst and a base is mentioned.
  • the total number of moles of one or more compounds represented by formula (200) used for the reaction is preferably excessive with respect to the total number of moles of one or more compounds represented by formula (100).
  • the total number of moles of one or more compounds represented by formula (200) used in the reaction is 1 mole
  • the total number of moles of one or more compounds represented by formula (100) is 0.6 to 0.00.
  • the amount is preferably 99 mol, more preferably 0.7 to 0.95 mol.
  • Examples of the halogen atom represented by T 1 and T 2 in Formula (200) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a bromine atom and an iodine atom are preferable, and a bromine atom is more preferable.
  • Examples of the alkyl sulfonate group represented by T 1 and T 2 in Formula (200) include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.
  • Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group.
  • a benzyl sulfonate group is illustrated as an aryl sulfonate group.
  • Examples of the palladium catalyst used in the Suzuki coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst.
  • Specific examples of the palladium catalyst include palladium [tetrakis (triphenylphosphine)], palladium acetates, dichlorobis (triphenylphosphine) palladium (II). Ease of reaction (polymerization) operation, reaction (polymerization) From the viewpoint of speed, dichlorobis (triphenylphosphine) palladium (II) and palladium acetates are preferable.
  • the addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 mol to 0.5 mol, preferably 1 mol, relative to 1 mol of the compound represented by the formula (100). 0.0003 mol to 0.1 mol.
  • the base used for the Suzuki coupling reaction is an inorganic base, an organic base, an inorganic salt, or the like.
  • the inorganic base include potassium carbonate, sodium carbonate, and barium hydroxide.
  • the organic base include triethylamine and tributylamine.
  • An example of the inorganic salt is cesium fluoride.
  • the addition amount of the base is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the compound represented by the formula (100). is there.
  • a phosphorus compound When using palladium acetate as the palladium catalyst, a phosphorus compound may be added as a ligand.
  • the phosphorus compound include triphenylphosphine, tri (o-tolyl) phosphine, and tri (o-methoxyphenyl) phosphine.
  • the addition amount is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the palladium catalyst. .
  • the reaction is usually performed in a solvent.
  • the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran. From the viewpoint of solubility of the polymer compound, toluene and tetrahydrofuran are preferred.
  • the base may be added to the reaction system as an aqueous solution, and the monomer may be reacted in a two-phase solvent of an aqueous phase and an organic phase.
  • an inorganic salt is used as the base, the monomer is usually reacted as an aqueous solution in the reaction system in a two-phase solvent.
  • phase transfer catalyst such as a quaternary ammonium salt may be added to the reaction system as necessary.
  • the temperature of the Suzuki coupling reaction is usually about 50 to 160 ° C., although it depends on the solvent. From the viewpoint of increasing the molecular weight of the polymer compound, 60 to 120 ° C. is preferable. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
  • the time (reaction time) for carrying out the Suzuki coupling reaction may be the end point when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours, preferably about 1 to 30 hours.
  • the Suzuki coupling reaction is performed in a reaction system in which the palladium catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas.
  • an inert atmosphere such as argon gas or nitrogen gas.
  • it is performed in a system sufficiently deaerated with argon gas or nitrogen gas.
  • reaction vessel After the inside of the reaction vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, a compound represented by the formula (100), a compound represented by the formula (200), Dichlorobis (triphenylphosphine) palladium (II) is charged, the reaction vessel is sufficiently replaced with nitrogen gas, degassed, and then degassed by bubbling with nitrogen gas in advance, for example, degassed toluene
  • a base degassed by bubbling with nitrogen gas in advance for example, a degassed sodium carbonate aqueous solution
  • heated and heated for example, at reflux temperature for 8 hours. Polymerize while maintaining an active atmosphere.
  • the compound of the present invention containing the structural unit represented by formula (8) contains energy to the compound containing the structural unit represented by formula (1) and not containing the structural unit represented by formula (8).
  • the divalent group represented by Y can be eliminated.
  • the starting compound has a plurality of divalent groups represented by Y, all of the divalent groups represented by Y may be eliminated, or a part of such groups may be eliminated. May be separated.
  • the solution of the present invention contains the compound of the present invention and a solvent.
  • the solvent include aromatic hydrocarbon solvents, halogen-substituted aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, halogen-substituted aliphatic hydrocarbon solvents, and ether solvents from the viewpoint of compound solubility.
  • the aromatic hydrocarbon solvent include xylene, mesitylene, anisole, and cyclohexylbenzene.
  • the halogen-substituted aromatic hydrocarbon solvent include chlorobenzene, dichlorobenzene, and trichlorobenzene.
  • An example of the aliphatic hydrocarbon solvent is tetralin.
  • halogen-substituted aliphatic hydrocarbon solvents include carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, and bromocyclohexane.
  • ether solvents include tetrahydrofuran and tetrahydropyran.
  • the boiling point of the solvent in the solution is preferably 150 ° C. or higher, and more preferably 200 ° C. or higher.
  • the method for producing the thin film containing the compound of the present invention is not particularly limited. However, from the viewpoint of ease of film formation, a method of forming the thin film by applying the solvent containing the compound of the present invention and the solvent to a substrate or the like is preferable. preferable.
  • a coating method a casting method, a spin coating method, a bar coating method, an ink jet method, a printing method using a relief plate, a printing method using a stencil, a transfer to a second plate after coating on the first plate, For example, a printing method using a plate.
  • the substrate is not particularly limited, and examples thereof include glass, polyethylene, polystyrene, plastics and films made of polystyrene or fluororesin, metals such as stainless steel and aluminum, and silicon wafers.
  • the thin film containing the compound of the present invention containing the structural unit represented by the formula (8) includes the structural unit represented by the formula (1) and does not contain the structural unit represented by the formula (8). It can be produced by applying energy to the thin film made of and removing a part of the divalent group represented by Y.
  • the laminate of the present invention is a laminate having a substrate and a thin film, and the thin film has a structure represented by the formula (1) by applying a solution containing the compound of the present invention and a solvent on the substrate. Forming a coating film containing the compound containing the unit, then applying energy to the coating film, and at least a part of the entire compound including the structural unit represented by the formula (1) contained in the coating film It is a laminated body which is a film
  • the energy include thermal energy and light energy.
  • any temperature can be set as long as the temperature is higher than the temperature at which the divalent group represented by Y is eliminated from the compound and lower than the temperature at which the compound decomposes. it can.
  • the range of 150 ° C. to 400 ° C. is preferable, and 200 ° C. to 350 ° C. is more preferable.
  • the heat treatment time can be selected within an industrial range, but is usually 1 minute to 50 hours, and preferably 10 minutes to 24 hours.
  • the atmosphere for the heat treatment is preferably an inert atmosphere, and examples thereof include nitrogen gas, argon gas, and vacuum.
  • oxygen is contained in the inert atmosphere, the oxygen concentration is preferably 100 ppm by volume or less, and more preferably 10 ppm or less.
  • the inert atmosphere is a vacuum
  • the oxygen partial pressure is preferably 200 Pa or less, more preferably 50 Pa.
  • a method for removing the divalent group represented by Y by light a method of irradiating ultraviolet rays having a wavelength of 400 nm or less is exemplified.
  • the light intensity is not particularly limited as long as the divalent group represented by Y can be eliminated.
  • the atmosphere in the case of irradiation with light is also preferably an inert atmosphere, and the range exemplified above can be suitably used.
  • the laminate of the present invention can be used for organic transistors, organic electroluminescence elements and the like.
  • the substrate may be a substrate such as glass or a film, may have a substrate and an electrode, or may have a substrate, an electrode, and an organic layer.
  • substrate consists of a board
  • substrate consists of a board
  • the method for producing a laminate of the present invention is a method for producing a laminate having a thin film and a substrate, wherein a solution containing the compound of the present invention and a solvent is applied onto the substrate, and is represented by the formula (1).
  • a step of forming a coating film containing a compound containing a structural unit, and applying energy to the coating film so that at least one of the entire compounds including the structural unit represented by formula (1) contained in the coating film And forming a thin film by converting the structural unit represented by formula (1) contained in the part into the structural unit represented by formula (8).
  • Organic transistor includes a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, and a gate electrode that controls the amount of current passing through the current path. Examples thereof include an electrically induced organic transistor.
  • a field effect thin film organic transistor includes a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, a gate electrode for controlling an amount of current passing through the current path, and an organic semiconductor layer and a gate. It is preferable to provide an insulating layer disposed between the electrodes.
  • the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer (active layer), and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween.
  • the static induction thin film organic transistor has a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, and a gate electrode for controlling the amount of current passing through the current path.
  • 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.
  • NMR measurement The NMR measurement was performed by dissolving the compound in deuterated chloroform and using an NMR apparatus (Varian, INOVA300).
  • the polystyrene-equivalent number average molecular weight and weight average molecular weight were determined by gel permeation chromatography (GPC).
  • GPC equipment is manufactured by Shimadzu Corporation, trade name: LC-10Avp (column: TsKgel SuperHM-H (manufactured by Tosoh)) and one TsKgel SuperH2000 (manufactured by Tosoh) in series, mobile phase: tetrahydrofuran, flow rate : 0.6 ml / min, sample concentration: about 0.5 wt%, detector: differential refractive index detector or UV detector, manufactured by Waters, trade name: Alliance GPC / V2000 (column: PLgel MIXED-B (Varian) 3) serial connection, column temperature: 140 ° C., mobile phase: orthodichlorobenzene, flow rate: 1 ml / min, sample concentration: about 0.77 wt%, detector: differential refractive index detector or UV detector) Using.
  • LC-10Avp column: TsKgel SuperHM-H (manufactured by Tosoh)
  • TsKgel SuperH2000 manufactured by
  • a spectrophotometer for example, JASCO-V670, UV-Vis near-infrared spectrophotometer manufactured by JASCO Corporation
  • the measurable wavelength range was 200 to 1500 nm, and thus measurement was performed in this wavelength range.
  • the absorption spectrum of the substrate used for measurement was measured.
  • a quartz substrate, a glass substrate, or the like was used as the substrate.
  • a solution containing a polymer compound was applied onto the substrate and dried to form a thin film containing the polymer compound.
  • substrate was measured. The difference between the absorption spectrum of the laminate of the thin film and the substrate and the absorption spectrum of the substrate was obtained as the absorption spectrum of the thin film.
  • reaction solution was separated with a column using chloroform as a developing solvent, and the separated product was reprecipitated with hexane to obtain 25.17 g of a colorless powdery anthracene crosslinked product (compound (C-2)).
  • chloroform was added to the organic layer and dissolved by heating, and then concentrated with an evaporator and dried under reduced pressure to obtain a crude product. Chloroform was added to the resulting crude purified product and dissolved by heating, and then purification treatment was performed three times using a column in which alumina and silica were laminated. The solution after column treatment was concentrated with an evaporator and dried under reduced pressure to obtain yellow powdery polymer compound 1. The yield of the high molecular compound 1 was 100 mg. The number average molecular weight of polystyrene conversion of the high molecular compound 1 was 17,100, and the weight average molecular weight of polystyrene conversion was 31,300.
  • the reaction was performed in an argon atmosphere. A base that is hardly soluble in the reaction solution was separated using a filter. The reaction solution was dried with an evaporator for about 30 minutes to remove the solvent. The reaction solution was separated by a column in the same manner as in Reference Example 1, and then the separated product was dissolved in a small amount of acetone, methanol was added and stirred, and a small amount of water was added, whereby compound (C-2 3.50 g of a bispinacol ester compound (compound (C-3)) was obtained. The yield of compound (C-3) was 60.9%, and the purity based on HPLC area percentage determined from liquid chromatography was 97.5%.
  • Example 3 Since the high molecular compound 1 was dissolved in chloroform, a chloroform solution containing 0.5% (wt)% of the high molecular compound 1 was prepared and applied on a silicon wafer and glass by spin coating to obtain a thin film.
  • the thin film on the silicon wafer and the thin film on the glass were heat-treated at 300 ° C. in a nitrogen atmosphere to produce a laminate.
  • the infrared absorption spectrum of the thin film before and behind heat processing was measured with the infrared spectrophotometer.
  • An infrared absorption spectrum 11 of the thin film before the heat treatment and an infrared absorption spectrum 12 of the thin film after the heat treatment are shown in FIG.
  • the ultraviolet-visible absorption spectrum of the thin film before and after the heat treatment was measured with an ultraviolet-visible spectrophotometer.
  • FIG. 2 shows an ultraviolet-visible absorption spectrum 21 of the thin film before the heat treatment and an ultraviolet-visible absorption spectrum 22 of the thin film after the heat treatment.
  • Reference example 3 (Production of organic transistors) Using the polymer compound 1, an organic thin film transistor having the structure shown in FIG. 3 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon oxide film 32.
  • a source electrode 33 and a drain electrode 34 (made of a film in which chromium and gold are stacked in this order from the silicon oxide film side) are formed on the silicon oxide film 32 by a photolithography process. did.
  • the surface of the substrate was silane-treated by spin coating using hexamethylene disilazane (HMDS).
  • HMDS hexamethylene disilazane
  • the high molecular compound 1 was melt
  • the filtered solution was applied on the surface-treated substrate by a spin coating method. Thereafter, a heat treatment was performed at 300 ° C. for 1 hour in a nitrogen atmosphere to form the organic semiconductor layer 35.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 5 ⁇ 10 ⁇ 3 cm 2 / Vs. The results are shown in Table 2.
  • an organic thin film transistor having the structure shown in FIG. 4 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon oxide film 32. After sufficiently washing the substrate thus obtained, the surface of the substrate was silane treated with octadecyltrichlorosilane which is a silane coupling agent. Next, the high molecular compound 2 was melt
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) Was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 2.4 ⁇ 10 ⁇ 4 cm 2 / Vs. The results are shown in Table 2.
  • the obtained reaction solution was washed with an aqueous solution of sodium N, N-diethyldithiocarbamate, and the polymer compound was filtered.
  • a soluble component in heated chloroform was passed through a column in which alumina and silica were laminated.
  • the liquid treated in the column was added to methanol, and the precipitate was collected and dried to obtain polymer compound 3.
  • the yield of the high molecular compound 3 was 100 mg.
  • the number average molecular weight of polystyrene conversion of the high molecular compound 3 was 17,500, and the weight average molecular weight of polystyrene conversion was 42,400.
  • an organic thin film transistor having the structure shown in FIG. 4 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon oxide film 32. After sufficiently washing the substrate thus obtained, the surface of the substrate was silane treated with octadecyltrichlorosilane which is a silane coupling agent. Next, the high molecular compound 3 was melt
  • a heat treatment was performed at 300 ° C. for 1 hour in a nitrogen atmosphere to form the organic semiconductor layer 35.
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 7.0 ⁇ 10 ⁇ 3 cm 2 / Vs. The results are shown in Table 2.
  • Polymer compound 4 was synthesized in the same manner as in Example 2 except that compound (E) was used instead of compound (B). The yield of the high molecular compound 4 was 35 mg.
  • an organic transistor having the structure shown in FIG. 4 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon oxide film 32. Next, the high molecular compound 4 was melt
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 1.2 ⁇ 10 ⁇ 3 cm 2 / Vs. The results are shown in Table 2.
  • Polymer compound 5 was synthesized in the same manner as in Example 2 except that compound (F) was used instead of compound (B).
  • the yield of the high molecular compound 5 was 190 mg.
  • the number average molecular weight of polystyrene conversion of the high molecular compound 5 was 60,000, and the weight average molecular weight of polystyrene conversion was 94,000.
  • Reference Example 7 (Production of organic transistors) Using the polymer compound 5, an organic transistor having the structure shown in FIG. 4 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon oxide film 32. After sufficiently washing the substrate thus obtained, the surface of the substrate was silane treated with octadecyltrichlorosilane which is a silane coupling agent. Next, the high molecular compound 5 was melt
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) Was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 7.5 ⁇ 10 ⁇ 4 cm 2 / Vs. The results are shown in Table 2.
  • Polymer compound 6 was synthesized in the same manner as in Example 2 except that compound (G) was used instead of compound (B).
  • the yield of the high molecular compound 6 was 100 mg.
  • the number average molecular weight of polystyrene conversion of the high molecular compound 6 was 20,000, and the weight average molecular weight of polystyrene conversion was 28,000.
  • Reference Example 8 (Production of organic transistors) Using the polymer compound 6, an organic transistor having the structure shown in FIG. 4 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon oxide film 32. After sufficiently washing the substrate thus obtained, the surface of the substrate was treated with silane using phenethyltrichlorosilane, which is a silane coupling agent. Next, the high molecular compound 6 was melt
  • a heat treatment was performed at 300 ° C. for 1 hour in a nitrogen atmosphere to form the organic semiconductor layer 35.
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 1.8 ⁇ 10 ⁇ 2 cm 2 / Vs. The results are shown in Table 2.
  • Polymer compound 7 was synthesized in the same manner as in Example 2 except that compound (H) was used instead of compound (B).
  • the yield of the high molecular compound 7 was 74 mg.
  • the number average molecular weight of polystyrene conversion of the high molecular compound 7 was 59,000, and the weight average molecular weight of polystyrene conversion was 89,000.
  • Reference Example 9 (Production of organic transistors) Using the polymer compound 7, an organic transistor having the structure shown in FIG. 4 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon oxide film 32. After sufficiently washing the substrate thus obtained, the surface of the substrate was treated with silane using phenethyltrichlorosilane, which is a silane coupling agent. Next, the high molecular compound 7 was melt
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) Was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 3.3 ⁇ 10 ⁇ 3 cm 2 / Vs. The results are shown in Table 2.
  • Polymer compound 8 was synthesized in the same manner as in Example 1 except that compound (C-4) was used instead of compound (C-3). The yield of the high molecular compound 8 was 100 mg.
  • Reference Example 10 (Production of organic transistors) An organic transistor having the structure shown in FIG. 4 was produced using the polymer compound 8 by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon oxide film 32. After sufficiently washing the substrate thus obtained, the surface of the substrate was treated with silane using phenethyltrichlorosilane, which is a silane coupling agent. Next, the high molecular compound 8 was melt
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) Was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 4.8 ⁇ 10 ⁇ 2 cm 2 / Vs. The results are shown in Table 2.
  • Polymer compound 9 was synthesized in the same manner as in Example 2 except that compound (J) was used instead of compound (B).
  • the yield of the high molecular compound 9 was 142 mg.
  • the number average molecular weight of polystyrene conversion of the high molecular compound 9 was 52,000, and the weight average molecular weight of polystyrene conversion was 82,000.
  • Reference Example 11 (Production of organic transistors) Using the polymer compound 9, an organic transistor having the structure shown in FIG. 4 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon oxide film 32. After sufficiently washing the substrate thus obtained, the surface of the substrate was treated with silane using phenethyltrichlorosilane, which is a silane coupling agent. Next, the high molecular compound 9 was melt
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) Was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 1.3 ⁇ 10 ⁇ 3 cm 2 / Vs. The results are shown in Table 2.
  • Polymer compound 10 was synthesized in the same manner as in Example 2 except that compound (K) was used instead of compound (B). The yield of the high molecular compound 10 was 133 mg.
  • the polymer compound 10 had a polystyrene-equivalent number average molecular weight of 54,000 and a polystyrene-equivalent weight average molecular weight of 90,000.
  • Reference Example 12 (Production of organic transistors) Using the polymer compound 10, an organic transistor having the structure shown in FIG. 4 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon film 32. After sufficiently washing the substrate thus obtained, the surface of the substrate was treated with silane using phenethyltrichlorosilane, which is a silane coupling agent. Next, the high molecular compound 10 was melt
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) Was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field effect mobility obtained from the measured characteristics was calculated to be 4.8 ⁇ 10 ⁇ 3 cm 2 / Vs. The results are shown in Table 2.
  • Polymer compound 11 was synthesized in the same manner as in Example 2 except that compound (L) was used instead of compound (B). The yield of the high molecular compound 11 was 145 mg.
  • the polymer compound 11 had a polystyrene-equivalent number average molecular weight of 25,000 and a polystyrene-equivalent weight average molecular weight of 41,000.
  • Reference Example 13 (Production of organic transistors) Using the polymer compound 11, an organic transistor having the structure shown in FIG. 4 was produced by the following method. First, the surface of a heavily doped n-type silicon substrate 31 to be a gate electrode was thermally oxidized to form a 100 nm silicon film 32. After sufficiently washing the substrate thus obtained, the surface of the substrate was treated with silane using phenethyltrichlorosilane, which is a silane coupling agent. Next, the high molecular compound 11 was melt
  • a source electrode 33 having a channel length of 20 ⁇ m and a channel width of 2 mm, and a drain electrode 34 (from the organic semiconductor layer side, MoO 3 and gold in this order) are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition process. ) Was produced.
  • the transistor characteristics were measured by applying a gate voltage Vg of 10 to ⁇ 60 V and a source-drain voltage Vsd of ⁇ 60 V to the produced organic thin film transistor.
  • the field-effect mobility obtained from the measured characteristics was calculated to be 2.9 ⁇ 10 ⁇ 4 cm 2 / Vs. The results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Thin Film Transistor (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

La présente invention concerne un composé ayant une structure π-conjuguée qui est utile en tant que composante d'une couche de semi-conducteur organique d'un transistor organique; une couche mince qui utilise le composé; un composé qui est un précurseur permettant d'obtenir le composé qui comprend la structure π-conjuguée. Le composé selon l'invention possède un motif de structure représenté par la formule (1), et un motif de structure ayant une structure π-conjuguée. [Dans la formule, R1 et R2 représentent chacun un substituant; R3 et R4 représentent chacun un atome d'hydrogène ou un substituant; n et m représentent chacun un nombre entier de 0 à 3; Y représente un radical divalent. S'il y a de multiples substituants R1, ceux-ci peuvent être identiques ou différents. S'il y a de multiples substituants R2, ceux-ci peuvent être identiques ou différents.]
PCT/JP2011/080022 2010-12-27 2011-12-26 Composé et couche mince le contenant WO2012090912A1 (fr)

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