WO2020022128A1 - Polymère organique, son procédé de production et son utilisation - Google Patents

Polymère organique, son procédé de production et son utilisation Download PDF

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WO2020022128A1
WO2020022128A1 PCT/JP2019/027991 JP2019027991W WO2020022128A1 WO 2020022128 A1 WO2020022128 A1 WO 2020022128A1 JP 2019027991 W JP2019027991 W JP 2019027991W WO 2020022128 A1 WO2020022128 A1 WO 2020022128A1
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ring
group
unit
organic polymer
formula
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岡本　敏宏
忠法 黒澤
純一 竹谷
大次 池田
明人 山元
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国立大学法人東京大学
株式会社ダイセル
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • 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
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule

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  • the present invention includes a novel organic polymer (semiconductor polymer) useful for forming an organic semiconductor used for a semiconductor element (for example, a field effect transistor, a photoelectric conversion element, and the like), a method for manufacturing the same, and the organic polymer.
  • a novel organic polymer semiconductor polymer
  • the present invention relates to a composition, an organic semiconductor, a method for producing the same, and a semiconductor device (or electronic device).
  • a highly planarized aromatic condensed ring compound such as a metal phthalocyanine compound and a polyacene compound such as pentacene is typically known.
  • Organic semiconductors formed of these low-molecular compounds are generally formed by forming a film on a substrate by a vacuum high-temperature process such as vapor deposition.
  • a vacuum high-temperature process such as vapor deposition.
  • organic polymers are suitable, and organic polymers having various structures are being developed.
  • Patent Document 1 discloses a repeating unit represented by the following formula (I) (a repeating unit in which an aromatic ring is ortho-condensed in a zigzag manner; hereinafter, simply referred to as a zigzag unit). ) Is disclosed.
  • ring A and ring B each independently represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring
  • n represents an integer of 0 to 6
  • R 1 to R 2 + n each independently represent A1 to a (2 + n) each independently represent an integer of 0 to 2
  • a ring C is arranged in a non-linear manner with respect to an adjacent benzene ring in accordance with the number of n. Represents an ortho-fused benzene ring).
  • an organic polymer having a repeating unit (zigzag-like unit) in which the rings A and B are thiophene rings and n is 2 in the above formula (I) is prepared.
  • a semiconductor element is manufactured by forming a film on a substrate by a spin coating method.
  • the mobility (carrier mobility) ⁇ of the obtained organic polymer was not sufficient.
  • an object of the present invention is to provide a novel organic polymer having high mobility (electric mobility or carrier mobility) and a method for producing the same, a composition and an organic semiconductor containing the organic polymer, a method for producing the same, and An electronic device including an organic semiconductor is provided.
  • Another object of the present invention is to provide an organic material that can be oriented with high orientation (molecular orientation or crystallinity) [or a small ⁇ stack distance d ⁇ ] even when a film is formed by a simple film forming method such as a spin coating method.
  • An object of the present invention is to provide a polymer and a method for producing the same, a composition and an organic semiconductor including the organic polymer, a method for producing the same, and an electronic device including the organic semiconductor.
  • Still another object of the present invention is to provide an organic polymer capable of achieving both high orientation and high solubility in an organic solvent and a method for producing the same, a composition containing the organic polymer, an organic semiconductor and a method for producing the same, and An electronic device including an organic semiconductor is provided.
  • Another object of the present invention is to provide a method for easily or efficiently producing the organic polymer.
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, the organic polymer having zigzag-like units described in Examples of Patent Document 1 is not oriented between molecules in film formation by spin coating. I discovered that.
  • the donor unit (D) containing a predetermined zigzag unit and the acceptor unit (A) are combined, the orientation between molecules is improved, and the mobility is improved. Have been found to be effectively improved, and the present invention has been completed.
  • the organic polymer of the present invention is an organic polymer having a donor unit (D) and an acceptor unit (A), and the donor unit (D) is represented by at least the following formula (I).
  • the donor unit (D1) is represented by at least the following formula (I).
  • ring A and ring B each independently represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring
  • n represents an integer of 0 to 6
  • R 1 to R 2 + n each independently represent A 1 to a 2 + n each independently represent an integer of 0 to 2
  • a ring C is formed in a non-linear manner with respect to an adjacent benzene ring in accordance with the number of n.
  • An ortho-fused benzene ring is shown).
  • the donor unit (D1) has a unit represented by at least one of the following formulas (I-1) to (I-5) (particularly, a unit represented by the formula (I-3)). It may be.
  • R 1 to R 6 each independently represent an alkyl group, an aryl group, an alkoxy group, or an alkylthio group; a 1 to a 6 each independently represent an integer of 0 to 2; Ring A and ring B are the same as described above).
  • R 1 to R 4 each independently represent an alkyl group, an aryl group, an alkoxy group or an alkylthio group, and at least one of R 1 to R 4 is linear or It may be a branched C 4-34 alkyl group or a linear or branched C 4-34 alkoxy group, and a 1 to a 4 may each independently be 0 or 1. At least one of a 1 to a 4 may be 1.
  • the ring A and the ring B may be an aromatic ring selected from a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, and a benzene ring.
  • the acceptor unit (A) may include a unit (A1) having a nitrogen atom and an aromatic heterocyclic skeleton containing a Group 16 atom of the periodic table.
  • This unit (A1) may include a unit represented by at least one formula selected from the following formulas (III-1) to (III-5).
  • rings E 1 and E 2 each independently represent an aromatic ring
  • Z 1 to Z 5 each independently represent an oxygen atom, a sulfur atom or a selenium atom
  • R A1 , R A2 and RA3 each independently represents an alkyl group, an aryl group, an alkoxy group, an alkylthio group or a halogen atom
  • m1, m2 and m3 each independently represent an integer of 0 or more
  • the ring E 1 may be a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, an isoquinoline ring, a phthalazine ring or a quinoxaline ring, and Z 1 is an oxygen atom or a sulfur atom.
  • R A1 may be an alkyl group, an alkoxy group or a halogen atom, and m1 may be an integer of about 0 to 2.
  • the organic polymer may be a block copolymer or an alternating copolymer of the donor unit (D) and the acceptor unit (A).
  • the donor unit (D) may include a unit having at least one substituent selected from a linear or branched alkyl group and a linear or branched alkoxy group
  • the sex unit (A) may include a unit having no linear or branched alkyl group and no linear or branched alkoxy group.
  • the present invention also includes a method for producing the organic polymer by subjecting a compound containing the donor unit (D) and a compound containing the acceptor unit (A) to a coupling reaction.
  • the coupling reaction may be a Suzuki coupling reaction, and the reaction may be performed under microwave irradiation.
  • the present invention provides an organic semiconductor containing the organic polymer (for example, in addition to the organic polymer, further includes a substrate, the organic polymer is edge-on orientation or face-on orientation with respect to the substrate A composition comprising the organic polymer and a solvent; a method of applying the composition to a substrate and removing the solvent to produce the organic semiconductor; and the organic semiconductor. Electronic devices including semiconductors are also included.
  • the novel organic polymer of the present invention combines a donor unit (D) containing a predetermined zigzag unit and an acceptor unit (A), the orientation between molecules is improved to achieve high mobility. it can. Further, even when the film is formed by a simple film forming method such as a spin coating method, the film can be oriented with high orientation (molecular orientation or crystallinity) [or low ⁇ stack distance d ⁇ ]. Further, it is possible to achieve both high orientation and high solubility in an organic solvent, which are contradictory characteristics. According to the method of the present invention, the organic polymer can be easily or efficiently produced.
  • FIG. 1 is a diagram showing a relationship between a two-dimensional diffraction image in a thin film X-ray analysis of a film formed by spin-coating the compound obtained in Example 1 and an annealing temperature
  • FIG. A two-dimensional diffraction image at 100 ° C. (b) a two-dimensional diffraction image at an annealing temperature of 150 ° C., (c) a two-dimensional diffraction image at an annealing temperature of 200 ° C., and (d) a two-dimensional diffraction image at an annealing temperature of 240 ° C. It is a two-dimensional diffraction image.
  • FIG. 1 is a diagram showing a relationship between a two-dimensional diffraction image in a thin film X-ray analysis of a film formed by spin-coating the compound obtained in Example 1 and an annealing temperature
  • FIG. A two-dimensional diffraction image at 100 ° C. (b) a two-dimensional
  • FIG. 2 is a diagram showing a relationship between a two-dimensional diffraction image in a thin film X-ray analysis of a film obtained by forming the compound obtained in Comparative Example 1 and a film forming method
  • FIG. 2B is a two-dimensional diffraction image when the film is formed
  • FIG. 3 is a schematic diagram of an element for measuring transistor characteristics.
  • the donor unit (D) contains at least a first donor unit (or zigzag unit) (D1) represented by the following formula (I).
  • ring A and ring B each independently represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring
  • n represents an integer of 0 to 6
  • R 1 to R 2 + n each independently represent A 1 to a 2 + n each independently represent an integer of 0 to 2
  • a ring C is formed in a non-linear manner with respect to an adjacent benzene ring in accordance with the number of n.
  • An ortho-fused benzene ring is shown).
  • Ring A and Ring B each independently represent an aromatic hydrocarbon ring (arene ring) or an aromatic heterocycle (heteroarene ring).
  • the aromatic hydrocarbon ring include a benzene ring; a fused bi to tetracyclic C 10-20 arene ring, for example, a bicyclic C 10-16 arene ring such as a naphthalene ring; a tricyclic arene ring (eg, anthracene, Condensed tricyclic C 12-16 arene ring such as phenanthrene) and the like.
  • Preferred aromatic hydrocarbon rings are benzene rings, naphthalene rings, especially benzene rings.
  • the aromatic heterocyclic ring includes a monocyclic ring or a condensed ring having at least one heteroatom as a ring constituent atom.
  • the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, a selenium atom, a phosphorus atom, a silicon atom, a titanium atom, a zinc atom, and a germanium atom.
  • the aromatic heterocycle may have multiple heteroatoms, for example, the same or different heteroatoms.
  • Preferred heteroatoms may be heteroatoms selected from oxygen, sulfur, nitrogen and selenium, preferably oxygen, sulfur and especially oxygen.
  • the heterocycle having a hetero atom may be a 3- to 10-membered ring, usually a 5- or 6-membered ring, and such a heterocycle includes an arene ring such as a benzene ring (for example, the aforementioned arene ring and the like). ) May be condensed.
  • a preferred aromatic heterocycle may be a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, or the like.
  • Ring A and ring B are usually an aromatic heterocycle (preferably a furan ring, a thiophene ring, and particularly a thiophene ring) in many cases.
  • the types of the ring A and the ring B may be different from each other, but are usually the same in many cases.
  • the condensed position of the adjacent benzene ring in the ring A and the ring B may be different from each other, but usually the same.
  • N represents an integer of 0 to 6, and may be usually about 0 to 5 (eg, 0 to 4), preferably about 1 to 3 (eg, 2 or 3).
  • the benzene ring represented by ring C is ortho-condensed to the adjacent benzene ring in a non-linear (preferably zigzag) manner sequentially according to the number of n.
  • One or more ring C (benzene ring) is different from an anthracene ring, a naphthacene ring, a pentacene ring or the like which is ortho-condensed linearly, and is ortho-condensed non-linearly in a major axis direction to benzene rings adjacent to each other.
  • Benzene ring may share the 1,2-position carbon atom and the 3,4-position carbon atom and may be ortho-condensed in a zigzag form.
  • the form is preferred.
  • substituent represented by R 1 to R 2 + n include, for example, a halogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heterocyclic group, and a hydroxyl group.
  • Examples of the halogen atom represented by R 1 to R 2 + n include a fluorine, chlorine, bromine or iodine atom.
  • Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, i-butyl, s-butyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, n Direct octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, 3-hexyltetradecyl, 3-octyltridecyl, 5-decylheptadecyl, etc.
  • Examples thereof include a linear or branched C 1-36 alkyl group.
  • the alkyl group may usually be a linear or branched C 4-34 alkyl group, and in order to enhance the solubility in an organic solvent, a long-chain alkyl group such as a linear or branched
  • a long-chain alkyl group such as a linear or branched
  • it is a C 6-32 alkyl group, preferably a straight-chain or branched C 6-30 alkyl group (eg a straight-chain or branched C 8-28 alkyl group).
  • branched alkyl groups are advantageous.
  • haloalkyl group examples include halogen atoms such as chloromethyl group, trichloromethyl group, trifluoromethyl group, pentafluoroethyl group, perchloroethyl group, perfluoroisopropyl group, and perfluorobutyl group (fluorine, chlorine, bromine atom, etc.). And the like, and a straight-chain or branched-chain C 1-36 alkyl group (for example, a halo C 1-12 alkyl group, preferably a halo C 1-6 alkyl group).
  • the alkyl group and / or the haloalkyl group may have a substituent.
  • a substituent include an alkoxy group (eg, a C 1-10 alkoxy group such as a methoxy group and an ethoxy group).
  • alkenyl group examples include a C 2-30 alkenyl group such as a vinyl group, an allyl group, a 2-butenyl group, and a 4-pentenyl group.
  • a linear or branched C 3-18 alkenyl group is exemplified.
  • it may be a linear or branched C 4-16 alkenyl group.
  • alkynyl group examples include, for example, a C 2-30 alkynyl group such as an ethynyl group, a 2-propynyl group, and a 1-pentynyl group.
  • a linear or branched C 3-18 alkynyl group for example, It may be a linear or branched C 4-16 alkynyl group.
  • Examples of the cycloalkyl group include a C 3-10 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • Examples of the aryl group include a C 6-12 aryl group such as a phenyl group and a naphthyl group, and a bi-C 6-12 aryl group such as a biphenyl group.
  • Examples of the aralkyl group include a C 6-12 aryl-C 1-4 alkyl group such as a benzyl group and a phenylethyl group (phenethyl group).
  • an aromatic heterocycle for example, pyridine, pyrazine, quinoline, naphthyridine, quinoxaline, phenazine, phenanthroline, nitrogen-containing heterocycle such as carbazole, furan, oxygen-containing heterocycle such as benzofuran,
  • sulfur-containing heterocycles such as thiophene, benzothiophene, dibenzothiophene, and thienothiophene
  • selenium-containing heterocycles such as selenophene and benzoselenophene
  • heterocycles having a plurality of heterogeneous heteroatoms such as thiazole and benzothiazole.
  • alkoxy group examples include a linear or branched C 1-32 alkoxy group corresponding to the alkyl group, for example, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a hexadecyloxy group, a 3-octyltri group.
  • alkoxy group examples include a decyloxy group and a 5-decylheptadecyloxy group.
  • the alkoxy group may usually be a linear or branched C 4-36 alkoxy group (for example, a linear or branched C 4-34 alkoxy group, etc.), and may be a long-chain alkoxy group, for example, Even a linear or branched C 6-32 alkoxy group, preferably a linear or branched C 6-30 alkoxy group (for example, a linear or branched C 8-28 alkoxy group).
  • the alkylthio group include a linear or branched C 4-36 alkylthio group corresponding to the above alkoxy group.
  • an alkoxy group for example, a long-chain alkoxy group
  • an alkylthio group for example, a long-chain alkylthio group
  • haloalkoxy group examples include a haloalkoxy group corresponding to the haloalkyl group, for example, a halogen atom such as a chloromethoxy group, a trichloromethoxy group, a trifluoromethoxy group, a trifluoroethoxy group, a perfluoroisopropoxy group, and a perfluorobutoxy group.
  • a linear or branched C 1-36 alkoxy group for example, a halo C 1-12 alkoxy group, and preferably a halo C 1-6 alkoxy group having a fluorine atom, a chlorine atom or a bromine atom.
  • haloalkylthio group examples include a haloalkylthio group corresponding to the haloalkoxy group.
  • Examples of the cycloalkyloxy group include a C 3-10 cycloalkyloxy group such as a cyclopentyloxy group, a cyclohexyloxy group, and a cyclooctyloxy group, and the cycloalkylthio group includes a C 3-10 corresponding to the cycloalkyloxy group.
  • An example is a 3-10 cycloalkylthio group.
  • aryloxy group examples include a C 6-12 aryloxy group such as a phenoxy group and a naphthoxy group
  • arylthio group examples include a C 6-12 arylthio group corresponding to the aryloxy group.
  • alkoxycarbonyl group examples include, for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, t-butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 3-octyltridecyloxycarbonyl And a linear or branched C 1-36 alkoxy-carbonyl group such as a 5-decylheptadecyloxycarbonyl group.
  • Examples of the cycloalkoxycarbonyl group include a C 3-10 cycloalkyloxy-carbonyl group such as a cyclohexyloxycarbonyl group, and examples of the aryloxycarbonyl group include a C 6-12 aryloxy group such as a phenoxycarbonyl group.
  • Examples of the alkylsulfonyl group include a linear or branched C 1-4 alkylsulfonyl group such as a methylsulfonyl group, and examples of the haloalkylsulfonyl group include a chloromethylsulfonyl group and a trifluoromethylsulfonyl group. And a straight-chain or branched-chain halo C 1-4 alkylsulfonyl group.
  • N-substituted amino group examples include N-mono C 1-6 alkylamino group such as N-methylamino group and N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, And N, N-diC 1-6 alkylamino groups such as N, N-dibutylamino group.
  • acyl group examples include a C 1-30 alkyl-carbonyl group such as an acetyl group and a propionyl group, and a C 6-10 aryl-carbonyl group such as a benzoyl group.
  • acyloxy group examples include a C 1-30 alkyl-carbonyloxy group such as an acetyloxy group and a propionyloxy group, and a C 6-10 aryl-carbonyloxy group such as a benzoyloxy group.
  • the alkyl silyl group for example, mono- to tri-C 1-4 alkylsilyl group such as trimethylsilyl group.
  • Examples of the alkyl silyl ethynyl group for example, mono- to tri-C 1-4 alkylsilyl such as trimethylsilyl ethynyl group
  • An ethynyl group can be exemplified.
  • the substituents R 1 to R 2 + n may be, for example, an electron accepting group such as a halogen atom, a cyano group, a haloalkyl group, a haloalkoxyl group, a haloalkylsulfonyl group, but improve the donor property (electron donating property).
  • the substituents R 1 ⁇ R 2 + n as alkyl group, alkoxy group, N- electron donating group such as a substituted amino group, or a substituent R 1 ⁇ embodiment having a hydrogen atom instead of R 2 + n (i.e., the coefficients a (1 to a 2 + n is 0 or 1).
  • substituents R 1 to R 2 + n may be the same or different, may be different depending on the position of a benzene ring interposed between ring A and ring B, or may be the same.
  • substituents in order to increase the solubility in an organic solvent, the above-mentioned alkyl group (linear or branched long-chain alkyl group), alkoxy group (linear or branched long-chain alkoxy group) Particularly, an alkyl group is preferable.
  • an aryl group may contribute to carrier mobility.
  • the alkyl group is preferably a branched alkyl group from the viewpoint of improving solubility, and more preferably a branched C 10-40 alkyl group (for example, a branched C 16-34 alkyl group). Group), more preferably a branched C 18-30 alkyl group (eg, a branched C 20-28 alkyl group such as a 3-octyl-tridecyl group, a 5-decyl-heptadecyl group), particularly a branched C 21 alkyl group.
  • a -26 alkyl group for example, a branched C 22-24 alkyl group such as a 4-octyl-tetradecyl group or a 5-octyl-pentadecyl group, particularly a branched C 22 alkyl group such as a 4-octyl-tetradecyl group); preferable.
  • the branched structure of the branched alkyl group is not particularly limited, but is usually a branched alkyl group having one branch point in many cases.
  • the position of the branch point in the branched alkyl group is not particularly limited, but is preferably in the 2 to 8-position (for example, 2 It is preferable to have a branch point at the (6-position), more preferably at the 3- to 5-position, especially at the 4-position.
  • the carbon numbers of the two linear alkyl groups extending from the branch point to the terminal are substantially the same, and in the two linear alkyl groups,
  • the difference in the number of carbon atoms may be, for example, about 0 to 6, preferably about 0 to 4, and more preferably about 0 to 2.
  • Specific examples of the two linear alkyl groups include a linear C 6-16 alkyl group, preferably a linear C 7-14 alkyl group, and more preferably a linear C 8 alkyl group such as a dodecyl group. It may be a -12 alkyl group (particularly, a linear C 8-10 alkyl group such as an octyl group and a decyl group).
  • the coefficients a 1 to a 2 + n each independently represent an integer of 0 to 2, and are usually 0 or 1 in many cases. Further, all of a 1 to a 2 + n may be simultaneously “0” (that is, unsubstituted), but usually, at least one of a 1 to a 2 + n is 1 or 2, that is, a 1 to a 2 + n Are not all “0” at the same time, and often have at least one of the substituents R 1 to R 2 + n .
  • the types of the substituents R 1 to R 2 + n may be the same or different. For example, the substituents on the same benzene ring may be the same or different, and the substituents on different benzene rings may be the same or different.
  • the substituents R 1 to R 2 + n may be substituted on any benzene ring interposed between the ring A and the ring B.
  • the substitution position of the substituents R 1 to R 2 + n with respect to a predetermined benzene ring interposed between the ring A and the ring B is not particularly limited.
  • a benzene ring adjacent to ring A and a benzene ring adjacent to ring B (the benzene ring located at both ends of the condensed benzene ring excluding ring A and ring B in formula (I)) Ring) often has substituents R 1 and R 2 + n (especially when a 1 and a 2 + n are 1).
  • the specific donor unit (D1) represented by the formula (I) is, for example, a unit represented by at least one of the following formulas (I-1) to (I-5). Is also good.
  • R 1 to R 6 and a 1 to a 6 are the same as those of R 1 to R 2 + n and a 1 to a 2 + n (where n is an integer of 0 to 4) Correspondingly the same).
  • R 1 to R 6 are each independently often an alkyl group, an aryl group, an alkoxy group or an alkylthio group (particularly, an alkyl group or an alkoxy group), and a 1 to a 6 are each independently It is often 0 or 1.
  • the donor unit (D1) may be contained alone or in combination of two or more.
  • a polymer having such a donor unit (D1) has high carrier mobility and is useful as an organic semiconductor.
  • these donor units (D1) from the viewpoints of carrier mobility, productivity (or moldability), etc., a unit represented by the above formula (I-2) having a phenanthrene ring and a chrysene ring are usually provided.
  • the unit represented by the formula (I-3), the unit represented by the formula (I-4) having a picene ring, and the like are widely used.
  • the unit represented by the formula (I-3) is useful. Typically, for example, it may be a unit represented by the following formula (I-3).
  • R 1 to R 4 are each independently the same as the substituents R 1 to R 2 + n including preferred embodiments, and at least one of R 1 to R 4 is linear or branched.
  • Ra represents a hydrogen atom, an alkyl group or an acyl group
  • R 1 to R 4 and a 1 to a 4 are the same as described above.
  • Examples of the alkyl group represented by Ra include a linear or branched C 1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
  • Examples of the acyl group include a linear or branched C 1-4 alkyl-carbonyl group such as an acetyl group and a propionyl group.
  • R 1 to R 4 is a long-chain alkyl group (for example, a linear or branched C 4 -32 alkyl group) and / or a long-chain alkoxy group (eg, a linear or branched C 4-32 alkoxy group), and a 1 to a 4 each independently represent 0 or 1 are shown, at least one of a 1 ⁇ a 4 is a 1 (i.e., does not a 1 ⁇ a 4 is 0 at the same time) often.
  • a long-chain alkyl group for example, a linear or branched C 4 -32 alkyl group
  • a long-chain alkoxy group eg, a linear or branched C 4-32 alkoxy group
  • Such a long-chain alkyl group and / or long-chain alkoxy group is often substituted on a benzene ring adjacent to the ring A and the ring B. That is, out of a 1 to a 4 , a 1 and a 4 are often 1.
  • Representative units of the unit represented by the formula (I-3) include, for example, the following formulas (I-3a1), (I-3b1), (I-3c1) or (I-3d1) [preferably the formula (I-3d1)] (I-3a1) or (I-3c1)].
  • R 1 and R 4 represent a linear or branched C 6-30 alkyl group or a linear or branched C 6-30 alkoxy group).
  • the first donor unit (D1) may be used alone or in combination of two or more. That is, the first donor unit (D1) belongs to the category represented by the formula (I) and may include a plurality of units of different types. For example, the first unit (D1) has a coefficient n (number of benzene rings).
  • n number of benzene rings
  • a plurality of units selected from different units [eg, a unit represented by the formula (I-2), a unit represented by the formula (I-3), a unit represented by the formula (I-5), etc.] It may contain a unit having a different vertical position (for example, a unit represented by the formula (I-3a1) and a unit represented by the formula (I-3b1)).
  • the donor unit (D) includes, in addition to the first donor unit (D1) represented by the formula (I), another unit having a donor property (second donor unit) (D2). May be.
  • the second donor unit (D2) for example, a substituent such as a thiophene unit, a dibenzothiophene unit, or a benzodithiophene unit [for example, a group exemplified as the substituents R 1 to R 2 + n in the formula (I); Similar substituents] may be used.
  • These donor units may be contained alone or in combination of two or more.
  • a donor unit represented by the following formula (II-1) is generally used.
  • R D1 represents a substituent
  • k represents an integer of 0 to 2.
  • examples of the substituent R D1 include the same substituents as those of the substituents R 1 to R 2 + n in the above formula (I), including preferred embodiments.
  • an alkyl group or an alkoxy group for example, , A linear or branched long-chain alkyl group, or a linear or branched long-chain alkoxy group in many cases.
  • the coefficient k is often 0 or 1.
  • the ratio of the donor unit (D1) represented by the formula (I) is selected from the range of, for example, about 10 to 100 mol% (eg, 30 to 100 mol%) based on the entire donor unit (D).
  • 50 to 100 mol% preferably 60 to 100 mol% (for example, 70 to 99 mol%), and more preferably 80 to 100 mol% (for example, 85 to 95 mol%) Mol%), especially about 90 to 100 mol% (eg, 95 to 100 mol%, preferably substantially 100 mol%).
  • the acceptor unit (A) is not particularly limited as long as it is a structural unit having an acceptor property (electron accepting property, electron deficiency or electron deficiency), and a conventional acceptor unit can be used.
  • a typical acceptor unit (A) for example, a unit (A1) having an aromatic heterocyclic skeleton containing a nitrogen atom and a Group 16 (or Group 6B) atom of the periodic table [First acceptor unit (A1) Also referred to].
  • the first acceptor unit (A1) is not particularly limited as long as it has a nitrogen atom and an aromatic heterocyclic skeleton containing a Group 16 atom in the periodic table.
  • Group 16 atoms in the periodic table include an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and a polonium atom (preferably an oxygen atom, a sulfur atom or a selenium atom, more preferably an oxygen atom or a sulfur atom, particularly a sulfur atom ).
  • the aromatic heterocyclic skeleton contained in the first acceptor unit (A1) usually has a 5- or 6-membered heterocyclic ring (preferably a 5-membered heterocyclic ring) containing a nitrogen atom and an atom of Group 16 of the periodic table (or an internal ring thereof).
  • S is often a skeleton. That is, the aromatic heterocyclic skeleton may be the 5- or 6-membered heterocyclic skeleton, but may include a plurality of aromatic rings (the arene ring) including the 5- or 6-membered heterocyclic ring (particularly, the 5-membered heterocyclic ring).
  • / or heteroarene ring may be a fused and / or fused ring (or linked by a single bond) polycyclic heterocyclic skeleton (in particular, a fused polycyclic heterocyclic skeleton in which the plurality of rings are fused). Good.
  • Examples of the typical first acceptor unit (A1) include units represented by the following formulas (III-1) to (III-5).
  • rings E 1 and E 2 each independently represent an aromatic ring
  • Z 1 to Z 5 each independently represent a Group 16 atom of the periodic table
  • R A1 , R A2 and R A3 Are each independently a substituent
  • m1, m2 and m3 are each independently an integer of 0 or more).
  • Group 16 atoms represented by Z 1 for example, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, such as polonium atom.
  • the aromatic ring represented by E 1 is not particularly limited as long as it can be condensed with a 5-membered heterocyclic ring containing atom Z 1 and two nitrogen atoms, ie, as long as it has two carbon atoms adjacent to each other. It may be a hydrogen ring (arene ring) or an aromatic heterocycle (heteroarene ring).
  • aromatic hydrocarbon ring for example, a monocyclic arene ring such as a benzene ring; a condensed polycyclic arene ring [for example, an indene ring, an indane ring, a naphthalene ring, a tetralin ring, an azulene ring, an indacene ring] , Acenaphthylene ring, biphenylene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, fluoranthene ring, aceanthrylene ring, acephenanthrylene ring, naphthacene ring, chrysene ring, pyrene ring, triphenylene ring, pentacene ring, pentaphene ring , A C 9-30 condensed polycyclic arene ring such as a picene ring,
  • Preferred aromatic hydrocarbon rings include a C 6-22 arene ring (eg, a C 6-18 arene ring), and more preferably a C 6-14 arene ring (eg, a C 6-10 arene ring such as a benzene ring or a naphthalene ring) Ring), especially a benzene ring.
  • aromatic heterocyclic ring examples include a monocyclic heteroarene ring [eg, a nitrogen (N) -containing monocyclic heteroarene ring (eg, a pyrrole ring, an imidazole ring, a pyrazole ring, Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, etc.); oxygen (O) -containing monocyclic heteroarene ring (eg, furan ring, pyran ring, etc.); sulfur (S) -containing monocyclic heteroarene ring (eg, A monocyclic heteroarene ring containing two or more heteroatoms (eg, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, thiazine ring, thiadiazine ring, etc.) A C 2-5 monocyclic heteroarene ring [eg, a nitrogen (N)
  • Preferred heteroarene rings include C 2-13 heteroarene rings (eg, nitrogen (N) -containing monocyclic or polycyclic C 2-13 heteroarene rings and the like), and more preferably C 3-9 heteroarene rings ( In particular, it may be a nitrogen (N) -containing monocyclic or bicyclic C 3-9 heteroarene ring such as a pyridine ring, a pyridazine ring, an isoquinoline ring, a phthalazine ring, and a quinoxaline ring.
  • N nitrogen
  • N nitrogen
  • bicyclic C 3-9 heteroarene ring such as a pyridine ring, a pyridazine ring, an isoquinoline ring, a phthalazine ring, and a quinoxaline ring.
  • Preferable ring E 1 includes a C 6-14 arene ring, a nitrogen (N) -containing C 3-10 heteroarene ring, and among others, a C 6-10 arene ring, a nitrogen (N) -containing monocyclic or A bicyclic C 4-8 heteroarene ring (particularly a C 6-10 arene ring such as a benzene ring) is preferred.
  • the ring E 1 is a benzene ring, a naphthalene ring, a pyridine ring, a pyridazine ring, an isoquinoline ring, a phthalazine ring, aromatic ring selected from a quinoxaline ring (particularly, benzene ring) is preferably.
  • the aromatic ring represented by E 1 condensation position between 5 membered heterocyclic ring containing atoms Z 1 and two nitrogen atoms is not particularly limited.
  • Examples of the substituent represented by R A1 include the same groups as the groups exemplified as R 1 to R 2 + n in the formula (I).
  • Preferable examples of the substituent R A1 include an alkyl group, an aryl group, an alkoxy group, an alkylthio group, and a halogen atom.
  • a long-chain alkyl group for example, a linear or branched C 6-36 alkyl group
  • a long-chain alkoxy group eg, a linear or branched C 6-36 alkoxy group
  • a halogen atom eg, a linear or branched C 6-36 alkoxy group
  • Coefficients m1 can be appropriately selected depending on the kind of ring E 1, for example, an integer of 0 to 4 (e.g., an integer of 0 to 3), preferably an integer of 0 to 2 (e.g., 0 or 1), more preferably May be 0.
  • an integer of 0 to 4 e.g., an integer of 0 to 3
  • an integer of 0 to 2 e.g., 0 or 1
  • more m1 is 2 or more
  • the types of the two or more substituents RA1 may be the same or different from each other.
  • Typical examples of the unit represented by the formula (III-1) include units represented by the following formulas (III-1a) to (III-1g).
  • the acceptor unit (A) may contain the units represented by the above formulas (III-1a) to (III-1g) alone or in combination of two or more.
  • the units represented by the formulas (III-1a) to (III-1g) are preferable. .
  • the periodic table Group 16 atom represented by Z 2 include the same atoms including Z 1 and preferred embodiments of the formula (III-1). Also, two atoms Z 2 may be the same or different from each other, usually, it is often the same.
  • the aromatic ring represented by E 2 can be condensed at two places with a 5-membered heterocyclic ring containing the atom Z 2 and two nitrogen atoms, that is, as long as it has two or more pairs of two carbon atoms adjacent to each other. It is not limited, and may be an aromatic hydrocarbon ring (arene ring) or an aromatic heterocyclic ring (heteroarene ring).
  • aromatic hydrocarbon ring for example, a monocyclic arene ring such as a benzene ring; a condensed polycyclic arene ring [for example, an indene ring, an indane ring, a naphthalene ring, a tetralin ring, an azulene ring, an indacene ring] , Acenaphthylene ring, biphenylene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, fluoranthene ring, aceanthrylene ring, acephenanthrylene ring, naphthacene ring, chrysene ring, pyrene ring, triphenylene ring, pentacene ring, pentaphene ring , A C 9-30 condensed polycyclic arene ring such as a picene ring,
  • Preferred aromatic hydrocarbon rings include a C 6-22 arene ring (eg, a C 6-18 arene ring), and more preferably a C 6-14 arene ring (eg, a C 6-10 arene ring such as a benzene ring or a naphthalene ring) Ring, etc.), especially a naphthalene ring.
  • aromatic heterocyclic ring examples include a polycyclic heteroarene ring [eg, a nitrogen (N) -containing polycyclic heteroarene ring (eg, an indolizine ring, an indole ring, a 3H-indole ring, Indole ring, 1H-indazole ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, 4aH-carbazole ring, ⁇ -carboline ring, acridine ring, A phenanthridine ring, a phenazine ring, a phenanthroline ring, a perimidine ring, etc.); an oxygen (O) -containing polycyclic heteroarene ring
  • N nitrogen
  • O oxygen
  • a sulfur (S) -containing polycyclic heteroarene ring ( In example, a benzothiophene ring, a thianthrene ring, etc.); polycyclic heteroarene ring containing two or more hetero atoms (e.g., a phenoxazine ring, a phenothiazine ring, phenoxathiin ring, C such as phenarsazine ring) 6- 20 polycyclic heteroarene rings, etc.].
  • a preferred heteroarene ring may be a C 6-13 heteroarene ring (eg, a nitrogen (N) -containing monocyclic or polycyclic C 6-13 heteroarene ring and the like).
  • Preferred ring E 2 include such C 6-14 arene ring, among others, a benzene ring, C 6-10 arene ring such as a naphthalene ring (especially a naphthalene ring) is preferred.
  • the aromatic ring represented by E 2 the condensation position of the 5-membered heterocyclic ring containing atoms Z 2 and the two nitrogen atoms is not particularly limited.
  • substituent represented by R A2 include the same groups as the groups exemplified as R 1 to R 2 + n in the formula (I).
  • Preferred substituents R A2 include an alkyl group, an aryl group, an alkoxy group, an alkylthio group, and a halogen atom.
  • a long-chain alkyl group for example, a linear or branched C 6-36 alkyl group
  • a long-chain alkoxy group eg, a linear or branched C 6-36 alkoxy group
  • halogen atom eg, a linear or branched C 6-36 alkoxy group
  • Factor m2 can be appropriately selected depending on the type of ring E 2, for example, an integer of 0 to 4 (e.g., an integer of 0 to 3), preferably an integer of 0 to 2 (e.g., 0 or 1), more preferably May be 0.
  • an integer of 0 to 4 e.g., an integer of 0 to 3
  • an integer of 0 to 2 e.g., 0 or 1
  • m2 is 2 or more, the types of the two or more substituents RA2 may be the same or different from each other.
  • Typical examples of the unit represented by the formula (III-2) include a unit represented by the following formula (III-2a).
  • m2a represents 0 or 1
  • Z 2 and R A2 are as defined above, including the preferred embodiments, respectively).
  • m2a is preferably 0. Further, the two m2a may be the same or different from each other.
  • examples of the atom belonging to Group 16 of the periodic table represented by Z 3 include the same atoms as those of Z 1 in the formula (III-1), including preferred embodiments.
  • examples of the atom belonging to Group 16 of the periodic table represented by Z 4 include the same atoms as those of Z 1 in the formula (III-1), including preferred embodiments. Also, two atoms Z 4 may be the same or different from each other, usually, it is often the same.
  • the periodic table Group 16 atom represented by Z 5 include the same atoms including Z 1 and preferred embodiments of the formula (III-1). Also, two atoms Z 5 may be the same or different from each other, usually, it is often the same.
  • R A3 examples include the same groups as the groups exemplified as R 1 to R 2 + n in the formula (I).
  • Preferred substituents R A3 include an alkyl group, an aryl group, an alkoxy group, an alkylthio group, and a halogen atom.
  • a long-chain alkyl group for example, a linear or branched C 6-36 alkyl group
  • a long-chain alkoxy group eg, a linear or branched C 6-36 alkoxy group.
  • the coefficient m3 is 0 or 1, preferably 0.
  • Two m3's may be the same or different from each other.
  • the types of the two substituents RA3 may be the same or different from each other.
  • first acceptor units (A1) may be used alone or in combination of two or more.
  • a unit represented by the formula (III-1) is preferable, and a unit represented by the formula (III-1a) is particularly preferable.
  • the acceptor unit (A) does not necessarily need to include the first acceptor unit (A1), and may include another acceptor unit (also referred to as a second acceptor unit (A2)).
  • the second acceptor unit (A2) may have, for example, a substituent [for example, the same substituent as the group exemplified as the substituents R 1 to R 2 + n in the formula (I)].
  • substituents for example, the same substituent as the group exemplified as the substituents R 1 to R 2 + n in the formula (I)].
  • Examples include units having an aromatic hydrocarbon ring skeleton in which at least a 5-membered carbon ring is fused, such as a cyclopenta [h, i] aceanthrylene unit (a unit represented by the following formula).
  • the acceptor unit (A) may be formed of a single unit or a combination of two or more units, and at least one selected from a first acceptor unit (A1) and a second acceptor unit (A2) (In particular, the first acceptor unit (A1)).
  • the ratio of the first acceptor unit (A1) is, for example, based on the entire acceptor unit (A). From about 10 to 100 mol% (for example, 30 to 100 mol%). In order to enhance carrier mobility, for example, 50 to 100 mol%, preferably 60 to 100 mol% (for example, 70 to 100 mol%) To 99 mol%), more preferably about 80 to 100 mol% (eg, 85 to 95 mol%), particularly about 90 to 100 mol% (eg, 95 to 100 mol%, and preferably substantially 100 mol%). It may be.
  • the organic polymer of the present invention may contain other conjugated units and / or non-conjugated units that do not belong to the donor unit (D) and the acceptor unit (A) (for example, alkylene units). Unit etc.).
  • the ratio of such a unit is, for example, 10 mol% or less (for example, 0 to 5 mol%), preferably 1 mol% or less (for example, 0.01 to 0.1 mol%), based on the entire constitutional unit of the organic polymer. (Approximately 1 mol%), and is preferably substantially not contained.
  • the organic polymer of the present invention is a copolymer containing at least a donor unit (D) (also simply referred to as a D unit) and an acceptor unit (A) (also simply referred to as an A unit). And a random copolymer of A units, but from the viewpoint that orientation (or crystallinity) is easily improved by intermolecular interaction, a form in which each unit is regularly arranged (or having a repeating unit) Form), and usually, preferably an alternating copolymer or a block copolymer (a copolymer represented by the following formula (1)).
  • the alternating copolymer may be any copolymer as long as D units and A units are alternately arranged, and in the formula (1), q and r are both 1.
  • the plurality of repeating D units and A units may include a plurality of types of units, but from the viewpoint of improving intermolecular interaction, both are usually formed of the same type or the same unit. (Eg, the following formula (i)).
  • the block copolymer only needs to form a block by combining or linking at least one of the D unit and the A unit.
  • at least one of q and r is repeated. It is a copolymer having a number of 2 or more.
  • a block copolymer represented by the following formula (ii) or (iii) may be used.
  • the organic polymer is preferably an alternating copolymer (particularly, a copolymer represented by the formula (i)) from the viewpoint of improving the intermolecular interaction.
  • the organic polymer of the present invention is a DA polymer, and has high orientation (or crystallinity) due to intermolecular interaction, so that the contradictory property of solubility tends to decrease. Therefore, from the viewpoint of achieving a good balance between high orientation and high solubility, the organic polymer is selected from linear or branched long-chain alkyl groups, and linear or branched long-chain alkoxy groups. It preferably contains a unit having at least one substituent.
  • the term “long chain” means that the number of carbon atoms forming a substituent is, for example, 4 or more (eg, 6 to 50), preferably 8 or more ( For example, 10 to 46), more preferably about 12 or more (eg, 16 to 40), particularly about 18 or more (eg, 22 to 32).
  • Such a substituent may be substituted on at least one (particularly, any one) unit of the D unit and the A unit, and usually, the D unit (particularly, the first donor unit (D1) ) Has the substituent, and the A unit often does not have the substituent. Both the D unit and the A unit may have the substituent, but the orientation (or crystallinity) may be reduced due to steric hindrance between adjacent substituents.
  • the organic polymer of the present invention is usually synthesized (or polymerized) by subjecting a compound containing a D unit and / or an A unit to a conventional coupling reaction to connect the units (or to form a bond between the units). )it can. Therefore, the organic polymer is a compound having both a D unit and an A unit (eg, a (D)-(A) type dimer, (A)-(D)-(A) type, (D)-( A)-(D) multimers or oligomers such as trimers) may be synthesized through a homocoupling reaction.
  • a compound having a D unit and a compound having an A unit are usually used. In many cases, the compound is synthesized by performing a cross-coupling reaction with a compound having the compound.
  • the compound having a D unit and / or an A unit may be a monomer (or a monomer) having a D unit or an A unit, or may be a multimer (or an oligomer) of a dimer or more.
  • the oligomer may include a single unit or a plurality of units selected from D units and A units. When a plurality (for example, three or more) units are included, the arrangement or order is not particularly limited.
  • the compound having a D unit and / or an A unit has a reactive group that can be coupled depending on the type of the coupling reaction.
  • the reactive group may be bonded or substituted at a position (usually two bonding positions) connecting the compound (or unit).
  • the compound having a D unit and / or an A unit may have both reactive groups out of a pair of reactive groups that can be coupled. However, from the viewpoint of productivity or procureability, the compound is usually used.
  • a compound having a D unit has one reactive group (a first reactive group), and the other reactive group (a second reactive group) that can be coupled to the reactive group is an A unit In many cases.
  • typical methods for producing the organic polymer of the present invention include, for example, a compound having a D unit represented by the following formula (2D) and a compound having an A unit represented by the following formula (2A). And a method of synthesizing an organic polymer represented by the formula (1) by a cross-coupling reaction.
  • X 1 each independently represents a first reactive group
  • X 2 each independently represents a second reactive group capable of being coupled to the first reactive group
  • D (A), p, q and r are the same as described above).
  • the coupling reaction is not particularly limited, and a conventional coupling reaction, for example, a coupling reaction using a palladium catalyst (for example, a palladium (0) catalyst) (for example, Negishi coupling reaction, Hiyama coupling reaction, Suzuki- Miyaura coupling reaction (Suzuki coupling reaction), Migita-Kosugi-Stille coupling reaction (Stille coupling reaction) and the like; coupling reaction using a nickel catalyst (for example, nickel (0) catalyst) (for example, Kumada-Tamao-Corriu coupling reaction and the like); Coupling reaction using an iron catalyst (eg, iron (III) catalyst) (eg, Kochi-Furstner coupling reaction and the like); Copper catalyst (eg.
  • a palladium catalyst for example, a palladium (0) catalyst
  • Negishi coupling reaction Hiyama coupling reaction, Suzuki- Miyaura coupling reaction (Suzuki coupling reaction), Migita-Kosugi-St
  • Copper (I) catalyst, etc. eg, Ullmann reaction, etc.
  • Coupling reactions without using a transition metal catalyst e.g., coupling reaction using an organic catalyst, a coupling reaction using a one-electron catalyst, such as a coupling reaction using a radical species, and the like.
  • a coupling reaction using a palladium (0) catalyst or a nickel (0) catalyst preferably a Suzuki-Miyaura coupling reaction, a Migita-Kosugi-Stile
  • a coupling reaction using a palladium (0) catalyst such as a coupling reaction (particularly a Suzuki-Miyaura coupling reaction) is preferred.
  • a nickel catalyst may be used instead of the palladium catalyst.
  • the first and second reactive groups X 1 and X 2 can be appropriately selected according to the coupling reaction.
  • one of the reactive groups includes, for example, a halogen atom or a fluorinated alkanesulfonyloxy group.
  • the halogen atom include an iodine atom, a bromine atom and a chlorine atom (preferably an iodine atom and a bromine atom).
  • fluorinated alkanesulfonyloxy group examples include a fluorinated C 1-4 alkanesulfonyloxy group such as a trifluoromethanesulfonyloxy group (group [—OTf]).
  • One of these reactive groups (for example, the first reactive group X 1 ) may be used alone or in combination of two or more.
  • a halogen atom for example, an iodine atom or a bromine atom
  • a bromine atom is generally used.
  • the other reactive group capable of coupling with the one reactive group (eg, the first reactive group X 1 ) includes , Boron-containing groups.
  • the boron-containing group include a boronic acid group or a dihydroxyboryl group (group [—B (OH) 2 ]); a boronic ester group [eg, a dialkoxyboryl group (eg, a dimethoxyboryl group, a diisopropoxyboryl group) , A diboroxyboryl group such as a diC 1-4 alkoxyboryl group, a cyclic boronic ester group (eg, a pinacolatoboryl group (group [—Bpin]), a 1,3,2-dioxaborinan-2-yl group, , 5-dimethyl-1,3,2-dioxaborinan-2-yl group) and the like].
  • These other reactive groups may be used alone or in combination of two or more.
  • a group [—B (OH) 2 ] a group [—Bpin], and the like are generally used.
  • one reactive group (for example, the first reactive group X 1 ) is exemplified as one reactive group in the Suzuki-Miyaura coupling reaction, for example. It may be the same as the halogen atom or the fluorinated alkanesulfonyloxy group including the preferred embodiment.
  • One of these reactive groups can be used alone or in combination of two or more.
  • the other reactive group capable of coupling with the one reactive group is a trialkylstannyl group (eg, And a tri-C 1-6 alkylstannyl group such as a trimethylstannyl group and a tri-n-butylstannyl group, and preferably a tri-C 1-4 alkylstannyl group such as a tri-n-butylstannyl group).
  • a trialkylstannyl group eg, And a tri-C 1-6 alkylstannyl group such as a trimethylstannyl group and a tri-n-butylstannyl group, and preferably a tri-C 1-4 alkylstannyl group such as a tri-n-butylstannyl group.
  • These other reactive groups can be used alone or in combination of two or more.
  • the first and second reactive groups X 1 and X 2 may be either a typical reactive groups described above.
  • the first reactive group X 1 may be a halogen atom or a fluorinated alkane sulfonyloxy group
  • the second reactive group X 2 may be a boron-containing group
  • reactive group X 1 is a boron-containing group
  • the second reactive group X 2 may be a halogen atom or a fluorinated alkane sulfonyloxy group.
  • the compound having a D unit represented by the formula (2D) for example, a compound in which q is 1 and (D) is formed by the first donor unit (D1), that is, a compound represented by the following formula (2D) -I) and the like.
  • the compound having a D unit represented by the formula (2D) can be used alone or in combination of two or more.
  • the compound having an A unit represented by the formula (2A) for example, a compound in which r is 1 and (A) is formed of the first acceptor unit (A1), that is, a compound represented by the following formula (2A) And a compound having the first acceptor unit (A1) such as a compound represented by -III-1).
  • the compound having the A unit represented by the formula (2A) can be used alone or in combination of two or more.
  • the reaction is carried out in the presence of a palladium catalyst, a nickel catalyst (eg, Ni (dppf) or the like), usually in the presence of a palladium catalyst.
  • a palladium catalyst eg, Ni (dppf) or the like
  • the palladium catalyst examples include a conventional coupling catalyst, for example, a palladium (0) catalyst ⁇ eg, tetrakis (triphenylphosphine) palladium (0) [Pd (PPh 3 ) 4 ], bis (tri-t-butylphosphine) palladium (0) palladium (0) -phosphine complex such as [Pd (P (t-Bu) 3 ) 2 ]; palladium (II) catalyst ⁇ for example, bis (triphenylphosphine) palladium (II) dichloride [PdCl 2 (PPh 3 ) 2 ], bis (tri-o-tolylphosphine) palladium (II) dichloride [PdCl 2 (P (o-tolyl) 3 ) 2 ], [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride [PdCl 2 (dppf)], [1,2-
  • the reaction is started by being reduced to a zero-valent complex by a reducing compound (for example, a phosphine, an amine, an organometallic reagent, and the like described later) in the reaction system.
  • a reducing compound for example, a phosphine, an amine, an organometallic reagent, and the like described later
  • catalysts can be used alone or in combination of two or more.
  • a palladium (0) -phosphine complex such as Pd (PPh 3 ) 4 is generally used.
  • the ratio of the catalyst is, for example, 0.01 to 0.1 mol (for example, 0.02 to 0.08 mol) in terms of metal per 1 mol of the compound having the D unit represented by the formula (2D). ).
  • the palladium catalyst may be prepared by adding a palladium catalyst precursor, a ligand and a reaction system.
  • the palladium catalyst precursor include a palladium (0) catalyst precursor ⁇ eg, tris (dibenzylideneacetone) dipalladium (0) chloroform complex [Pd 2 (dba) 3 .CHCl 3 ], bis (dibenzylideneacetone) Palladium (0) -dba complex such as palladium (0) [Pd (dba) 2 ]; palladium (II) catalyst precursor ⁇ eg, palladium (II) acetate [Pd (OAc)], palladium (II) chloride [PdCl 2 ], bis (acetonitrile) palladium (II) dichloride [PdCl 2 (CH 3 CN) 2 ], bis (benzonitrile) palladium (II) dichloride [PdCl 2 (PhCN) 2 ], allyl palladium
  • the ligand examples include phosphines (eg, triarylphosphines such as triphenylphosphine and tolylphosphine, trialkylphosphines such as tri-t-butylphosphine, and tricycloalkylphosphines such as tricyclohexylphosphine); Nitrogen-containing heterocyclic carbene (eg, imidazole-based carbene such as 1,3-diisopropylimidazolium tetrafluoroborate, 1,3-di-t-butylimidazole-2-ylidene) and the like. These ligands can be used alone or in combination of two or more. Usually, phosphines such as triphenylphosphine are widely used.
  • the ratio of the palladium catalyst precursor and the ligand may be about the same as the molar ratio (or equivalent ratio) in the target palladium catalyst.
  • the Suzuki-Miyaura coupling reaction may be usually performed in the presence of a base.
  • a base usually, an inorganic base, for example, a metal hydroxide (eg, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, an alkaline earth metal hydroxide such as barium hydroxide, Thallium (I) hydroxide, etc.), metal carbonates or bicarbonates (eg, alkali metal carbonates or bicarbonates such as sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, thallium (I) carbonate, etc.), Metal phosphates (eg, alkali metal phosphates such as tripotassium phosphate), metal fluorides (eg, alkali metal fluorides such as potassium fluoride and cesium fluoride), metal alkoxides (eg, sodium methoxy) Alkali metal alkoxides such as sodium ethoxide, etc.), metal organic
  • bases can be used alone or in combination of two or more.
  • metal phosphates such as tripotassium phosphate are widely used.
  • the ratio of the base may be, for example, about 0.1 to 50 mol (eg, 1 to 25 mol) based on 1 mol of the compound having the D unit represented by the formula (2D).
  • the coupling reaction may be performed in the absence or presence of a solvent inert to the reaction.
  • the solvent include hydrocarbons (eg, aliphatic hydrocarbons (hexane, dodecane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), alcohols (Such as methanol and ethanol), ethers (such as cyclic ethers such as dioxane and tetrahydrofuran, and chain ethers such as diethyl ether and diisopropyl ether), ketones (such as acetone and methyl ethyl ketone), esters (such as ethyl acetate), and nitrile (Such as acetonitrile and benzonitrile), amides (such as N, N-dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone), sulfoxides (
  • solvents may be used alone or as a mixed solvent.
  • a mixed solvent of water and hydrocarbons for example, water and aromatic hydrocarbons
  • a mixed solvent of water and ethers water and THF, etc.
  • the coupling reaction may be performed in the presence or absence of a phase transfer catalyst.
  • phase transfer catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide and trioctylmethylammonium chloride.
  • Aliquat (registered trademark) 336 manufactured by Sigma @ Aldrich) can be used.
  • phase transfer catalysts can be used alone or in combination of two or more. Usually, trioctylmethylammonium chloride and the like are widely used.
  • the ratio of the phase transfer catalyst is, for example, about 0.01 to 3 mol (for example, 0.1 to 1 mol) with respect to 1 mol of the compound having the D unit represented by the formula (2D). Good.
  • the coupling reaction may be performed in an atmosphere of an inert gas (for example, nitrogen gas; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about 50 to 200 ° C, preferably about 70 to 150 ° C.
  • the reaction time is not particularly limited, and may be, for example, about 1 minute to 5 days, preferably about 30 minutes to 3 days.
  • the coupling reaction is usually performed under heating, and may be performed under microwave irradiation.
  • the reaction temperature may be the same as the above range.
  • the irradiation time (or reaction time) may be, for example, about 10 minutes to 3 hours (eg, 20 minutes to 1 hour).
  • the Suzuki-Miyaura coupling reaction is performed under microwave irradiation, the reaction time is significantly shortened and the yield is increased with a high yield as compared with the case where the reaction is performed without microwave irradiation.
  • Organic polymers can be prepared.
  • the reaction yield is, for example, 50% or more (for example, 55 to 100%), preferably 60% or more (for example, 65 to 99%), and more preferably 70% or more (for example, 85 to 98.5%). Degree).
  • an aromatic hydrocarbon such as toluene
  • the yield may be more easily improved in some cases.
  • the reaction mixture is purified by a conventional separation and purification method, such as washing, extraction, concentration, decantation, reprecipitation, chromatography, a method combining these, and the organic polymer is separated and purified. You may. If necessary, the organic polymer may be fractionated into one or a plurality of components having a predetermined molecular weight by operations such as chromatography and extraction.
  • the compound having a D unit represented by the formula (2D) can be synthesized by a conventional method, for example, a method according to Patent Document 1 or Example 10 of WO 2010/024388. Specifically, for example, a compound represented by the following formula (2D-I-3) may be prepared by the following method.
  • R b represents an alkyl group
  • X 3 represents a halogen atom
  • ring A, ring B, R 1 to R 4 , a 1 to a 4 and X 1 are the same as those described above including preferred embodiments
  • the compound represented by the formula (5-I-3) is prepared by lithiating a predetermined portion of the ring A and the ring B of the compound represented by the formula (3-I-3) with a lithiating agent (4a).
  • Lithium is silylated with a silylating agent or a protecting agent (R b 3 SiCl: R b represents an alkyl group) (4b), and a predetermined site is protected with a silyl group (—SiR b 3 ).
  • n-butyllithium (n-BuLi) is used as a lithiating agent
  • triisopropylsilyl chloride (TIPSCl) is used as a silylating agent
  • trialkylsilyl is A group (—SiR b 3 ) has been introduced.
  • Examples of the lithiation agent (4a) include conventional lithiation agents such as alkyllithium (eg, C 1-6 alkyllithium such as methyllithium, n-butyllithium, s-butyllithium and t-butyllithium); Aryl lithium (phenyllithium, etc.), lithium amides (lithium diisopropylamide (LDA), lithium-2,2,6,6-tetramethylpiperidine (LiTMP), lithium-bis (trimethylsilyl) amide (LHMDS), etc.) No.
  • the lithiating agents may be used alone or in combination of two or more.
  • the amount of the lithiating agent used may be about 1 to 5 equivalents (for example, 1.5 to 3 equivalents) to the compound represented by the formula (3-I-3).
  • the perithiation reaction may be performed in the presence of a solvent inert to the reaction.
  • a solvent inert for example, ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran (THF) and dioxane), and aliphatic or alicyclic hydrocarbons (such as cyclohexane) may be used.
  • THF tetrahydrofuran
  • cyclohexane aliphatic or alicyclic hydrocarbons
  • the reaction is carried out in an atmosphere of an inert gas (nitrogen gas; rare gas such as helium, argon, etc.) at a temperature of about ⁇ 100 ° C. to 30 ° C. (normally ⁇ 80 ° C.
  • reaction solution may be purified by a conventional separation and purification means, but the reaction solution containing the obtained lithiated product may be subjected to the next silylation reaction without purification.
  • silylating agent (4b) (or protecting agent) include tri-linear or branched C such as trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride (TIPSCl), tributylsilyl chloride, and triisobutylsilyl chloride. Examples thereof include 1-6 alkylsilyl halide. These silylating agents can be used alone or in combination of two or more. The amount of the silylating agent used may be about 1 to 5 equivalents (for example, 1.5 to 3 equivalents) to the compound represented by the formula (3-I-3).
  • the silylation reaction is carried out in a solvent similar to the above lithiation reaction, in an inert atmosphere, at a temperature of about -100 ° C to 40 ° C (normally -80 ° C to 30 ° C), for a reaction time of 1 to 48 hours (normally 12 hours). (About 24 hours).
  • the product may be purified by a conventional separation and purification means (column chromatography, filtration, recrystallization, etc.).
  • a conventional boration method using a catalyst such as an iridium catalyst, a rhenium catalyst, and a rhodium catalyst, for example, an iridium catalyst and a bipyridyl ligand
  • a catalyst such as an iridium catalyst, a rhenium catalyst, and a rhodium catalyst
  • a ligand such as a diimine ligand or a phosphine ligand (such as triphenylphosphine) is exemplified.
  • These catalysts and ligands can be used alone or in combination of two or more.
  • the amount of the catalyst such as an iridium catalyst may be about 0.1 to 10 mol% (for example, 2 to 8 mol%) based on the compound represented by the formula (5-I-3).
  • the amount of a ligand such as a bipyridyl ligand may be about 1.5 to 5 times the molar amount of the catalyst.
  • boronating agent or the boron compound (6) a compound capable of forming a boronic acid ester, for example, (BPin) 2 , or a conventional compound, for example, diboronic acid, pinacol borane, or the like can be used.
  • the boron compound (6) can be used alone or in combination of two or more.
  • the amount of the boron compound (6) used may be about 1.1 to 5 equivalents (eg, 1.5 to 3 equivalents) to the compound represented by the formula (5-I-3).
  • the boration reaction is carried out in an inert solvent such as the aforementioned organic solvent or alicyclic hydrocarbons (eg, cyclohexane) under an inert atmosphere at a temperature of about 30 to 120 ° C. (eg, 50 to 100 ° C.) for a reaction time of It may be performed for about 1 to 36 hours (usually, 18 to 24 hours).
  • an inert solvent such as the aforementioned organic solvent or alicyclic hydrocarbons (eg, cyclohexane)
  • a reaction time of It may be performed for about 1 to 36 hours (usually, 18 to 24 hours).
  • the product may be purified by conventional separation and purification means (filtration, washing, etc.).
  • examples of the halogen atom represented by X 3 include a chlorine, bromine, iodine atom and the like, and usually, it is often bromine.
  • Two halogen atoms X 3 may be different from each other, but typically are the same.
  • halogenating agent (8) examples include copper (II) halides such as copper (II) chloride, copper (II) bromide, and copper (II) iodide [Cu (X 3 ) 2 (II)]. Can be exemplified.
  • the amount of the halogenating agent (8) such as copper halide to be used may be about 2 to 10 equivalents (for example, 5 to 8 equivalents) relative to the compound represented by the formula (7-I-3). .
  • a solvent inert to the reaction for example, a mixed solvent of water and a water-soluble solvent (cyclic ethers, alcohols such as methanol, amides such as N-methyl-2-pyrrolidone (NMP), etc.) And so on.
  • a mixed solvent of alcohols, amides and water for example, a mixed solvent of methanol, NMP and water, etc.
  • the reaction may be performed under an inert atmosphere at a temperature of about 30 to 120 ° C. (eg, 50 to 100 ° C.) for a reaction time of about 5 to 48 hours (generally, 18 to 24 hours).
  • the product may be purified by conventional separation and purification means (filtration, extraction, washing, etc.).
  • the alkylating agent (10) for example, Grignard reagents, alkyl zinc halides, dialkyl zinc, lithium zincate or magnesium zincate [M + R 1 3 Zn - and / or M + R 4 3 Zn - ( M is lithium or magnesium And R 1 and R 4 represent an alkyl group.)], And a conventional alkylating agent such as an alkylating metal can be used.
  • These alkylating agents (10) can be used alone or in combination of two or more.
  • a zinc reagent lithium zincate or magnesium zincate
  • the zinc reagent includes, for example, an alkyl magnesium halide (10A), a zinc compound (10B) (eg, a zinc halide such as zinc chloride), and a lithium compound (10C) (a lithium halide such as lithium chloride). May be formed.
  • an alkyl magnesium halide (10A) an alkyl magnesium halide (chloride, bromide, iodide) corresponding to R 1 and R 4 can be used.
  • the amount of the alkyl magnesium halide (10A) to be used may be, for example, about 1.5 to 10 equivalents (for example, 2 to 5 equivalents) to the compound represented by the formula (9-I-3).
  • the amount of the zinc compound (10B) and the amount of the lithium compound (10C) used may be, for example, about 0.8 to 1.2 times the molar amount of the alkyl magnesium halide (10A).
  • the amount of the alkylating agent or zinc reagent (10) to be used may be about 1.5 to 5 equivalents (for example, 2 to 3 equivalents) relative to the compound represented by the formula (9-I-3). .
  • the reaction for preparing the zinc reagent is carried out, for example, in a solvent inert to the reaction (ethers such as diethyl ether and THF) under an inert atmosphere at a reaction temperature of 10 to 70 ° C (for example, room temperature of about 20 to 25 ° C). ), The reaction may be performed for about 10 minutes to 12 hours.
  • the obtained reaction solution may be purified as necessary, or may be subjected to a coupling reaction without purification.
  • the palladium catalyst in addition to the above-mentioned catalyst, the palladium catalyst exemplified in the Suzuki-Miyaura coupling reaction can be exemplified.
  • the catalysts and ligands can be used alone or in combination of two or more.
  • the amount of the palladium catalyst used may be, for example, about 1 to 50 mol% (for example, 5 to 25 mol%) based on the compound represented by the formula (9-I-3).
  • the Negishi coupling reaction is carried out in the presence of a solvent inert to the reaction (eg, a cyclic ether such as THF) under an inert atmosphere at a reaction temperature of about 30 to 120 ° C. (eg, 50 to 100 ° C.).
  • a solvent inert to the reaction eg, a cyclic ether such as THF
  • the reaction can be performed for about 1 to 48 hours (usually 12 to 24 hours).
  • the product may be purified by a conventional separation and purification means (extraction, washing, column chromatography, etc.).
  • the compound represented by the formula (13-I-3) in which X 1 in the formula (2DI) corresponds to a hydrogen atom is represented by the formula (11-I-3) It can be prepared by subjecting the compound represented by -3) to a deprotection reaction.
  • conventional deprotecting agents (12) such as acids and bases, for example, alkali metal carbonates such as potassium carbonate, fluoride ions such as tetrabutylammonium fluoride (TBAF) and the like can be used.
  • the deprotecting agent (12) can be used alone or in combination of two or more. Usually, TBAF or the like is widely used.
  • the use amount of the deprotecting agent (12) may be about 1 to 10 equivalents (for example, 2 to 5 equivalents) to the compound represented by the formula (11-I-3).
  • the deprotection reaction is carried out in the presence of a solvent inert to the reaction (eg, a cyclic ether such as THF) in an inert atmosphere at a reaction temperature of about ⁇ 20 ° C. to 50 ° C. (eg, ⁇ 10 ° C. to 30 ° C.). And the reaction time is about 10 minutes to 12 hours (usually 30 minutes to 3 hours).
  • a solvent inert to the reaction eg, a cyclic ether such as THF
  • THF cyclic ether
  • the reaction time is about 10 minutes to 12 hours (usually 30 minutes to 3 hours).
  • the reaction product may be purified by conventional separation and purification means (filtration, washing, column chromatography, etc.).
  • the same lithiation agent as the lithiation agent (4a) can be used, and it can be used alone or in combination of two or more.
  • the amount of the lithiating agent used may be about 1.5 to 10 equivalents (for example, 2 to 5 equivalents) to the compound represented by the formula (13-I-3).
  • the lithiation reaction may be performed in the presence of an inert solvent (such as a cyclic ether such as THF) as in the lithiation reaction.
  • the reaction may be carried out in an inert gas atmosphere at a temperature of about -100 to 30 ° C (normally -80 to -10 ° C) for a reaction time of about 1 minute to 12 hours (normally 1 to 3 hours).
  • the reaction solution may be purified by a conventional separation and purification means, but the reaction solution containing the obtained lithiated product may be subjected to the next halogenation reaction without purification.
  • halogenating agent (14b) a conventional halogen compound, for example, a halogenated alkane such as 1,2-dibromo-1,1,2,2-tetrachloroethane or a simple halogen such as chlorine, bromine or iodine is used. it can. Usually, halogenated alkanes and the like are widely used.
  • the amount of the halogenating agent (14b) used is about the same as the amount of the lithiating agent (14a) used.
  • the halogenation reaction is carried out in an inert atmosphere in the presence of a solvent inert to the reaction (eg, a cyclic ether such as THF) at a reaction temperature of about ⁇ 50 ° C. to 50 ° C. (eg, ⁇ 30 ° C. to 30 ° C.). The reaction may be performed for about 10 minutes to 48 hours (usually, 12 to 24 hours).
  • a solvent inert to the reaction eg, a cycl
  • a predetermined compound is purified by a conventional separation and purification method, for example, filtration, concentration, crystallization or precipitation, recrystallization, extraction, washing, chromatography, a method combining these, and the like.
  • the compound may be separated and purified and used for the subsequent reaction, or a predetermined compound may be used for the subsequent reaction without separation and purification from the reaction mixture.
  • the molecular weight of the organic polymer of the present invention is not particularly limited.
  • the number average molecular weight Mn is 500 to 5,000,000 (for example, 1000 to 1,000,000) in terms of polystyrene, It may be preferably about 3,000 to 500,000 (eg, 5,000 to 100,000), more preferably about 8,000 to 50,000 (eg, 10,000 to 25,000), and has a weight average molecular weight Mw of 1,000 to 100,000,000 (eg, 3,000 to 1,000,000).
  • the molecular weight distribution (Mw / Mn) is, for example, 1 to 20 (for example, 1.1 to 10), preferably 1.2 to 8 (for example, 1.3 to 5), and more preferably 1.4 to 3 (for example). For example, it may be about 1.5 to 2), and usually about 1.5 to 15 (for example, 6 to 8).
  • the degree of polymerization DPn is, for example, about 3 to 100 (eg, 5 to 50), preferably about 7 to 30 (eg, 10 to 25), and more preferably about 11 to 23 (eg, 17 to 21). Is also good.
  • the organic polymer of the present invention has high heat resistance, and the 5% mass defect temperature T 95 can be measured by TG-DTA (thermogravimetric / differential thermal analyzer), for example, 200 to 600 ° C.
  • the temperature may be about 300 to 500 ° C.), preferably about 350 to 450 ° C.
  • the organic polymer (semiconductor polymer or ⁇ -conjugated polymer) of the present invention has a first donor unit (D1), which is expected to have low orientation (or crystallinity) [a plurality of adjacent benzene rings have a zigzag shape. To a zigzag-like unit which is ortho-condensed to), surprisingly, it exhibits extremely excellent orientation (or crystallinity). Therefore, even if the film is formed by a simple method such as spin coating, High orientation can be maintained. Therefore, high mobility can be realized, and it can be effectively used as an organic semiconductor.
  • D1 first donor unit
  • the distance (plane distance) d ⁇ between the ⁇ stacks of the organic polymer is, for example, 3.3 to 3.7 ° (eg, 3.35 to 3.6 °), preferably 3 0.4 to 3.55 ° (for example, about 3.4 to 3.5 °.
  • D ⁇ of a general organic semiconductor polymer is about 3.4 to 3.75 °.
  • the distance (inter-plane distance) d ⁇ is too large, the mobility (carrier mobility) may be reduced, and the distance between the lamella structures (inter-plane distance) d 1 is determined by the side chain of the organic polymer or It can be adjusted according to the substituent [eg, R 1 to R 2 + n (especially, a long-chain alkyl group, etc.) and the like], for example, 10 to 50 ° (eg, 15 to 40 °), preferably 20 to 35 ° (eg, 25 °). The distance between the surfaces may be, for example, about 30 °). It can be measured by thin film X-ray analysis as described in the Examples below.
  • the present invention also includes a composition containing an organic polymer and an organic solvent.
  • a composition is useful for forming a thin film of an organic semiconductor, and a thin film (organic semiconductor thin film) can be formed by a simple method such as printing or coating (coating).
  • the organic polymer of the present invention has excellent semiconductor properties and film-forming properties as described above, and can be effectively used as an organic semiconductor.
  • the organic semiconductor may include at least the organic polymer, and may include a conventional semiconductor material, an additive, and the like, as needed, in a range that does not impair the carrier transportability.
  • Such semiconductor materials include, for example, acenes (eg, naphthacene, chrysene, pyrene, pentacene, picene, perylene, hexacene, heptacene, dibenzopentacene, coronene, tetrabenzopentacene, ovalene, etc.); phthalocyanines (eg, phthalocyanine (Eg, copper phthalocyanine), naphthalocyanine, subphthalocyanine, etc .; carbazoles [eg, 1,3,5-tris [2,7- (N, N- (p-methoxyphenyl) amino) -9H-carbazole-9] -Yl] benzene (SGT405) and the like]; thiophenes [eg, 2,5-bis [4- (N, N-bis (p-methoxyphenyl) amino) phenyl] -3,4-ethylenedioxythiophene (H
  • additives examples include a leveling agent, an adhesion improver (such as a silane coupling agent), and a dopant. These additives can be used alone or in combination of two or more.
  • the ratio of the organic polymer (DA type polymer) is, for example, 10% by mass or more (eg, 30 to 100% by mass), preferably 50% by mass, based on the whole organic semiconductor. % (Eg, 70 to 99.9% by mass), more preferably about 80% by mass (eg, 90 to 99% by mass), and substantially 100% by mass (eg, the organic polymer (D -A type polymer) only).
  • the organic semiconductor (organic semiconductor thin film or organic semiconductor layer) of the present invention may be formed by a dry process such as a vacuum deposition method or a sputtering method, but the organic polymer (DA type polymer) has a high solubility. May be formed by a wet process (such as coating).
  • the wet process includes a film forming step of applying a composition (or a solution) containing the organic polymer and a solvent to at least one surface of a substrate (or a substrate) and removing the solvent. .
  • the substrate is not particularly limited, and may be, for example, a glass plate, a silicon wafer, or a plastic film (for example, a transparent resin film such as a polyethylene terephthalate film). If necessary, these substrates may have one or more functional layers (for example, a conductive layer such as ITO, an insulating layer such as SiO 2 ), a self-assembly such as ⁇ -phenethyltrimethoxysilane ( ⁇ -PTS) on the surface. Monolayer (SAM) or the like may be formed.
  • a conductive layer such as ITO
  • an insulating layer such as SiO 2
  • ⁇ -PTS ⁇ -phenethyltrimethoxysilane
  • SAM Monolayer
  • the composition may be prepared by a conventional method, for example, by mixing an organic polymer and a solvent to dissolve the organic polymer and, if necessary, filtering.
  • the solvent include aromatic hydrocarbons (eg, benzene, toluene, xylene, anisole, etc.); halogenated hydrocarbons (eg, halo C 1-6 alkanes such as dichloromethane, chloroform, 1,2-dichloroethane, etc.) Chlorobenzene, dichlorobenzene); alcohols (eg, C 1-6 alkane monool such as methanol, ethanol, 2-propanol, n-butanol, t-butanol; C 2-4 alkanediol such as ethylene glycol); ethers (Chain ethers such as diethyl ether and diisopropyl ether, cyclic ethers such as tetrahydrofuran and dioxane); glycol ethers [
  • ketones acetone, chain ketones such as methyl ethyl ketone, cyclic ketones such as cyclohexanone, esters (ethyl acetate, etc.
  • lactate esters such as methyl lactate, etc.
  • carbonates chain carbonates such as dimethyl carbonate, cyclic carbonates such as ethylene carbonate, propylene carbonate, etc.
  • nitriles acetonitrile, propionitrile, benzonitrile, etc.
  • Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone
  • sulfoxides such as dimethyl sulfoxide
  • mixed solvents thereof such as aromatic hydrocarbons, halogenated hydrocarbons (eg, o-dichlorobenzene, etc.) are widely used.
  • the concentration (solid content) of the organic polymer can be selected according to the coating method and the like, and is, for example, 0.001 to 20% by mass (eg, 0.01 to 10% by mass). Preferably, it may be about 0.1 to 5% by mass (eg, 0.5 to 3% by mass), particularly about 0.6 to 2% by mass (eg, 0.7 to 1.3% by mass).
  • the coating method is not particularly limited, and a conventional coating method, for example, an air knife coating method, a roll coating method, a gravure coating method, a blade coating method, a bar coating method, a die coating method, a dip coating method, a spray coating method, a spin coating method , A casting method, an edge casting method, a drop casting method, a screen printing method, an ink jet printing method, a compression orientation method, and the like.
  • a spin coating method, an edge casting method, a drop casting method, an ink jet printing method and the like are generally used, and a spin coating method and the like are preferable from the viewpoint of easy film formation (or productivity).
  • An organic semiconductor (layer) can be formed by removing the solvent by a conventional drying method, for example, natural drying, drying by heat treatment, or the like.
  • the temperature in the heat treatment may be, for example, about 30 to 100 ° C., preferably about 40 to 80 ° C.
  • the obtained coating film may be subjected to an annealing treatment as needed.
  • the annealing temperature can be selected, for example, from the range of about 50 to 400 ° C. (for example, 80 to 380 ° C.), for example, 100 to 360 ° C. (for example, 150 to 350 ° C.), preferably 200 to 340 ° C. (for example, (250-330 ° C.), more preferably about 280-320 ° C.
  • the annealing time may be, for example, about 10 minutes to 12 hours, preferably about 30 minutes to 8 hours, and more preferably about 1 to 6 hours (eg, about 2 to 4 hours).
  • the annealing treatment may be performed in an air atmosphere, may be performed in an inert gas atmosphere such as a nitrogen gas or a rare gas (such as helium or argon), or may be performed in an inert gas (particularly argon) atmosphere. Is preferred.
  • the thickness of the organic semiconductor (layer) thus obtained may be, for example, about 1 to 5000 nm, preferably about 30 to 1000 nm, and more preferably about 50 to 500 nm, depending on the use.
  • the organic semiconductor of the present invention may be an n-type semiconductor, a p-type semiconductor, or an intrinsic semiconductor. Since the organic semiconductor of the present invention has a high mobility (carrier mobility or electric mobility) of electrons and / or holes (holes), semiconductors such as electronic devices such as switching elements, rectifiers (diodes), and transistors are used. It can be used as a material for an element, a photoelectric conversion device, or a material for a photoelectric conversion element (such as a solar cell element and an organic electroluminescence (EL) element).
  • EL organic electroluminescence
  • the organic polymer may have face-on orientation (or in-plane orientation) with respect to the substrate, but usually has edge-on orientation (or out-of-plane orientation). Orientation). Therefore, it can be effectively used as an organic thin film transistor.
  • Such an organic thin film transistor includes a gate electrode layer, a gate insulating layer, a source / drain electrode layer, and an organic semiconductor layer. According to the stacked structure of these layers, the organic thin film transistor can be classified into a top gate type and a bottom gate type (top contact type, bottom contact type). For example, by forming an organic semiconductor film on a gate electrode (such as a p-type silicon wafer on which an oxide film is formed) and forming source / drain electrodes (gold electrodes) on the organic semiconductor film, a top-contact type electric field is formed. An effect transistor can be manufactured. Further, a carrier injection layer (dopant layer) may be formed between the source / drain electrode layer and the organic semiconductor layer.
  • a carrier injection layer dopant layer
  • Such carrier injection layers include, for example, TCNQs such as tetracyanoquinonedimethane (TCNQ) and 2,3,5,6-tetrafluorotetracyanoquinonedimethane (F 4 TCNQ), and iron (III) chloride.
  • TCNQs such as tetracyanoquinonedimethane (TCNQ) and 2,3,5,6-tetrafluorotetracyanoquinonedimethane (F 4 TCNQ)
  • F 4 TCNQ 2,3,5,6-tetrafluorotetracyanoquinonedimethane
  • iron (III) chloride iron
  • the threshold voltage Vth at a drain voltage Vd of -150 V may be, for example, -100 V or more and less than 0 V (for example, about -70 to -0.01 V), preferably -60. It may be about -0.1V. Note that the mobility and the threshold voltage Vth may be measured by a method described in an embodiment described later.
  • the target compound (3-1) (chryseno) was prepared according to the methods described in Synthesis Examples 1 to 5 of WO2017 / 170245 (Patent Document 1). [2,1-b: 8,7-b '] difuran) was prepared.
  • TIPSCl triisopropylsilyl chloride
  • Diiridium (I) complex [Ir (OMe) (COD)] 2 , 69 mg, 0.11 mmol), 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy, 56 mg, 0.2 mmol) ), 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bis-1,3,2-dioxaboronate [(4) Bpin) 2 ] (1.2 g, 4.6 mmol). The resulting suspension was further stirred at 80 ° C. for 22 hours. The reaction mixture was diluted with methanol, filtered, and washed with methanol to obtain the desired compound (7-1) (1.5 g, 83% yield).
  • Halogenation is performed while stirring a suspension of compound (7-1) (1.4 g, 1.6 mmol) / N-methylpyrrolidone (120 mL) / methanol (40 mL) / water (20 mL) at room temperature under an argon atmosphere. Copper (II) bromide (2.4 g, 10.6 mmol) as agent (8) was added. The resulting dark green suspension was stirred at 80 ° C. for 21 hours. After methanol was added to the reaction mixture at 0 ° C., the mixture was stirred, filtered, and washed with methanol to obtain the target compound (9-1) as a solid (1.1 g, 90% yield).
  • the reaction mixture was reprecipitated in methanol, and the resulting precipitate was subjected to extraction (or washing) of impurities using a Soxhlet extractor in the order of methanol and acetone. Extraction of the washed precipitate with hexane resulted in no residue.
  • the target compound (1-1) was obtained as a reddish brown solid (77 mg, 98% yield) by removing hexane from the obtained hexane solution.
  • the obtained target compound (1-1) was measured by GPC (gel permeation chromatography) in terms of polystyrene, the number average molecular weight Mn was 13477, the weight average molecular weight Mw was 23713, and the molecular weight distribution Mw / Mn was 1.76.
  • the polymerization degree DPn was 11.2.
  • the 5% mass loss temperature T 95 of the obtained target compound (1-1) was measured by TG-DTA (thermogravimetric / differential thermal analyzer), and was 385 ° C.
  • Example 2 (Suzuki coupling polymerization using microwave) Under an argon atmosphere, compound (2D-1) (122 mg, 0.1 mmol), compound (2A-1) (39 mg, 0.1 mmol), tetrakistriphenylphosphine palladium (0) complex (Pd (PPh 3 ) 4 , 5 .8mg, 0.005mmol), Aliquat (registered trademark) 336 (Sigma Aldrich Corporation, 1 drop), tripotassium phosphate aqueous 2M (K 3 PO 4, 1mL , 2.0mmol), THF (1.0mL) was added and mixed, and the mixture was heated and stirred for 40 minutes using a microwave irradiation apparatus (“Initiator +” manufactured by Biotage Japan, Inc., conditions: 130 ° C.).
  • a microwave irradiation apparatus (“Initiator +” manufactured by Biotage Japan, Inc., conditions: 130 ° C.).
  • the obtained reaction mixture was washed and extracted in the same manner as in Example 1 to obtain the desired compound (1-1) (91 mg, yield 76%).
  • the obtained target compound (1-1) was measured by GPC (gel permeation chromatography) in terms of polystyrene, the number average molecular weight Mn was 18625, the weight average molecular weight Mw was 37935, the molecular weight distribution Mw / Mn was 2.0, The polymerization degree DPn was 15.5.
  • Example 3 The desired compound (1-1) was obtained in the same manner as in Example 2 except that toluene (1.6 mL) was used instead of THF (1.0 mL) (114 mg, 94% yield).
  • toluene 1.6 mL
  • THF 1.0 mL
  • the obtained target compound (1-1) was measured by GPC (gel permeation chromatography) in terms of polystyrene, the number average molecular weight Mn was 16,460, the weight average molecular weight Mw was 38358, the molecular weight distribution Mw / Mn was 2.3, The polymerization degree DPn was 13.8.
  • Second fraction (B) described in Example 4 of WO2017 / 170245 Patent Document 1 (compound represented by the following formula, degree of polymerization DPn: 9.9, number average molecular weight Mn: 9175) , Weight average molecular weight Mw: 14662, molecular weight distribution Mw / Mn: 1.6).
  • R 11 represents a 3-octyltridecyl group
  • R 1b represents a 5-octyl-pentadecyl group; the same applies hereinafter).
  • compound (2D-2) 114 mg, 0.1 mmol
  • compound (2A-1) 39 mg, 0.1 mol
  • tetrakistriphenylphosphine palladium (0) complex Pd (PPh 3 ) 4 , 12 mg , 0.01 mmol
  • Aliquat® 336 Sigma Aldrich, 1 drop
  • 2M aqueous potassium carbonate K 2 CO 3 , 1 mL, 2 mmol
  • THF 1.6 mL
  • the obtained reaction mixture was washed and extracted in the same manner as in Example 1 to obtain the desired compound (1-2) (95 mg, 85% yield).
  • the obtained target compound (1-2) was measured in terms of polystyrene by GPC (gel permeation chromatography)
  • the number average molecular weight Mn was 13,267
  • the weight average molecular weight Mw was 51352
  • the z average molecular weight Mz was 638208
  • the molecular weight distribution Mw. / Mn was 3.9 and the degree of polymerization DPn was 11.9.
  • R 1c represents a 4-octyl-tetradecyl group; the same applies hereinafter).
  • compound (2D-3) (112 mg, 0.1 mmol), compound (2A-1) (39 mg, 0.1 mol), tetrakistriphenylphosphine palladium (0) complex (Pd (PPh 3 ) 4 , 12 mg , 0.01 mmol), Aliquat® 336 (Sigma Aldrich, 1 drop), 2M aqueous potassium carbonate (K 2 CO 3 , 1 mL, 2 mmol), THF (1.6 mL), and mix. The mixture was heated and stirred for 40 minutes using a wave irradiation device (“Initiator +” manufactured by Biotage Japan, Inc., conditions: 130 ° C.).
  • a wave irradiation device (“Initiator +” manufactured by Biotage Japan, Inc., conditions: 130 ° C.).
  • the obtained reaction mixture was washed and extracted in the same manner as in Example 1 to obtain the desired compound (1-3) (52 mg, 46 (% yield).
  • the obtained desired compound (1-3) ) was measured by GPC (gel permeation chromatography) in terms of polystyrene.
  • the number average molecular weight Mn was 12995
  • the weight average molecular weight Mw was 84204
  • the z average molecular weight Mz was 386585
  • the molecular weight distribution Mw / Mn was 6.5
  • the degree of polymerization was calculated.
  • DPn was 11.6.
  • Example 6 In the same manner as in Example 5, the target compound (1-3) was obtained (32 mg, 29% yield).
  • the obtained target compound (1-3) was measured by GPC (gel permeation chromatography) in terms of polystyrene, the number average molecular weight Mn was 21,624, the weight average molecular weight Mw was 155918, the z average molecular weight Mz was 1461778, and the molecular weight distribution Mw. / Mn was 7.2 and the degree of polymerization DPn was 19.3.
  • Example preparation A silicon (Si) substrate provided with a silicon dioxide (SiO 2 ) insulating film (thickness: 500 nm) was subjected to ultrasonic cleaning with acetone and 2-propanol for 3 minutes each, and dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes. A self-assembled monolayer (SAM) of decyltriethoxysilane (DTS) was formed on the cleaned substrate surface by a vapor method.
  • SAM self-assembled monolayer
  • DTS decyltriethoxysilane
  • Example 1 Using the compound (1-1) obtained in Example 1, a solution of the compound (1-1) / orthodichlorobenzene (oDCB) at a concentration of 1.0% by mass dissolved at 80 ° C. on the surface of the monomolecular film. was dropped, and the film was formed by a spin coating method (at a rotation speed of 500 rpm and a rotation time of 5 s, and further at a rotation speed of 2,000 rpm and a rotation time of 30 s). Then, under an argon atmosphere, (a) 100 ° C., (b) 150 ° C. After annealing at (c) 200 ° C. or (d) 240 ° C. for 30 minutes, it was dried under vacuum at 100 ° C. for 12 hours to form a coating film.
  • oDCB orthodichlorobenzene
  • Samples using the compound obtained in Comparative Example 1 were prepared by a spin coating method and a compression alignment method capable of improving the molecular orientation compared to the spin coating method.
  • the sample prepared by the spin coating method was prepared in the same manner as the sample of Example 1 except that the compound obtained in Comparative Example 1 was used instead of the compound (1-1) obtained in Example 1. .
  • the annealing was performed at 150 ° C. for 30 minutes.
  • a self-assembled monolayer (SAM) of perfluorodecyltrichlorosilane (F-SAM) is formed on the surface of the substrate subjected to the above-mentioned cleaning treatment by an evaporation method, and the surface of the monomolecular film is formed.
  • SAM self-assembled monolayer
  • F-SAM perfluorodecyltrichlorosilane
  • FIG. 1 spin coating
  • FIG. 2 ((a) spin coating) shows the measurement results of the sample obtained in Comparative Example 1.
  • (b) compression orientation shows the measurement results of the compound (1-1) obtained in Example 1
  • spin coating shows the measurement results of the compound (1-1) obtained in Example 1
  • FIG. 2 shows the measurement results of the sample obtained in Comparative Example 1.
  • (b) compression orientation shows the measurement results of the sample obtained in Comparative Example 1.
  • the edge-on (edge-on) orientation [the planar skeleton of the molecule (main chain plane) is perpendicular to the substrate]. Orientation]. More specifically, peaks (100), (200), (300), (400), and (500) are observed on the qz axis indicating the property in the direction perpendicular to the substrate, and the distance between the planes (lamella distance) d l between the structures are 27.5 ⁇ at any annealing temperature is considered to correspond to the alkyl group represented by R 1a.
  • a peak of (010) is observed on the qxy axis indicating the property of the direction parallel to the substrate (plane direction of the substrate), and the inter-plane distance (distance between ⁇ stacks) d ⁇ is 3. 45 ° (annealing temperature: 100 ° C., 200 ° C., 240 ° C.) or 3.47 ° (150 ° C.). Since d ⁇ of a general organic semiconductor polymer is about 3.4 to 3.75 °, the compound (1-1) has a small d ⁇ even when a film is formed by a spin coating method which cannot improve the orientation much. It was found that the compound was extremely excellent in orientation (or crystallinity). Further, it was found that as the annealing temperature increased, each peak appeared more clearly, and the orientation could be further improved.
  • Example 2 A solution of the compound (1-1) / orthodichlorobenzene (oDCB) obtained in Example 1 at a concentration of 2.0% by mass and dissolved at 70 ° C. was dropped on the surface of the monomolecular film, and spin coating was performed. After forming the film at a number of 1000 rpm and a rotation time of 30 s), the film was annealed at 100 ° C. for 30 minutes in an argon atmosphere and dried at 60 ° C. under reduced pressure for 12 hours.
  • oDCB orthodichlorobenzene
  • FIG. 3 shows a schematic diagram of the device.
  • a silicon (Si) substrate provided with a silicon dioxide (SiO 2 ) insulating film (thickness: 500 nm) was subjected to ultrasonic cleaning in the order of acetone and 2-propanol for 3 minutes each, and then dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes.
  • a self-assembled monolayer (SAM) of ⁇ -phenethyltrichlorosilane ( ⁇ -PTS) was formed on the surface of the substrate subjected to the UV ozone treatment by a vapor method.
  • a solution of the compound (1-2) / orthodichlorobenzene (oDCB) obtained in Example 4 at a concentration of 2.0% by mass dissolved at 70 ° C. was dropped on the surface of the monomolecular film, and the solution was spin-coated (rotation). After forming the film at a number of 1000 rpm and a rotation time of 30 s), the film was annealed at 300 ° C. for 30 minutes in an argon atmosphere and dried at 100 ° C. under reduced pressure for 12 hours.
  • FIG. 3 shows a schematic diagram of the device.
  • a device was formed by a drop casting method. Specifically, the compound (1-3) obtained in Example 5 having a concentration of 0.1% by mass dissolved at room temperature (about 25 ° C.) / Ortho-dichlorobenzene was dissolved on the surface of the monomolecular film of the substrate on which the SAM was formed. The (oDCB) solution was added dropwise, and a film was formed at 120 ° C. using a hot plate, and then dried at 40 ° C. under reduced pressure for 12 hours. Thereafter, the device element shown in FIG. 3 was manufactured in the same manner as the element manufactured by the spin coating method.
  • a silicon (Si) substrate provided with a silicon dioxide (SiO 2 ) insulating film (thickness: 500 nm) was subjected to ultrasonic cleaning in the order of acetone and 2-propanol for 3 minutes each, and then dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes.
  • a self-assembled monolayer (SAM) of decyltriethoxysilane (DTS) was formed on the surface of the substrate subjected to the UV ozone treatment by a vapor method.
  • FIG. 3 shows a schematic diagram of the device.
  • a silicon (Si) substrate provided with a silicon dioxide (SiO 2 ) insulating film (thickness: 500 nm) was subjected to ultrasonic cleaning in the order of acetone and 2-propanol for 3 minutes each, and then dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes.
  • a self-assembled monolayer (SAM) of ⁇ -phenethyltrichlorosilane ( ⁇ -PTS) was formed on the surface of the substrate subjected to the UV ozone treatment by a vapor method.
  • FIG. 3 shows a schematic diagram of the device.
  • an organic semiconductor containing the compound can be used in various electronic devices such as a rectifying element (diode), a switching element, or a transistor (organic). It can be effectively used as an organic semiconductor device such as a thin film transistor (for example, a junction transistor (bipolar transistor), a field effect transistor (unipolar transistor), etc.) and a photoelectric conversion element (solar cell element, organic EL element, etc.).
  • a thin film transistor for example, a junction transistor (bipolar transistor), a field effect transistor (unipolar transistor), etc.
  • a photoelectric conversion element solar cell element, organic EL element, etc.

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Abstract

La présente invention concerne : un nouveau polymère organique présentant une mobilité élevée (mobilité électrique ou mobilité des porteurs) ; et un procédé de production de ce polymère organique. Ce polymère organique comporte un motif donneur (D) et un motif accepteur (A) ; et le motif donneur (D) contient au moins un motif donneur (D1) qui est représenté par la formule (I). (Dans la formule, le cycle A et le cycle B représentent indépendamment un cycle hydrocarbure aromatique ou un cycle hétérocyclique aromatique ; n représente un nombre entier de 0 à 6 ; chacun des R1-R2+n représente indépendamment un substituant ; chacun des a1-a2+n représente indépendamment un nombre entier de 0 à 2 ; et le cycle C représente des cycles benzène qui sont séquentiellement ortho-condensés à un cycle benzène adjacent de manière non linéaire conformément au nombre n.)
PCT/JP2019/027991 2018-07-27 2019-07-17 Polymère organique, son procédé de production et son utilisation WO2020022128A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014078729A (ja) * 2008-08-29 2014-05-01 Idemitsu Kosan Co Ltd 有機薄膜トランジスタ用化合物及びそれを用いた有機薄膜トランジスタ
WO2017022758A1 (fr) * 2015-08-04 2017-02-09 富士フイルム株式会社 Transistor à film mince organique et son procédé de fabrication, matériau pour transistor à film mince organique, composition pour transistor à film mince organique, composé et film semi-conducteur organique
WO2017022761A1 (fr) * 2015-08-04 2017-02-09 富士フイルム株式会社 Transistor à couches minces organiques et son procédé de fabrication, matériau pour transistor à couches minces organiques, composition pour transistor à couches minces organiques, composé, et film semi-conducteur organique
WO2017170245A1 (fr) * 2016-03-29 2017-10-05 国立大学法人東京大学 Nouveau polymère organique et son procédé de production
WO2017170279A1 (fr) * 2016-04-01 2017-10-05 富士フイルム株式会社 Élément à semi-conducteur organique, polymère, composition semi-conductrice organique et film semi-conducteur organique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014078729A (ja) * 2008-08-29 2014-05-01 Idemitsu Kosan Co Ltd 有機薄膜トランジスタ用化合物及びそれを用いた有機薄膜トランジスタ
WO2017022758A1 (fr) * 2015-08-04 2017-02-09 富士フイルム株式会社 Transistor à film mince organique et son procédé de fabrication, matériau pour transistor à film mince organique, composition pour transistor à film mince organique, composé et film semi-conducteur organique
WO2017022761A1 (fr) * 2015-08-04 2017-02-09 富士フイルム株式会社 Transistor à couches minces organiques et son procédé de fabrication, matériau pour transistor à couches minces organiques, composition pour transistor à couches minces organiques, composé, et film semi-conducteur organique
WO2017170245A1 (fr) * 2016-03-29 2017-10-05 国立大学法人東京大学 Nouveau polymère organique et son procédé de production
WO2017170279A1 (fr) * 2016-04-01 2017-10-05 富士フイルム株式会社 Élément à semi-conducteur organique, polymère, composition semi-conductrice organique et film semi-conducteur organique

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