WO2021177417A1 - 芳香族化合物、有機半導体層、及び有機薄膜トランジスタ - Google Patents

芳香族化合物、有機半導体層、及び有機薄膜トランジスタ Download PDF

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WO2021177417A1
WO2021177417A1 PCT/JP2021/008511 JP2021008511W WO2021177417A1 WO 2021177417 A1 WO2021177417 A1 WO 2021177417A1 JP 2021008511 W JP2021008511 W JP 2021008511W WO 2021177417 A1 WO2021177417 A1 WO 2021177417A1
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真人 宮下
渡辺　真人
慎也 奥
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Tosoh Corp
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Priority to KR1020227032469A priority patent/KR20220150316A/ko
Priority to US17/905,455 priority patent/US20230142592A1/en
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Definitions

  • the present invention relates to a novel aromatic compound that can be applied to electronic materials such as organic semiconductor materials, an organic semiconductor layer using the same, and an organic thin film, and is particularly excellent in solubility and heat resistance. It relates to an aromatic compound having a specific substituent applicable to a device fabrication process, an organic semiconductor layer using the same, and an organic thin film.
  • Organic semiconductor devices represented by organic thin film transistors have been attracting attention in recent years because they have features such as energy saving, low cost, and flexibility that are not found in inorganic semiconductor devices.
  • This organic semiconductor device is composed of several kinds of materials such as an organic semiconductor layer, a substrate, an insulating layer, and an electrode. Among them, the organic semiconductor layer responsible for charge carrier transfer plays a central role in the device. Since the performance of an organic semiconductor device depends on the carrier mobility of the organic semiconductor material constituting the organic semiconductor layer, the appearance of an organic semiconductor material that gives high carrier mobility is desired.
  • the coating method can be carried out by using printing technology without using high-temperature and high-vacuum conditions, so that it can be expected to significantly reduce the manufacturing cost of device fabrication, which is an economically preferable process.
  • the organic semiconductor material used in such a coating method has a heat resistance of 130 ° C. or higher and a solubility at room temperature of 0.1% by weight or more from the viewpoint of high carrier mobility and device manufacturing process. Is preferable.
  • the carrier mobility is preferably 1.0 cm 2 / V ⁇ sec or more.
  • a small molecule semiconductor having a rod-shaped molecular major axis of a condensed ring system tends to exhibit high carrier mobility because it has higher crystallinity than a polymer semiconductor.
  • small molecule semiconductors have a problem of low solubility, and although semiconductors in which an alkyl group is introduced to improve solubility have been reported, there is a problem that carrier mobility and heat resistance are lowered. .. Further, a semiconductor having an aromatic substituent introduced for the purpose of developing high carrier mobility by ⁇ stack has been reported, but it has been reported that the solubility is significantly reduced in exchange for the development of high mobility.
  • Non-Patent Document 2 The 2,7-diphenyl [1] benzothiophene [3,2-b] [1] benzothiophene described in Non-Patent Document 2 is generally hardly soluble in an organic solvent, and has a problem in solubility.
  • alkyl-substituted dithienobiphenylene derivative described in Patent Document 2 has both high heat resistance and appropriate solubility and can be suitably used for organic semiconductors, but a compound having even higher carrier mobility has been desired. ..
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a novel coating type organic semiconductor material having high carrier mobility, high heat resistance, and appropriate solubility.
  • the present invention relates to an aromatic compound represented by either the following formula (1-I) or formula (1-II), an organic semiconductor layer containing the aromatic compound, and an organic thin film transistor provided with the semiconductor layer. It is a thing.
  • Ar indicates a single ring or 2 to 6 fused rings.
  • Y 1 and Y 2 each independently indicate either CR 6 or a nitrogen atom.
  • R 1 to R 6 independently indicate a hydrogen atom, a halogen atom, and the like.
  • L and n are independent of each other.
  • Indicates 0 or 1 m represents an integer from 1 to 20.
  • Z 1 and Z 2 represent one of a group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms, which are the same or different in their respective appearances. )]
  • the novel aromatic compound of the present invention provides high carrier mobility, high heat resistance and appropriate solubility. Therefore, it is possible to provide an organic thin film transistor that exhibits excellent semiconductor characteristics by coating, and the effect is extremely high.
  • the present invention is an aromatic compound represented by either the above formula (1-I) or the above formula (1-II) (hereinafter, referred to as "the compound of the present invention").
  • Ar in formulas (1-I) and (1-II) represents a single ring or 2 to 6 fused rings.
  • Ar is preferably 2 to 4 fused rings in order to show higher carrier mobility, and more preferably 2 to 3 fused rings to show higher solubility.
  • the individual rings constituting the single ring or 2 to 6 fused rings are 4 to 8 membered rings, and 4 to 6 membered rings are preferable because ⁇ stacking is facilitated.
  • Specific examples of the monocyclic ring or 2 to 6 fused rings represented by Ar include a cyclobutene ring, a thiophene ring, a furan ring, a selenophene ring, a thiazole ring, an oxazole ring, a pyrrole ring, an imidazole ring, a benzene ring, a pyridine ring and the like.
  • Fused rings such as monocyclic, thienothiophene ring, naphthalene ring, biphenylene ring, anthracene ring, dithienothiophene ring, dithienobenzo ring, benzothienobenzothiophene ring, tetracene ring, bis (dithieno) benzo ring, bis (benzothieno) benzo ring, etc.
  • thienothiophene ring In order to exhibit higher carrier mobility, 2 to 4 fused rings of thienothiophene ring, naphthalene ring, biphenylene ring, anthracene ring, dithienothiophene ring, and benzothienobenzothiophene ring are preferable, and thieno. Two or three fused rings of a thiophene ring, a naphthalene ring, a biphenylene ring, and an anthracene ring are more preferable.
  • R 1 to R 6 in the formulas (1-I) and (1-II) are independently hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, respectively.
  • At least one of R 1 to R 6 is a group represented by the formula (2).
  • halogen atom in R 1 to R 6 for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are shown, and any of a fluorine atom and a chlorine atom is preferable because they are stable.
  • Examples of the alkyl group having 1 to 20 carbon atoms in R 1 to R 6 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group and an isovaleryl group.
  • n-hexyl group isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n- Examples thereof include linear, branched or cyclic alkyl groups such as octadecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group.
  • an alkyl group having 1 to 14 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc. n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group having 1 to 1 carbon atoms.
  • a linear alkyl group of 14 is even more preferred.
  • Examples of the alkenyl group having 2 to 20 carbon atoms in R 1 to R 6 include an ethenyl group, a propenyl group, a butenyl group, a 2-methylpropenyl group, an n-pentenyl group, a 2-methylbutenyl group and an n-hexenyl group.
  • Examples of the alkynyl group having 2 to 20 carbon atoms in R 1 to R 6 include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptinyl group, an n-octynyl group, and n.
  • -Noninyl group, n-decynyl group, n-dodecynyl group and the like can be mentioned.
  • Examples of the alkazienyl group having 4 to 22 carbon atoms in R 1 to R 6 include a butadienyl group, a pentadienyl group, a hexadienyl group, an n-heptadienyl group, an n-octadienyl group, an n-nonazienyl group, an n-decadienyl group, and n.
  • -Dodecadienyl group, n-tridecadienyl group and the like can be mentioned, and an arc-1,3-dienyl group having 4 to 22 carbon atoms is preferable, and a hexa-1,3-dienyl group and an n-hepta-1,3- A dienyl group, an n-octa-1,3-dienyl group, an n-nona-1,3-dienyl group, and an n-deca-1,3-dienyl group are more preferable.
  • Examples of the alkadynyl group having 4 to 22 carbon atoms in R 1 to R 6 include a butadynyl group, a pentadiynyl group, a hexadiynyl group, an n-heptadinyl group, an n-octadynyl group, an n-nonadynyl group, and an n-decadinyl group.
  • Examples thereof include an n-dodecadynyl group and an n-tridecadynyl group, preferably a 1,3-alkadynyl group having 4 to 22 carbon atoms, a hexa-1,3-diynyl group and an n-hepta-1,3-.
  • a diynyl group, an n-octa-1,3-diynyl group, an n-nona-1,3-diynyl group, and an n-deca-1,3-diynyl group are more preferable.
  • the aryl groups having 4 to 26 carbon atoms in R 1 to R 6 include heteroaryl groups having 4 to 24 carbon atoms.
  • Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; a p-tolyl group, a p- (n-hexyl) phenyl group, a p- (n-octyl) phenyl group, and a p- (2-ethylhexyl) phenyl group.
  • Alkyl-substituted phenyl groups such as groups; 2-furyl group, 2-thienyl group; 5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5- (n-) Propyl) -2-furyl group, 5- (n-butyl) -2-furyl group, 5- (n-pentyl) -2-furyl group, 5- (n-hexyl) -2-furyl group, 5-( n-octyl) -2-furyl group, 5- (2-ethylhexyl) -2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5- (n-propyl) -2-thienyl group, 5- (n-butyl) -2-thienyl group, 5- (n-pentyl) -2-thienyl
  • R 1 to R 6 hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, and 4 carbon atoms for stability. It is preferably one of a group consisting of an aryl group of up to 26 or a group represented by the formula (2), and has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a formula (2) because of its high solubility.
  • R 1 and R 2 indicates a group represented by the formula (2), and R 3 It is more preferable that ⁇ R 6 is a hydrogen atom.
  • a in the formula (2) represents one of a group consisting of an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 4 to 26 carbon atoms, and exhibits a higher carrier mobility. Therefore, an aryl group having 4 to 26 carbon atoms is more preferable.
  • Examples of the alkenyl group having 2 to 20 carbon atoms in the formula (2) include an ethenyl group, a propenyl group, a butenyl group, a 2-methylpropenyl group, an n-pentenyl group, a 2-methylbutenyl group, an n-hexenyl group and 2-.
  • Examples of the alkynyl group having 2 to 20 carbon atoms in the formula (2) include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptinyl group, an n-octynyl group and an n-noninyl group.
  • Examples thereof include a group, an n-decynyl group, an n-dodecynyl group, a 2-phenylethynyl group, a 1-phenylethynyl group, a 2- (4-methylphenyl) ethynyl, a 2- (4-n-butyl) ethynyl and the like.
  • the aryl group having 4 to 26 carbon atoms in the formula (2) contains a heteroaryl group having 4 to 24 carbon atoms.
  • Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; a p-tolyl group, a p-ethylphenyl group, a p- (n-propyl) phenyl group, a p- (isopropyl) phenyl group, and a p- (n).
  • -Butyl) phenyl group p- (2-methylpropyl) phenyl group, p- (n-pentyl) phenyl group, p- (3-methylbutyl) phenyl group, p- (n-hexyl) phenyl group, p-( 4-Methylpentyl) phenyl group, p- (n-heptyl) phenyl group, p- (n-octyl) phenyl group, p- (2-ethylhexyl) phenyl group, m-ethylphenyl group, m- (n-propyl) ) Alkyl such as phenyl group, m- (n-butyl) phenyl group, m- (2-methylpropyl) phenyl group, o-ethylphenyl group, o- (n-propyl) phenyl group, indanyl-5-y
  • phenyl group substituted phenyl group; p-methoxyphenyl group, p-ethoxyphenyl group, p- (n-propyloxy) phenyl group, p- (n-butylphenyloxy) phenyl group, p- (n-pentyloxy) phenyl group, p- (n-hexyloxy) phenyl group, p- (n-heptyloxy) phenyl group, p- (n-octyloxy) phenyl group, m-methoxyphenyl group, m- (n-propyloxy) phenyl group, o-methoxyphenyl group, o- (n-propyloxy) phenyl group, 3,4-methylenedioxyphenyl group, 3,4-ethylenedioxyphenyl group, 2,3-dihydrobenzofuran-5-yl, 2, Alkyloxy-substituted phen
  • L and n in the formula (2) independently represent 0 or 1, respectively, and n is preferably 0 for ease of synthesis, and both l and n are 0 for high carrier mobility.
  • m represents an integer of 1 to 20
  • m is preferably an integer of 1 to 8 due to high solubility
  • m is more preferably an integer of 1 to 4 due to high carrier mobility. Is even more preferable.
  • Z 1 and Z 2 in the formula (2) are the same or different in their respective appearances, and represent one of a group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms.
  • a halogen atom in Z 1 and Z 2 for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are shown, and any of a fluorine atom and a chlorine atom is preferable because they are stable.
  • Examples of the alkyl group having 1 to 20 carbon atoms in Z 1 and Z 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group and an isovaleryl group.
  • n-hexyl group isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n- Examples thereof include linear, branched or cyclic alkyl groups such as octadecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group.
  • an alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, and an n-propyl group are more preferable because the aromatic compound exhibits high carrier mobility and high solubility.
  • the Z 1 and Z 2 are preferably either hydrogen atoms or halogen atoms because of their high carrier mobility, and more preferably hydrogen atoms.
  • A is either a phenyl group or an alkyl-substituted phenyl group, l and n are both 0, m is an integer of 1 to 4, and Z 1 and Z 2 are hydrogen atoms or halogens. It is preferably one of the atoms.
  • the group represented by the formula (2) is preferably a 2-phenylethyl group or a 2-alkyl-substituted phenylethyl group because of its high carrier mobility, and a 2-phenylethyl group or 2- (2) because of its high heat resistance and high solubility.
  • the aromatic compound of the formula (1-I) or the formula (1-II) is represented by one of the groups consisting of the following formulas (3-1) to (3-6) because of its ease of synthesis. Is preferable.
  • R 7 Of the two adjacent combinations of ⁇ R 10 only one set constitutes the following formula (4), and of the two adjacent combinations of R 11 to R 14 , only one set has the following formula. (4-2) is formed to form a 5- or 6-membered ring, respectively.
  • R 7 to R 14 and R 15 to R 19 which do not form the following formula (4) and the following formula (4-2) are Independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkazienyl group having 4 to 22 carbon atoms, and 4 carbon atoms.
  • Y 3 indicates either CR 24 or a nitrogen atom.
  • ⁇ R 24 independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an alkazienyl having 4 to 22 carbon atoms.
  • Arukajii alkenyl group having a carbon number of 4 to 22 represents one of the group consisting of groups represented by the aryl group having 4 to 26 carbon atoms, or the formula, (2), R 20 in the formula (2) It is a group represented.)
  • R 20b represents a hydrogen atom, a halogen atom, a carbon Alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, alkadienyl group having 4 to 22 carbon atoms, alkaziyl group having 4 to 22 carbon atoms, and 4 to 26 carbon atoms.
  • R 20 is a group represented by the formula (2).
  • R 20b is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkazienyl group having 4 to 22 carbon atoms, and 4 to 22 carbon atoms.
  • the formula (4-2) is preferably the following formula (4-3).
  • R 20c is a hydrogen atom, a halogen atom, a carbon
  • R 20c is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkazienyl group having 4 to 22 carbon atoms, and 4 to 22 carbon atoms. It is one of a group consisting of 22 alkadynyl groups or groups represented by aryl groups having 4 to 26 carbon atoms, and is preferably a hydrogen atom or a fluorine atom because of its high mobility. Is more preferable.
  • the formula (4-2) is preferably the following formula (4-4).
  • R 21 ⁇ R 24 represents a X 6, Y 3, R 21 ⁇ R 24 and as defined in the formula (4)
  • R 20d is represented by the formula (2) Is the basis.
  • Examples of the halogen atom in the R 7 to R 19 , R 21 to R 24 , R 20b , and R 20c indicate a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and since they are stable, they are a fluorine atom or a chlorine atom. Is preferable.
  • Examples of the alkyl group having 1 to 20 carbon atoms in R 7 to R 19 , R 21 to R 24 , R 20b , and R 20c include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • Branched or cyclic alkyl groups can be mentioned.
  • an alkyl group having 1 to 14 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.
  • a linear alkyl group of 14 is even more preferred.
  • Examples of the alkenyl group having 2 to 20 carbon atoms in R 7 to R 24 include an ethenyl group, a propenyl group, a butenyl group, a 2-methylpropenyl group, an n-pentenyl group, a 2-methylbutenyl group and an n-hexenyl group.
  • Examples of the alkynyl group having 2 to 20 carbon atoms in R 7 to R 19 , R 21 to R 24 , R 20b , and R 20c include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, and an n-hexynyl group. , N-heptynyl group, n-octynyl group, n-noninyl group, n-decynyl group, n-dodecynyl group and the like.
  • Examples of the alkazienyl group having 4 to 22 carbon atoms in R 7 to R 19 , R 21 to R 24 , R 20b , and R 20c include a butadienyl group, a pentadienyl group, a hexadienyl group, an n-heptadienyl group, and an n-octadienyl group.
  • N-nonadienyl group, n-decadienyl group, n-dodecadienyl group, n-tridecadienyl group and the like preferably an alka-1,3-dienyl group having 4 to 22 carbon atoms, and hexa-1,3 -Dienyl group, n-hepta-1,3-dienyl group, n-octa-1,3-dienyl group, n-nona-1,3-dienyl group, n-deca-1,3-dienyl group are more preferable. ..
  • Examples of the alkaziyl group having 4 to 22 carbon atoms in the R 7 to R 19 , R 21 to R 24 , R 20b , and R 20c include a butadynyl group, a pentadiynyl group, a hexadiynyl group, an n-heptadiynyl group, and an n-octadinyl group.
  • Examples thereof include a group, an n-nonadynyl group, an n-decadynyl group, an n-dodecadynyl group, an n-toridecadynyl group, and the like, preferably a 1,3-alkadynyl group having 4 to 22 carbon atoms, preferably hexa-1,3. -Diynyl group, n-hepta-1,3-diynyl group, n-octa-1,3-diynyl group, n-nona-1,3-diynyl group, n-deca-1,3-diynyl group are more preferable. ..
  • the aryl groups having 4 to 26 carbon atoms in the R 7 to R 19 , R 21 to R 24 , R 20b , and R 20c include heteroaryl groups having 4 to 24 carbon atoms.
  • Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; a p-tolyl group, a p- (n-hexyl) phenyl group, a p- (n-octyl) phenyl group, and a p- (2-ethylhexyl) phenyl group.
  • Alkyl-substituted phenyl groups such as groups; 2-furyl group, 2-thienyl group; 5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5- (n-) Propyl) -2-furyl group, 5- (n-butyl) -2-furyl group, 5- (n-pentyl) -2-furyl group, 5- (n-hexyl) -2-furyl group, 5-( n-octyl) -2-furyl group, 5- (2-ethylhexyl) -2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5- (n-propyl) -2-thienyl group, 5- (n-butyl) -2-thienyl group, 5- (n-pentyl) -2-thienyl
  • the R 7 to R 19 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 4 to 26 carbon atoms.
  • One of the group consisting of the aryl group of the above or the group represented by the formula (2) is preferable, and an alkyl group having a hydrogen atom and 1 to 20 carbon atoms is more preferable because of its high solubility.
  • the R 21 to R 24 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 4 to 26 carbon atoms.
  • One of the group consisting of the aryl group of the above or the group represented by the formula (2) is preferable, and R 21 to R 24 are selected from one of the group consisting of a hydrogen atom and a methyl group because of the high carrier mobility. More preferably, and even more preferably, a hydrogen atom.
  • Y 3 in the formula (4) and (4-2) - (4-3) indicates either a CR 24 or nitrogen atom, for stability CR 24 is preferred.
  • aromatic compounds represented by the formulas (3-1) to (3-6) have high carrier mobility, a structure that is point-symmetrical or axisymmetric is preferable, and a point-symmetrical structure is more preferable.
  • the aromatic compounds represented by the formulas (3-1) to (3-6) are preferably the formula (3-1) or the formula (3-2) because of their high solubility and high heat resistance.
  • the aromatic compound represented by the formula (1-I) or the formula (1-II) is preferably an aromatic compound represented by the following formula (5) or the following formula (5-2).
  • R 33b represents a hydrogen atom, a halogen atom, a carbon Alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, alkadienyl group having 4 to 22 carbon atoms, alkaziyl group having 4 to 22 carbon atoms, and 4 to 26 carbon atoms. Indicates one of the group consisting of the aryl group of the above, or the group represented by the above formula (2).
  • R 33 is a group represented by the formula (2).
  • R 33b is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkazienyl group having 4 to 22 carbon atoms, and 4 to 22 carbon atoms.
  • the formula (6-2) is preferably the following formula (6-3).
  • R 34 ⁇ R 37 are the same meaning as X 7, Y 4, R 34 ⁇ R 37 in the formula (6)
  • R 33c is a hydrogen atom, a halogen atom, a carbon
  • R 33c is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkazienyl group having 4 to 22 carbon atoms, and 4 to 22 carbon atoms. It is one of a group consisting of 22 alkadynyl groups or groups represented by aryl groups having 4 to 26 carbon atoms, and is preferably a hydrogen atom or a fluorine atom because of its high mobility. Is more preferable.
  • the formula (6-2) is preferably the following formula (6-4). (Wherein, X 7, Y 4, R 34 ⁇ R 37 are the same meaning as X 7, Y 4, R 34 ⁇ R 37 in the formula (6), R 33d is represented by the formula (2) Is the basis.)
  • the halogen atoms in the R 25 to R 32 , R 34 to R 37 , R 69 , R 70 , R 33b , and R 33c show, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and are stable. Preferably either a fluorine atom or a chlorine atom.
  • Examples of the alkyl group having 1 to 20 carbon atoms in R 25 to R 32 , R 34 to R 37 , R 69 , R 70 , R 33b , and R 33c include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • n-butyl group isobutyl group, n-pentyl group, isovaleryl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group , N-dodecyl group, n-tridecyl group, n-tetradecyl group, n-octadecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl Examples include linear, branched, or cyclic alkyl groups such as groups.
  • an alkyl group having 1 to 14 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc. n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group having 1 to 1 carbon atoms.
  • a linear alkyl group of 14 is even more preferred.
  • Examples of the alkenyl group having 2 to 20 carbon atoms in the R 25 to R 32 , R 34 to R 37 , R 69 , R 70 , R 33b , and R 33c include an ethenyl group, a propenyl group, a butenyl group, and 2-methyl.
  • Examples of the alkynyl group having 2 to 20 carbon atoms in the R 25 to R 32 , R 34 to R 37 , R 69 , R 70 , R 33b , and R 33c include an ethynyl group, a propynyl group, a butynyl group, and an n-pentynyl group. Examples thereof include a group, an n-hexynyl group, an n-heptinyl group, an n-octynyl group, an n-noninyl group, an n-decynyl group, an n-dodecynyl group and the like.
  • Examples of the alkazienyl group having 4 to 22 carbon atoms in R 25 to R 32 , R 34 to R 37 , R 69 , R 70 , R 33b , and R 33c include a butadienyl group, a pentadienyl group, a hexadienyl group, and an n-heptadienyl group.
  • Examples thereof include a group, an n-octadienyl group, an n-nonazienyl group, an n-decadienyl group, an n-dodecadienyl group, an n-tridecadienyl group and the like, and an arc-1,3-dienyl group having 4 to 22 carbon atoms is preferable.
  • Hexa-1,3-dienyl group, n-hepta-1,3-dienyl group, n-octa-1,3-dienyl group, n-nona-1,3-dienyl group, n-deca-1,3 -Dienyl groups are more preferred.
  • Examples of the alkadynyl group having 4 to 22 carbon atoms in the R 25 to R 32 , R 34 to R 37 , R 69 , R 70 , R 33b , and R 33c include a butadynyl group, a pentadiynyl group, a hexadiynyl group, and n-.
  • Examples thereof include a heptadiynyl group, an n-octadynyl group, an n-nonadynyl group, an n-decadynyl group, an n-dodecadynyl group, an n-toridecadynyl group, and the like, preferably a 1,3-alkadynyl group having 4 to 22 carbon atoms.
  • Hexa-1,3-diynyl group, n-hepta-1,3-diynyl group, n-octa-1,3-diynyl group, n-nona-1,3-diynyl group, n-deca-1,3 -Diynyl groups are more preferred.
  • the aryl groups having 4 to 26 carbon atoms in the R 25 to R 32 , R 34 to R 37 , R 69 , R 70 , R 33b , and R 33c include heteroaryl groups having 4 to 24 carbon atoms.
  • Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; a p-tolyl group, a p- (n-hexyl) phenyl group, a p- (n-octyl) phenyl group, and a p- (2-ethylhexyl) phenyl group.
  • Alkyl-substituted phenyl groups such as groups; 2-furyl group, 2-thienyl group; 5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5- (n-) Propyl) -2-furyl group, 5- (n-butyl) -2-furyl group, 5- (n-pentyl) -2-furyl group, 5- (n-hexyl) -2-furyl group, 5-( n-octyl) -2-furyl group, 5- (2-ethylhexyl) -2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5- (n-propyl) -2-thienyl group, 5- (n-butyl) -2-thienyl group, 5- (n-pentyl) -2-thienyl
  • the R 25 to R 32 , R 69 , and R 70 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms.
  • One of the group consisting of an aryl group having 4 to 26 carbon atoms or a group represented by the formula (2) is preferable, and a hydrogen atom and an alkyl group having 1 to 20 carbon atoms are more preferable because of high solubility, and hydrogen. It is more preferable to be selected from one of the group consisting of an atom and a methyl group.
  • R 34 to R 37 have a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 4 to 26 carbon atoms.
  • One of the group consisting of the aryl group of the above, or the group represented by the formula (2) is preferable, and because of its high carrier mobility, it is represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or the formula (2). Groups are more preferred, and R 34 to R 37 are even more preferably hydrogen atoms.
  • Y 4 in formula (6) and (6-2) - (6-4) represents a CR 37 or nitrogen atom, for stability CR 37 is preferred.
  • aromatic compounds represented by the formulas (5) and (5-2) have high carrier mobility, a structure that is point-symmetrical or axisymmetric is preferable, and a point-symmetrical structure is more preferable.
  • the aromatic compound represented by the formula (5) and the formula (5-2) is preferably the formula (5) because of its high solubility.
  • the aromatic compound represented by the formula (5) or the formula (5-2) is one of the compounds in the group consisting of the following formulas (7-1) to (7-5) due to the ease of synthesis. Is preferable.
  • X 8 and X 9 independently represent one of a group consisting of an oxygen atom, a sulfur atom, a selenium atom, or an NR 44.
  • Y 5 and Y 6 are independent and CR. Indicates either 45 or a nitrogen atom.
  • R 38 to R 45 , R 71 , and R 72 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkenyl having 2 to 20 carbon atoms.
  • an alkynyl group having 2 to 20 carbon atoms From a group, an alkynyl group having 2 to 20 carbon atoms, an alkadienyl group having 4 to 22 carbon atoms, an alkadiynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the formula (2).
  • At least one of R 38 to R 45 is a group represented by the formula (2)
  • at least one of R 38 and R 41 is a group represented by the formula (2). .
  • X 8 and X 9 of the formulas (7-1) to (7-5) independently represent one of a group consisting of an oxygen atom, a sulfur atom, a selenium atom, and an NR 44, and sulfur for stability. Atoms, oxygen atoms, sulfur atoms and selenium atoms are preferable, and sulfur atoms are more preferable because of high carrier mobility.
  • Y 5 and Y 6 of the formulas (7-1) to (7-5) independently represent either CR 45 or a nitrogen atom, and CR 45 is preferable for stability.
  • R 38 to R 45 , R 71 , and R 72 of the formulas (7-1) to (7-5) are independently hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms, respectively.
  • R 38 and R 41 of the formulas (7-1) to (7-5) are groups represented by the formula (2) in only one or both of them.
  • the definition of the group represented by the formula (2) in the formulas (7-1) to (7-5) is the definition of the formula (2) in the above formulas (1-I) and (1-II). It has the same meaning as.
  • halogen atom in the R 38 to R 45 , R 71 , and R 72 for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are shown, and any of a fluorine atom and a chlorine atom is preferable because they are stable.
  • alkyl group having 1 to 20 carbon atoms in the R 38 to R 45 , R 71 , and R 72 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and n-.
  • Pentyl group isovaleryl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n -A straight chain, branched or cyclic alkyl group such as a tetradecyl group, an n-octadecyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 3-ethyldecyl, a 2-hexyldecyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.
  • an alkyl group having 1 to 14 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc. n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group having 1 to 1 carbon atoms.
  • a linear alkyl group of 14 is even more preferred.
  • Examples of the alkenyl group having 2 to 20 carbon atoms in the R 38 to R 45 , R 71 and R 72 include an ethenyl group, a propenyl group, a butenyl group, a 2-methylpropenyl group, an n-pentenyl group and a 2-methylbutenyl group.
  • N-hexenyl group 2-methylpentenyl group, n-heptenyl group, n-octenyl group, 2-ethylhexenyl group, n-nonel group, 2-ethylheptenyl group, n-decenyl group, n-dodecenyl group, cyclopentenyl
  • Examples thereof include a -1- group, a cyclohexenyl-1- group, a cycloheptenyl-1- group and the like.
  • Examples of the alkynyl group having 2 to 20 carbon atoms in the R 38 to R 45 , R 71 , and R 72 include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, and an n-heptinyl group. Examples thereof include an n-octynyl group, an n-noninyl group, an n-decynyl group and an n-dodecynyl group.
  • Examples of the alkadienyl group having 4 to 22 carbon atoms in the R 38 to R 45 , R 71 , and R 72 include a butadienyl group, a pentadienyl group, a hexadienyl group, an n-heptadienyl group, an n-octadienyl group, and an n-nonazienyl group.
  • Examples thereof include an n-decadienyl group, an n-dodecadienyl group, an n-toridecadienyl group, and the like, preferably an alka-1,3-dienyl group having 4 to 22 carbon atoms, and a hexa-1,3-dienyl group, n-. Hepta-1,3-dienyl group, n-octa-1,3-dienyl group, n-nona-1,3-dienyl group and n-deca-1,3-dienyl group are more preferable.
  • Examples of the alkadynyl group having 4 to 22 carbon atoms in the R 38 to R 45 , R 71 , and R 72 include a butadynyl group, a pentadiynyl group, a hexadiynyl group, an n-heptadinyl group, an n-octadynyl group, and an n-nonadynyl group.
  • N-decadynyl group, n-dodecadynyl group, n-tridecadynyl group and the like preferably 1,3-alkadynyl group having 4 to 22 carbon atoms, hexa-1,3-diynyl group, n- Hepta-1,3-diynyl group, n-octa-1,3-diynyl group, n-nona-1,3-diynyl group and n-deca-1,3-diynyl group are more preferable.
  • the aryl groups having 4 to 26 carbon atoms in the R 38 to R 45 , R 71 , and R 72 include heteroaryl groups having 4 to 24 carbon atoms.
  • Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; a p-tolyl group, a p- (n-hexyl) phenyl group, a p- (n-octyl) phenyl group, and a p- (2-ethylhexyl) phenyl group.
  • Alkyl-substituted phenyl groups such as groups; 2-furyl group, 2-thienyl group; 5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5- (n-) Propyl) -2-furyl group, 5- (n-butyl) -2-furyl group, 5- (n-pentyl) -2-furyl group, 5- (n-hexyl) -2-furyl group, 5-( n-octyl) -2-furyl group, 5- (2-ethylhexyl) -2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5- (n-propyl) -2-thienyl group, 5- (n-butyl) -2-thienyl group, 5- (n-pentyl) -2-thienyl
  • the R 38 to R 45 , R 71 , and R 72 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms.
  • One of the group consisting of an aryl group having 4 to 26 carbon atoms or a group represented by the formula (2) is preferable, and because of its high solubility, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a formula (2). ) Is more preferable.
  • R 38 and R 41 are preferably one of a group consisting of a group represented by the above formula (2), a hydrogen atom and a fluorine atom, and are represented by the above formula (2). It is more preferable that it is one of a group consisting of a group and a hydrogen atom, and it is further preferable that both R 38 and R 41 are represented by the above formula (2). It is even more preferable that R 39 , R 40 , R 42 to R 45 , R 71 , and R 72 be selected from one of the group consisting of a hydrogen atom and a methyl group, and a hydrogen atom is even more preferable.
  • aromatic compounds represented by the above formulas (7-1) to (7-5) have high carrier mobility, a structure that is point-symmetrical or axisymmetric is preferable, and a point-symmetrical structure is more preferable.
  • any of the formulas (7-1), (7-2) or (7-5) is preferable because of high solubility, and high carrier mobility is used. It is more preferable that the equation (7-1) is used because of the mobility.
  • a more preferable compound structure of the compound of the present invention is represented by one of the groups consisting of the following formulas (8-1) to (8-11) in addition to the above formulas (7-1) to (7-5).
  • a group consisting of (7-1) to (7-5) and (8-2) to (8-9) having 4 to 5 fused rings It is preferable that it is one of the aromatic compounds of the above, and the formulas (7-1) to (7-5), (8-2) to (8-3), ( It is more preferable that it is one kind of aromatic compound in the group consisting of 8-5) to (8-8).
  • R 46 to R. 61 are independently hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and alkazienyl groups having 4 to 22 carbon atoms.
  • It represents one of a group consisting of an alkadynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the formula (2), and at least one of R 46 to R 61 is of the formula ( It is a group represented by 2), and at least one of R 46 and R 47 is a group represented by the formula (2).
  • O represents 0 or 1).
  • One of the group consisting of a sulfur atom and a selenium atom is preferable, and a sulfur atom is more preferable because of high carrier mobility.
  • Y in the formulas (8-1) to (8-11) represents either CR 61 or a nitrogen atom, and CR 61 is preferable for stability.
  • R 46 to R 61 of the formulas (8-1) to (8-11) are independently hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, and carbon.
  • the definition of the group represented by the formula (2) in the formulas (8-1) to (8-11) has the same meaning as the definitions of the above formulas (1-I) and (1-II). ..
  • halogen atom in R 46 to R 61 for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are shown, and any of a fluorine atom and a chlorine atom is preferable because they are stable.
  • alkyl group having 1 to 20 carbon atoms in R 46 to R 61 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group and an isovaleryl group.
  • n-hexyl group isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n- Examples thereof include linear, branched or cyclic alkyl groups such as octadecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group.
  • an alkyl group having 1 to 14 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc. n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group having 1 to 1 carbon atoms.
  • a linear alkyl group of 14 is even more preferred.
  • Examples of the alkenyl group having 2 to 20 carbon atoms in R 46 to R 61 include an ethenyl group, a propenyl group, a butenyl group, a 2-methylpropenyl group, an n-pentenyl group, a 2-methylbutenyl group and an n-hexenyl group.
  • Examples of the alkynyl group having 2 to 20 carbon atoms in R 46 to R 61 include an ethynyl group, a propynyl group, a butynyl group, an n-pentynyl group, an n-hexynyl group, an n-heptinyl group, an n-octynyl group, and n.
  • -Noninyl group, n-decynyl group, n-dodecynyl group and the like can be mentioned.
  • Examples of the alkadienyl group having 4 to 22 carbon atoms in R 46 to R 61 include a butadienyl group, a pentadienyl group, a hexadienyl group, an n-heptadienyl group, an n-octadienyl group, an n-nonazienyl group, an n-decadienyl group, and n.
  • -Dodecadienyl group, n-tridecadienyl group and the like can be mentioned, and an arc-1,3-dienyl group having 4 to 22 carbon atoms is preferable, and a hexa-1,3-dienyl group and an n-hepta-1,3- A dienyl group, an n-octa-1,3-dienyl group, an n-nona-1,3-dienyl group, and an n-deca-1,3-dienyl group are more preferable.
  • Examples of the alkadynyl group having 4 to 22 carbon atoms in R 46 to R 61 include a butadynyl group, a pentadiynyl group, a hexadiynyl group, an n-heptadinyl group, an n-octadynyl group, an n-nonadynyl group, and an n-decadinyl group.
  • Examples thereof include an n-dodecadynyl group and an n-tridecadynyl group, preferably a 1,3-alkadynyl group having 4 to 22 carbon atoms, a hexa-1,3-diynyl group and an n-hepta-1,3-.
  • a diynyl group, an n-octa-1,3-diynyl group, an n-nona-1,3-diynyl group, and an n-deca-1,3-diynyl group are more preferable.
  • the aryl group having 4 to 26 carbon atoms in the R 46 to R 61 contains a heteroaryl group having 4 to 24 carbon atoms.
  • Examples of the aryl group having 4 to 26 carbon atoms include a phenyl group; a p-tolyl group, a p- (n-hexyl) phenyl group, a p- (n-octyl) phenyl group, and a p- (2-ethylhexyl) phenyl group.
  • Alkyl-substituted phenyl groups such as groups; 2-furyl group, 2-thienyl group; 5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5- (n-) Propyl) -2-furyl group, 5- (n-butyl) -2-furyl group, 5- (n-pentyl) -2-furyl group, 5- (n-hexyl) -2-furyl group, 5-( n-octyl) -2-furyl group, 5- (2-ethylhexyl) -2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5- (n-propyl) -2-thienyl group, 5- (n-butyl) -2-thienyl group, 5- (n-pentyl) -2-thienyl
  • the R 46 to R 61 have a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 4 to 26 carbon atoms. It is preferably one of the group consisting of the aryl group of the above, or the group represented by the formula (2). From the viewpoint of high carrier mobility, R 46 and R 47 are preferably one of a group consisting of a group represented by the formula (2), a hydrogen atom and a fluorine atom, and the group represented by the formula (2).
  • R 48 to R 61 are preferably selected from one of the group consisting of a hydrogen atom and a methyl group, and more preferably a hydrogen atom.
  • O in the formulas (8-5) and (8-6) indicates 0 or 1, and 1 is preferable because of high carrier mobility.
  • any production method can be used as long as the compound can be produced.
  • X 8 and X 9 of the formula (7-1) are sulfur atoms
  • Y 5 and Y 6 are CH
  • R 38 and R 41 are formulas ( The groups represented by 2)
  • R 39 , R 40 , R 42 , and R 43 are hydrogen atoms
  • l and n in the formula (2) are 0, respectively
  • Z 1 and Z 2 are hydrogen atoms.
  • a certain aromatic compound (7-1a) can be produced by the method of going through the following steps A1 to C1.
  • Step A1 A method of synthesizing a dibromodibiphenylene derivative (Compound 2) with butyl lithium as a dilithium salt and synthesizing a dibromodithionovylene derivative (Compound 3) with a bromoating agent (Step B1); reacting an alkyl bromide derivative with magnesium.
  • Step B1 A method for producing an alkylmagnesium bromide.
  • Step C1 Aromatic by reacting the alkylzinc chloride derived from the alkylmagnesium bromide obtained in the B1 step with the dibromodithienobiphenylene derivative (Compound 3) synthesized in the A1 step in the presence of a palladium catalyst.
  • the A1 step is a method for producing a dibromo compound by converting a dithienobiphenylene derivative into a dilithium salt with 2 equivalents or more of butyllithium and reacting it with a bromoating agent.
  • a dilithium salt for example, 2 to 3 equivalents of n-butyllithium or tert-butyllithium are used, and the dilithium salt is prepared in a solvent such as THF or diethyl ether in a temperature range of ⁇ 80 ° C. to 20 ° C. be able to.
  • the brominating agent tetrabromomethane, 1,2-dibromotetrachloroethane, N-bromosuccinimide (hereinafter abbreviated as "NBS" and the like can be used.
  • the B1 step is a method for producing an alkylmagnesium bromide by reacting an alkyl bromide derivative with magnesium.
  • a condition for preparing the magnesium salt for example, 1 to 2 equivalents of magnesium can be used, and the magnesium salt can be prepared in a solvent such as THF or diethyl ether in a temperature range of 25 ° C. to 60 ° C.
  • alkyl bromide derivative in the B1 step examples include benzyl bromide, 2-phenylethyl bromide, 3-phenylpropyl bromide, 4-phenylbutyl bromide, 4-methylphenethyl bromide, 1- (2-bromoethyl) -4-ethylbenzene, and 1 -(2-Bromoethyl) -4-propylbenzene, 1- (2-bromoethyl) -4-butylbenzene, 1- (2-bromoethyl) -4-pentylbenzene, 1- (2-bromoethyl) -4-hexylbenzene , 1- (2-bromoethyl) -4-heptylbenzene, 1- (2-bromoethyl) -4-octylbenzene, 5- (2-bromoethyl) -2,3-dihydrobenzofuran and the like.
  • Examples of the palladium catalyst in the C1 step include [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II), tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium and the like.
  • the reaction temperature can be in the range of 20 ° C. to 60 ° C.
  • X 8 and X 9 of the formula (7-2) are sulfur atoms
  • Y 5 and Y 6 are CH
  • R 38 and R 41 are groups represented by the formula (2)
  • R 40 , R 42 , and R 43 are hydrogen atoms
  • l and n in the formula (2) are 0, respectively
  • the aromatic compound (7-2a) in which Z 1 and Z 2 are hydrogen atoms is the following D1. It can be produced by a method that goes through the steps of ⁇ G1.
  • Step D1 1,5-bis (trimethylsilylethynyl) -2,6- by sonogashira coupling of 1,5-difluoro-2,6-diiodohalobiphenylene and trimethylsilylacetylene in the presence of palladium / copper catalyst.
  • Step E1; 1,5-bis (trimethylsilylethynyl) -2,6-difluorobiphenylene obtained by step D1 and sodium sulfide were subjected to the reaction, and biphenyleno [2,1-b: 6,5-b'].
  • the process of producing dithiophene 1,5-bis (trimethylsilylethynyl) -2,6- by sonogashira coupling of 1,5-difluoro-2,6-diiodohalobiphenylene and trimethylsilylacetylene in the presence of palladium / copper catalyst.
  • the D1 step is 1,5-bis (trimethylsilylethynyl) -2,6 by sonogashira coupling of 2,6-difluoro-1,5-diiodohalobiphenylene and trimethylsilylacetylene in the presence of palladium catalyst and copper catalyst.
  • -A process for producing difluorobiphenylene examples include tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium, and examples of the copper catalyst include copper iodide (I), copper bromide (I), and copper chloride. (I) and the like can be mentioned.
  • the Sonogashira coupling can be carried out in a solvent such as triethylamine, diisopropylamine, diisopropylethylamine, piperidine, and pyridine in a temperature range of 20 ° C. to 80 ° C.
  • a solvent such as triethylamine, diisopropylamine, diisopropylethylamine, piperidine, and pyridine in a temperature range of 20 ° C. to 80 ° C.
  • toluene, THF and the like may be added as a solvent.
  • E1 process In the E1 step, biphenyleno [2,1-b: 6,5-b'] dithiophene was produced by the reaction of 1,5-bis (trimethylsilylethynyl) -2,6-difluorobiphenylene obtained in the D1 step with sodium sulfide. This is the manufacturing process.
  • the reaction is carried out in a solvent such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), N, N-dimethylformamide (hereinafter abbreviated as DMF), N-methylpyrrolidone (hereinafter abbreviated as NMP) and the like.
  • DMSO dimethyl sulfoxide
  • DMF N-dimethylformamide
  • NMP N-methylpyrrolidone
  • the step can also be carried out using known reaction conditions for synthesizing a benzothiophene ring from 2-haloalkynylbenz
  • biphenyleno [2,1-b: 6,5-b'] dithiophene obtained by the E1 step is converted into a dilithium salt with 2 equivalents or more of butyllithium and reacted with a bromoating agent to form a dibromo compound.
  • a manufacturing method As conditions for preparing the dilithium salt, for example, 2 to 3 equivalents of n-butyllithium or tert-butyllithium are used, and the dilithium salt is prepared in a solvent such as THF or diethyl ether in a temperature range of ⁇ 80 ° C. to 20 ° C. be able to.
  • the brominating agent tetrabromomethane, 1,2-dibromotetrachloroethane, NBS and the like can be used.
  • Examples of the palladium catalyst in the G1 step include [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II), tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium and the like.
  • the reaction temperature can be in the range of 20 ° C. to 60 ° C.
  • X 8 and X 9 are sulfur atoms
  • Y 5 and Y 6 are CH
  • R 38 and R 41 are groups represented by formula (2)
  • R 39 and R are groups represented by formula (2)
  • Step A2 Method of synthesizing a dibromoanthradithiophene derivative (Compound 20) with a dilithium salt of anthradithiophene derivative (Compound 19) with butyllithium and a bromoating agent (Step C2); Alkyl obtained by Step B1.
  • the A2 step is a method for producing a dibromo compound by converting an anthradithiophene derivative into a dilithium salt with 2 equivalents or more of butyllithium and reacting it with a bromoating agent.
  • a bromoating agent for example, 2 to 3 equivalents of n-butyllithium or tert-butyllithium are used, and the dilithium salt is prepared in a solvent such as THF or diethyl ether in a temperature range of ⁇ 80 ° C. to 20 ° C. be able to.
  • the brominating agent tetrabromomethane, 1,2-dibromotetrachloroethane and the like can be used.
  • Examples of the palladium catalyst in the C2 step include [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II), tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium and the like.
  • the reaction temperature can be in the range of 20 ° C. to 60 ° C.
  • X 8 and X 9 are sulfur atoms
  • Y 5 and Y 6 are CH
  • R 38 is a group represented by formula (2)
  • R 39 to R 43 are hydrogen.
  • Step A3 A method of synthesizing a monobromodiphenylene biphenylene derivative (Compound 21) with a monolithium salt of butyllithium and a monobromodithienobiphenylene derivative (Compound 21) with a brominating agent (Step C3); A method for producing an aromatic compound (7-1b) by reacting an alkylzinc bromide derived from an alkylmagnesium bromide with a monobromodithienobiphenylene derivative (Compound 21) synthesized in the A3 step in the presence of a palladium catalyst.
  • the A3 step is a method for producing a monobromo compound by converting a dithienobiphenylene derivative into a monolithium salt with 1.0 equivalent of butyllithium and reacting it with a bromoating agent.
  • a bromoating agent for example, 0.5 to 1.5 equivalents of n-butyllithium or tert-butyllithium are used, and the temperature is -80 ° C to 20 ° C in a solvent such as THF or diethyl ether. It can be carried out in the temperature range.
  • the brominating agent tetrabromomethane, 1,2-dibromotetrachloroethane and the like can be used.
  • Examples of the palladium catalyst in the C3 step include [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II), tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium and the like.
  • the reaction temperature can be in the range of 20 ° C. to 60 ° C.
  • X 8 and X 9 are sulfur atoms
  • Y 5 and Y 6 are CH
  • R 38 is a group represented by formula (2), R 39 to R 41 , R.
  • the aromatic compound (7-5b) in which 42, R 43 , R 71 , and R 72 are hydrogen atoms, l and n in the formula (2) are 0, respectively, and Z 1 and Z 2 are hydrogen atoms is described above. It can be produced by isolation as a by-product of the C2 step, or by the method of going through the steps of A4 below, B1 below, and C4 below.
  • An aromatic compound (7-5b) is produced by reacting an alkylzinc bromide derived from the above alkylmagnesium bromide with a monobromoanthradithiophene derivative (Compound 22) synthesized in the A4 step in the presence of a palladium catalyst.
  • the A4 step is a method for producing a monobromo compound by converting an anthradithiophene derivative into a monolithium salt with 1 equivalent of butyllithium and reacting it with a bromoating agent.
  • a bromoating agent for example, 0.5-1.5 equivalents of n-butyllithium or tert-butyllithium are used, and the temperature is ⁇ 80 ° C. to 20 ° C. in a solvent such as THF or diethyl ether. It can be carried out in the temperature range.
  • the brominating agent tetrabromomethane, 1,2-dibromotetrachloroethane and the like can be used.
  • an aromatic compound is formed by reacting an alkylzinc chloride derived from the alkylmagnesium bromide obtained in the B1 step with a monobromoanthradithiophene derivative (Compound 22) synthesized in the A4 step in the presence of a palladium catalyst.
  • 7-5b) is a method for producing.
  • zinc chloride can be used and carried out in a solvent such as THF or diethyl ether in a temperature range of 0 ° C. to 25 ° C.
  • Examples of the palladium catalyst in the C4 step include [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II), tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium and the like.
  • the reaction temperature can be in the range of 20 ° C. to 60 ° C.
  • the compound of the present invention can be made into a solution for forming an organic semiconductor layer containing the compound by dissolving it in an appropriate solvent.
  • the solvent any solvent may be used as long as it can dissolve the aromatic compound represented by the formula (1-I) or the formula (1-II), and an organic semiconductor layer is formed.
  • an organic solvent having a boiling point at normal pressure of 100 ° C. or higher is preferable because the drying speed of the solvent can be made suitable.
  • the solvent that can be used in the present invention is not particularly limited, and for example, aromatics such as toluene, mesityrene, o-xylene, isopropylbenzene, pentylbenzene, cyclohexylbenzene, 1,2,4-trimethylbenzene, tetralin, and indan.
  • aromatics such as toluene, mesityrene, o-xylene, isopropylbenzene, pentylbenzene, cyclohexylbenzene, 1,2,4-trimethylbenzene, tetralin, and indan.
  • Aromatic ethers such as methylenedioxybenzene and 1,2-ethylenedioxybenzene; chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-difluorobenzene, Aromatic halogen compounds such as 1,3-difluorobenzene and 1,4-difluorobenzene; thiophene, 3-chlorothiophene, 2-chlorothiophene, 3-methylthiophene, 2-methylthiophene, benzothiophene, 2-methylbenzothiophene , 2,3-Dihydrobenzothiophene, furan, 3-methylfuran, 2-methylfuran
  • the temperature at which the aromatic compound represented by the formula (1-I) or the formula (1-II) is mixed and dissolved in the solvent may be in the temperature range of 0 to 80 ° C. for the purpose of accelerating the dissolution. It is preferable, and it is more preferable to carry out in the temperature range of 10 to 60 ° C.
  • the time for dissolving and mixing the aromatic compound represented by the formula (1-I) or the formula (1-II) in an organic solvent is preferably 1 minute to 1 hour in order to obtain a uniform solution.
  • the concentration of the aromatic compound represented by the formula (1-I) or the formula (1-II) in the solution for forming an organic semiconductor layer of the present invention is in the range of 0.1 to 10.0% by weight. It becomes easy to handle and becomes more efficient in forming the organic semiconductor layer. Further, when the viscosity of the solution for forming an organic semiconductor layer is in the range of 0.3 to 10 mPa ⁇ s, more suitable coatability is exhibited. Since the aromatic compound itself has appropriate cohesiveness, the solution can be prepared at a relatively low temperature, and since it has oxidation resistance, it is suitably applied to the production of an organic thin film by a coating method. can. That is, since it is not necessary to remove air from the atmosphere, the coating process can be simplified.
  • the solution is, for example, polystyrene, poly ( ⁇ -methylstyrene), poly (4-methylstyrene), poly (1-vinylnaphthalene), poly (2-vinylnaphthalene), poly (styrene-block-butadiene-block).
  • the glass transition temperature (Tg) of the polymer binder is preferably 105 ° C. or higher, more preferably 120 ° C. or higher, and more preferably 150 ° C. or higher, because it is more suitable for dealing with the process temperature during the manufacture of electronic devices. Is particularly preferable.
  • the molecular weight of the polymer is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, because it is suitable for obtaining an organic thin film transistor having a higher carrier mobility. Of particular preference is 20,000 to 100,000.
  • the molecular weight of the polymer refers to the polystyrene-equivalent weight average molecular weight (Mw).
  • the polymer has an effect as a general polymer binder and improves the film forming property of the obtained organic semiconductor layer, and an insulating polymer and a semiconductor polymer can also be used.
  • Specific examples of the polymer that can be used as the polymer binder in the present invention include, for example, polar cyclic polyolefins, polysulfones, acrylonitrile-styrene copolymers, and methyl methacrylate-styrenes, in addition to the polymers listed above. Polymers and the like can be mentioned.
  • the polar cyclic polyolefins are more preferably polymers represented by the following formula (9).
  • R 62 to R 64 are independently hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and alkyloxycarbonyl group having 2 to 20 carbon atoms.
  • Z represents a halogen atom, an alkyloxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, and 1 to 1 carbon atoms.
  • P is an integer of 20 to 5,000. Shown, q and r each independently represent an integer of 0 to 2.
  • a bond consisting of a solid line and a dotted line indicates a single bond or a double bond.
  • R 62 to R 64 in the formula (9) are independently hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and alkyloxycarbonyl having 2 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms in R 62 to R 64 is, for example, a linear chain such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or an n-pentyl group.
  • a branched alkyl group can be mentioned.
  • the aryl group having 6 to 20 carbon atoms includes, for example, a phenyl group, a p-tolyl group, a p- (n-hexyl) phenyl group, a p- (n-octyl) phenyl group, a p- (2-ethylhexyl) phenyl group and the like. Can be mentioned.
  • Examples of the alkyloxycarbonyl group having 2 to 20 carbon atoms include a methyloxycarbonyl group, an ethyloxycarbonyl group, an n-propyloxycarbonyl group and the like.
  • Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include a phenoxycarbonyl group and a 4-methylphenoxycarbonyl group.
  • Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group and the like.
  • Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group and 4-methylphenoxy.
  • Examples of the alkylamino group having 1 to 20 carbon atoms include a methylamino group, an ethylamino group, an n-propylamino group and the like.
  • the substituent R 60 is preferably a methyl group, an ethyl group, or an n-propyl group, and the substituents R 63 and R 64 are preferably hydrogen atoms because of high heat resistance.
  • Z in the formula (9) is a halogen atom, an alkyloxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of carbon atoms.
  • the alkyloxycarbonyl group having 2 to 20 carbon atoms in the substituent Z includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an n-butoxycarbonyl group, an n-hexyloxycarbonyl group, a cyclohexyloxycarbonyl group and the like.
  • Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, a 2,4-dimethylphenoxycarbonyl group, and a 4-ethylphenoxycarbonyl group.
  • Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group and an ethoxy group.
  • Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group and 4-methylphenoxy.
  • Examples of the alkylamino group having 1 to 20 carbon atoms include a methylamino group, an ethylamino group, an n-propylamino group and the like.
  • It is preferably an alkyloxycarbonyl group having 2 to 20 carbon atoms because of its high solubility and high heat resistance.
  • p represents an integer of 20 to 5,000 and is preferably 40 to 2,000 because it is suitable for obtaining an organic thin film transistor having a higher carrier mobility.
  • q represents an integer of 0 to 2, preferably 1.
  • r represents an integer of 0 to 2, preferably 0 or 1. More preferably, it is 0.
  • the bond consisting of a solid line and a dotted line indicates a single bond or a double bond, and is preferably a single bond because of thermal stability.
  • the polysulfones used as the polymer binder in the present invention are not particularly limited as long as they have a polysulfone structure, and more specific examples thereof include the polysulfones represented by the following polysulfones 1 to 5.
  • substituents R 65 to R 68 independently represent an alkyl group having 1 to 20 carbon atoms, and s represents an integer of 10 to 20,000.
  • the alkyl groups having 1 to 20 carbon atoms in the substituents R 65 to R 68 are, for example, methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group and isohexyl.
  • s represents an integer of 10 to 20,000, preferably an integer of 10 to 10,000.
  • the acrylonitrile-styrene copolymer used as the polymer binder in the present invention is a copolymer of an arbitrary ratio of acrylonitrile and styrene, exhibits good electrical properties, and changes in the threshold voltage when bias stress is applied.
  • the ratio of acrylonitrile to styrene is preferably 10:90 to 50:50, and more preferably 20:80 to 40:60, because reliability is improved such as a smaller one.
  • the methyl methacrylate-styrene copolymer used as the polymer binder in the present invention is a copolymer of any ratio of methyl methacrylate and styrene, exhibits good electrical characteristics, and changes in threshold voltage when bias stress is applied.
  • the molar ratio of methyl methacrylate to styrene is preferably 1:99 to 90:10, and more preferably 1:99 to 70:30, because reliability is improved, such as a smaller ratio.
  • a polymer whose surface energy is adjusted with a surface treatment agent can be used.
  • a silane coupling agent can be used, and specific examples thereof include 1,1,1,3,3,3-hexamethyldisilazane, phenyltrimethoxysilane, and octyltrichlorosilane.
  • polystyrene resin examples thereof include ⁇ -phenyltilt trichlorosilane and ⁇ -phenyltilt trimethoxysilane.
  • the polymer used in the present invention can be used alone or as a mixture of two or more kinds of polymers. Furthermore, it is also possible to use a mixture of polymers having different molecular weights.
  • the coating method for forming the organic semiconductor layer using the solution for forming the organic semiconductor layer of the present invention is not particularly limited as long as it can form the organic semiconductor layer, and is, for example, spin coating, drop casting, or dipping.
  • Simple coating methods such as coating and cast coating; printing methods such as dispenser, inkjet, slit coating, blade coating, flexo printing, screen printing, gravure printing, offset printing, etc. can be mentioned, and among them, easily and efficiently with organic semiconductor layers.
  • Spin coating, drop casting, and inkjet are preferable because they can be used.
  • the drying conditions are not particularly limited, and for example, the solvent can be dried and removed under normal pressure or reduced pressure.
  • the temperature at which the organic solvent is dried and removed from the applied organic semiconductor layer is not particularly limited, but the organic solvent can be efficiently dried and removed from the applied organic semiconductor layer, and the organic semiconductor layer can be formed. It is preferably carried out in a temperature range of 10 to 150 ° C.
  • the crystal growth of the aromatic compound represented by the formula (1-I) or the formula (1-II) is performed by adjusting the vaporization rate of the organic solvent to be removed. It is possible to control.
  • the film thickness of the organic semiconductor layer formed by the solution for forming an organic semiconductor layer of the present invention is not limited, and good carrier transfer can be obtained. Therefore, the range is preferably in the range of 1 nm to 1 ⁇ m, and in the range of 10 nm to 300 nm. Is more preferable. Further, the obtained organic semiconductor layer may be annealed at 40 to 180 ° C. after forming the organic semiconductor layer.
  • the organic semiconductor layer formed from the solution for forming an organic semiconductor layer of the present invention can be used as an organic semiconductor device including the organic semiconductor layer, particularly as an organic thin film transistor including the organic semiconductor layer.
  • the organic thin film can be obtained by laminating an organic semiconductor layer having a source electrode and a drain electrode attached on a substrate and a gate electrode via an insulating layer, and is used for forming the organic semiconductor layer of the present invention on the organic semiconductor layer.
  • the organic semiconductor layer formed by the solution it is possible to obtain an organic thin film exhibiting excellent semiconductor and electrical characteristics.
  • FIG. 1 shows a structure of a general organic thin film transistor based on the cross-sectional shape.
  • (A) is a bottom gate-top contact type
  • (B) is a bottom gate-bottom contact type
  • (C) is a top gate-top contact type
  • (D) is a top gate-bottom contact type.
  • 1 is an organic semiconductor layer
  • 2 is a substrate
  • 3 is a gate electrode
  • 4 is a gate insulating layer
  • 5 is a source electrode
  • 6 is a drain electrode, which are formed from the organic semiconductor layer forming solution of the present invention.
  • the organic semiconductor layer to be formed can be applied to any organic thin film transistor.
  • the substrate according to the present invention is not particularly limited, and for example, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, fluorinated cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, etc.
  • Plastic substrates such as polyvinyl alcohol, poly (diisopropyl fumarate), poly (diethyl fumarate), poly (diisopropyl maleate), polyether sulfone, polyphenylene sulfide, cellulose triacetate; glass, quartz, aluminum oxide, silicon, high-doped silicon , Inorganic material substrates such as silicon oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide; metal substrates such as gold, copper, chromium, titanium and aluminum. When high-doped silicon is used for the substrate, the substrate can also serve as a gate electrode.
  • the gate electrode according to the present invention is not particularly limited, and for example, aluminum, gold, silver, copper, high-doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, graphene, carbon nanotubes and the like.
  • Inorganic materials organic materials such as doped conductive polymers (eg PEDOT-PSS) can be mentioned. Further, the above-mentioned inorganic material can be used as a metal nanoparticle ink without any problem.
  • the solvent is a polar solvent such as water, methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, etc.
  • the gate insulating layer according to the present invention is not particularly limited, and for example, silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, and titanium oxide.
  • Inorganic materials such as barium acid acid, bismuth titanate; polymethylmethacrylate, polymethylacrylate, polyimide, polycarbonate polyamic acid, polyvinylphenol, polyvinyl alcohol, poly (diisopropylfumarate), poly (diethylfumarate), polyethylene terephthalate, polyethylene na Phtalate, ethyl polysilicate, methyl polysilicate, ethyl polycrotonate, polyethersulfone, polypropylene-co-1-butene, polyisobutylene, polypropylene, polycyclopentane, polycyclohexane, polycyclohexane-ethylene copolymer, Polyfluorinated cyclopentane, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer, BCB resin (trade name: cycloten, manufactured by Dow Chemical Co., Ltd.), Cytop TM,
  • the solvent used for dissolving the polymer material is not particularly limited, and is, for example, an aliphatic hydrocarbon solvent having 6 to 14 carbon atoms such as hexane, heptane, octane, decane, dodecane, tetradecane; THF, 1,2-dimethoxy.
  • Ether-based solvents such as ethane and dioxane; alcohol-based solvents such as ethanol, isopropyl alcohol, 1-butanol, 2-butanol, 2-ethylhexanol and tetrahydrofurfuryl alcohol; Ketone solvent; ester solvent such as ethyl acetate, ⁇ -butyrolactone, cyclohexanol acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate; amide solvent such as DMF, NMP; dipropylene glycol Dimethyl ether, dipropylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol di Glycol-
  • the concentration of the polymer insulating material is, for example, 0.1 to 10.0% by weight at a temperature of 20 to 40 ° C.
  • the film thickness of the insulating layer obtained at this concentration is not limited, and is preferably 100 nm to 1 ⁇ m, more preferably 150 nm to 900 nm from the viewpoint of insulation resistance.
  • gate insulating layers are, for example, octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, ⁇ -phenethyllichlorosilane, ⁇ -phenetyltrimethoxysilane, and phenyltri.
  • Silanes such as chlorosilane and phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid and octylphosphonic acid; those modified with silylamines such as hexamethyldisilazane can also be used.
  • phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid and octylphosphonic acid
  • those modified with silylamines such as hexamethyldisilazane
  • the material of the source electrode and the drain electrode of the organic thin film transistor of the present invention is not particularly limited, and the same material as the gate electrode can be used, and the material may be the same as or different from that of the gate electrode, and different materials. May be laminated.
  • surface treatment can be performed on these electrode materials in order to increase the efficiency of carrier injection. Examples of the expression treatment agent used for the surface treatment include benzenethiol, pentafluorobenzenethiol, 4-fluorobenzenethiol, 4-methoxybenzenethiol and the like.
  • the organic thin film transistor of the present invention preferably has a carrier mobility of 1.00 cm 2 / V ⁇ sec or more because of its high operability. Moreover, because of the high switching characteristics, current on-off ratio, is preferably 1.0 ⁇ 10 6 or more.
  • the organic thin film transistor of the present invention is used for organic semiconductor layers of transistors such as electronic papers, organic EL displays, liquid crystal displays, IC tags (RFID tags), pressure sensors, and biosensors; organic EL display materials; organic semiconductor laser materials; organic thin films.
  • a thin film transistor that can be used as an electronic material such as a solar cell material; a photonic crystal material; a semiconductor material for an image pickup element, and an aromatic compound represented by the formula (1-I) or the formula (1-II) is crystalline. Therefore, it is preferable to use it as a semiconductor layer application of an organic thin film transistor.
  • a DSC Densilic Acid Meltiometer was used to measure the melting point of aromatic compounds.
  • Synthesis Example 1 Synthesis of dibromodithienobiphenylene derivative (Compound 3) (A1 step) 89.0 mg (0.336 mmol) of a dithienobiphenylene derivative (Compound 2 in the publication) synthesized by the method described in JP-A-2018-174322 in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, THF (Fuji Film Wako Pure Chemical Industries, Ltd.) (Derivative grade) 9 ml was added. The mixture was cooled to ⁇ 80 ° C., 0.75 mL (1.20 mmol) of 1.6 M normal butyllithium (Tokyo Chemical Industry) was added, and the mixture was stirred for 5 minutes and then stirred at room temperature for 25 minutes.
  • THF Fluji Film Wako Pure Chemical Industries, Ltd.
  • the mixture was aged at 0 ° C. for 220 minutes to prepare a 5-octylthiophene-2-ylmagnesium chloride solution.
  • 527 mg (3.86 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 7 ml of THF (dehydration grade) were added to a 100 ml Schlenk reaction vessel, and the mixture was cooled to 0 ° C.
  • the previously prepared 5-octylthiophene-2-ylmagnesium chloride solution was added dropwise to the obtained white fine slurry solution using a Teflon (registered trademark) cannula, and further using 2 ml of THF (dehydrated grade).
  • Synthesis Example 5 1,4-Bis (5-octylthiophene-2-yl) -2,5-dietinylbenzene Under a nitrogen atmosphere, the 1,4-bis (5-) synthesized in Synthesis Example 4 was placed in a 100 ml Schlenk reaction vessel. 540 mg (0.819 mmol) of octylthiophene-2-yl) -2,5-bis (trimethylsilylethynyl) benzene, 7 ml of THF, 3.5 ml of methanol, and 45.8 mg (0.331 mmol) of potassium carbonate were added. The mixture was stirred at room temperature for 3 hours.
  • Example 2 (Preparation of a solution for forming an organic semiconductor layer)
  • Compound 1 2,7-di (2-phenylethyl) dithienobiphenylene
  • 434 mg of toluene (Fuji Film Wako Pure Chemical Industries, Ltd., Pure Grade) synthesized in Example 1 were added.
  • the mixture was added, dissolved by heating at 50 ° C., and then allowed to cool at room temperature (25 ° C.) to prepare a solution for forming an organic semiconductor layer.
  • the solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 1 was 0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Example 3 (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor) A top gate-bottom contact type p-type organic thin film transistor was produced using the solution for forming an organic semiconductor layer obtained in Example 2.
  • Table 1 shows the materials of each component and the film forming method. Results were evaluated in the transfer characteristics of the transistor element, the carrier mobility of holes 1.45 cm 2 / V ⁇ sec, the current on-off ratio was 1.6 ⁇ 10 6. Further, the electrical characteristics of this organic thin film transistor after being annealed at 130 ° C. for 10 minutes were measured. Carrier mobility of holes 1.40cm 2 / V ⁇ sec, the current on-off ratio was 1.2 ⁇ 10 6, was hardly observed performance degradation due to heat treatment.
  • Example 4 (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor) Using the organic semiconductor layer forming solution obtained in Example 2, a bottom gate-bottom contact type p-type organic thin film transistor was produced using the materials and film forming methods of the constituent members shown in Example 3. Results were evaluated in the transfer characteristics of the transistor element, the carrier mobility of holes 2.29cm 2 / V ⁇ sec, the current on-off ratio was 1.5 ⁇ 10 6. Further, the electrical characteristics of this organic thin film transistor after being annealed at 130 ° C. for 10 minutes were measured. Carrier mobility of holes 2.25cm 2 / V ⁇ sec, the current on-off ratio was 1.0 ⁇ 10 6, was hardly observed performance degradation due to heat treatment.
  • Synthesis Example 7 Synthesis of 4-propylbenzene Ethanol In a nitrogen atmosphere, in a 100 ml Schlenk reaction vessel, 5.03 g (25.3 mmol) of 1-bromo-4-propylbenzene (Tokyo Chemical Industry) and THF (Fuji Film Wako Pure Chemical Industries, Ltd., dehydration) Grade) 80 ml was added. The mixture was cooled to ⁇ 78 ° C., 19.0 mL (30.4 mmol) of 1.6 M normal butyllithium (Tokyo Chemical Industry) was added, and the mixture was stirred at ⁇ 78 ° C. for 90 minutes.
  • Synthesis Example 8 Synthesis of 1- (2-bromoethyl) -4-propylbenzene 1.07 g (6.54 mmol) of 4-propylbenzene ethanol synthesized in Synthesis Example 7 and dichloromethane (Fuji Film) in a 100 ml two-necked flask under a nitrogen atmosphere. Wako Pure Chemical Industries, Ltd. (dehydrated grade) 30 ml was added. This solution was ice-cooled, 0.60 ml (6.32 mmol) of phosphorus tribromide was added, and the mixture was stirred for 20 minutes and then at room temperature for 22 hours.
  • the reaction solution was poured into ice, neutralized with saturated aqueous sodium hydrogen carbonate solution, and dichloromethane was added to separate the phases.
  • the organic phase was washed with saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (solvent; dichloromethane) to obtain 489 mg of a colorless liquid of 1- (2-bromoethyl) -4-propylbenzene (yield 33%).
  • Synthesis Example 9 Synthesis of 2- (4-propylphenyl) ethylmagnesium bromide (B1 step) Synthesis of magnesium (Fuji Film Wako Pure Chemical Industries, Ltd., shavings) 42.1 mg (1.73 mmol) in a 100 mL two-necked flask under a nitrogen atmosphere. Was added and stirred under vacuum for 2 hours. Under a nitrogen atmosphere, add 5 mL of a THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydration grade) solution of 1- (2-bromoethyl) -4-propylbenzene 231 mg (1.02 mmol) synthesized in Synthesis Example 8 at room temperature for 90 minutes. The mixture was stirred at 40 ° C. for 1 hour. The solid was removed by filtration to give a 0.2M 2- (4-propylphenyl) ethylmagnesium bromide / THF solution.
  • THF Flujifilm Wako Pure Chemical Industries, Ltd
  • Synthesis Example 10 Synthesis of 4-butylbenzene ethanol In a nitrogen atmosphere, in a 300 ml Schlenk reaction vessel, 4.34 g (20.4 mmol) of 1-bromo-4-butylbenzene (Tokyo Chemical Industry) and THF (Fuji Film Wako Pure Chemical Industries, Ltd., dehydration) Grade) 80 ml was added. The mixture was cooled to ⁇ 78 ° C., 26.0 mL (41.6 mmol) of 1.6 M normal butyllithium (Tokyo Chemical Industry) was added, and the mixture was stirred at ⁇ 78 ° C. for 2 hours.
  • Synthesis Example 11 Synthesis of 1- (2-bromoethyl) -4-butylbenzene 2.20 g (12.3 mmol) and dichloromethane (Fuji film) of 4-butylbenzene ethanol synthesized in Synthesis Example 10 in a 100 ml two-necked flask under a nitrogen atmosphere. Wako Pure Chemical Industries, dehydration grade) 30 ml was added. This solution was ice-cooled, 2.40 ml (25.2 mmol) of phosphorus tribromide was added, and the mixture was stirred for 10 minutes and then at room temperature for 25 hours.
  • the reaction solution was poured into ice, neutralized with saturated aqueous sodium hydrogen carbonate solution, and dichloromethane was added to separate the phases.
  • the organic phase was washed with saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (solvent; dichloromethane) to obtain 922 mg of a colorless liquid of 1- (2-bromoethyl) -4-butylbenzene (yield 31%).
  • Synthesis Example 12 Synthesis of 2- (4-butylphenyl) ethylmagnesium bromide (B1 step) Synthesis of magnesium (Fuji Film Wako Pure Chemical Industries, Ltd., shavings) 41.2 mg (1.69 mmol) in a 100 mL two-necked flask under a nitrogen atmosphere. Was added and stirred under vacuum for 2 hours. Under a nitrogen atmosphere, add 5 mL of a 1- (2-bromoethyl) -4-butylbenzene 248 mg (1.03 mmol) THF (Fujifilm Wako Pure Chemical Industries, Ltd. dehydration grade) solution synthesized in Synthesis Example 11 and leave at room temperature for 30 minutes. The mixture was stirred at 40 ° C. for 1 hour. The solid was removed by filtration to give a 0.2M 2- (4-butylphenyl) ethylmagnesium bromide / THF solution.
  • the reaction solution was poured into ice, neutralized with saturated aqueous sodium hydrogen carbonate solution, and dichloromethane was added to separate the phases.
  • the organic phase was washed with saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (solvent; dichloromethane) to obtain 1.74 g of a colorless liquid of 1- (2-bromoethyl) -4-heptylbenzene (yield 43%).
  • Synthesis Example 15 Synthesis of 2- (4-heptylphenyl) ethylmagnesium bromide (B1 step) Synthesis of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., shavings) 42.1 mg (1.73 mmol) in a 100 mL two-necked flask under a nitrogen atmosphere. Was added and stirred under vacuum for 2 hours. Under a nitrogen atmosphere, 5 mL of a THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydration grade) solution of 1- (2-bromoethyl) -4-heptylbenzene synthesized in Synthesis Example 14 of 288 mg (1.02 mmol) was added, and the mixture was added at room temperature for 40 minutes. The mixture was stirred at 40 ° C. for 1 hour. The solid was removed by filtration to give a 0.2M 2- (4-heptylphenyl) ethylmagnesium bromide / THF solution.
  • Synthesis Example 16 Synthesis of 2- (2,3-dihydrobenzofuran-5-yl) ethylmagnesium bromide (B1 step) Synthesis of magnesium (Fuji Film Wako Pure Chemical Industries, Ltd., shavings) 369 mg (Fuji Film Wako Pure Chemical Industries, Ltd.) in a 100 mL two-necked flask under a nitrogen atmosphere. 15.2 mmol) was added, and the mixture was stirred under vacuum for 2 hours.
  • Example 8 Synthesis of aromatic compound (Compound 7) (C1 step) Under a nitrogen atmosphere, 173 mg (1.30 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 5 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydration grade) were added to a 50 mL Schlenk tube, and the mixture was stirred under ice cooling. Add 2.50 mL (1.00 mmol) of the 0.4M 2- (2,3-dihydrobenzofuran-5-yl) ethylmagnesium bromide / THF solution synthesized in Synthesis Example 16 under ice-cooling for 30 minutes under ice-cooling.
  • zinc chloride Flujifilm Wako Pure Chemical Industries, Ltd.
  • THF Flujifilm Wako Pure Chemical Industries, Ltd., dehydration grade
  • Synthesis Example 18 4- (2-bromoethyl) -1,2-methylenedioxybenzene synthesis 2- (1,2-methylenedioxybenzene-4-) synthesized in Synthesis Example 17 in a 100 ml two-necked flask under a nitrogen atmosphere. Ill) 2.78 g (16.7 mmol) of ethanol and 20 ml of dichloromethane (Fuji Film Wako Pure Chemical Industries, Ltd., dehydration grade) were added. This solution was ice-cooled, 1.60 ml (16.8 mmol) of phosphorus tribromide was added, and the mixture was stirred for 30 minutes and then stirred at room temperature for 20 hours.
  • dichloromethane Fluji Film Wako Pure Chemical Industries, Ltd., dehydration grade
  • the reaction solution was poured into ice, neutralized with saturated aqueous sodium hydrogen carbonate solution, and dichloromethane was added to separate the phases.
  • the organic phase was washed with saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
  • a zinc reagent solution was prepared by stirring for 1 hour at room temperature for 15 hours.
  • (Sigma-Aldrich) 10.8 mg (0.0148 mmol) and THF (Fuji Film Wako Pure Chemical Industries, Ltd., dehydration grade) 8 mL were added.
  • Synthesis Example 21 Synthesis of 1,4-bis (thiophene-2-yl) -2,5-dietinylbenzene Under a nitrogen atmosphere, 1,4-bis (thiophene-2-yl) synthesized in Synthesis Example 20 was placed in a 300 ml eggplant flask. 5.38 g (12.4 mmol) of benzene-2,5-bis (trimethylsilylethynyl) benzene, 100 ml of THF, 50 ml of methanol, and 801 mg (5.79 mmol) of potassium carbonate were added. The mixture was stirred at room temperature for 6 hours. The obtained reaction mixture was ice-cooled and the reaction was stopped by adding 1M hydrochloric acid.
  • Synthesis Example 22 Synthesis of anthra [1,2-b: 5,6-b'] dithiophene (Compound 19) 1,4-bis (thiophene-2) synthesized in Synthesis Example 21 in a 200 ml Schlenk reaction vessel under a nitrogen atmosphere.
  • -Il) -2,5-dietinylbenzene 1.74 g (6.00 mmol), N, N-dimethylformamide 60 ml, and platinum chloride (Fuji Film Wako Pure Chemical Industries, Ltd.) 323 mg (1.21 mmol) were added.
  • the obtained mixture was stirred at 80 ° C. for 4 hours, and then the solvent was distilled off under reduced pressure.
  • Synthesis Example 23 Synthesis of 2,8-dibromoanthra [1,2-b: 5,6-b'] dithiophene (Compound 20) (step A-2) Anthra [1,2-b: 5,6-b'] dithiophene (Compound 19) 602 mg (2.07 mmol) synthesized in Synthesis Example 22 and THF (Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere. , Dehydration grade) 50 ml was added.
  • the mixture was cooled to ⁇ 78 ° C., 6.00 mL (9.60 mmol) of 1.6 M normal butyllithium (Tokyo Chemical Industry) was added, and the mixture was stirred for 20 minutes and then stirred at room temperature for 50 minutes.
  • the mixture was cooled to ⁇ 78 ° C., 25 mL of a THF solution (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) of 3.45 g (10.6 mmol) of 1,2-dibromotetrachloroethane was added, and the mixture was stirred while raising the temperature to room temperature.
  • a THF solution Flujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade
  • the obtained solid was rinsed with methanol, recrystallized from toluene and purified from 2,8-di (2-phenylethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 10). 73.2 mg of a yellow solid was obtained (yield 42%).
  • Example 11 Synthesis of 2- (2-phenylethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 15) (C2 step) Another component obtained by silica gel column chromatography of Example 10 was recrystallized from hexane to purify 2- (2-phenylethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 15). ) was obtained in an amount of 2.0 mg (yield 1.5%).
  • reaction mixture was ice-cooled, 1M hydrochloric acid was added, and then toluene was added to separate the phases.
  • the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
  • Example 13 Synthesis of 2- (2- (4-normal butylphenyl) ethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 17) (C2 step) Another component obtained by silica gel column chromatography of Example 12 was recrystallized from hexane and purified into 2- (2- (4-normal butylphenyl) ethyl) anthra [1,2-b: 5,6-b. '] 5.8 mg of a yellow solid of dithiophene (Compound 17) was obtained (yield 15%).
  • Example 15 Synthesis of 2- (2- (4-normal heptylphenyl) ethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 18) (step C2) Another component obtained by silica gel column chromatography of Example 14 was recrystallized from hexane and purified to 2- (2- (4-normal heptylphenyl) ethyl) anthra [1,2-b: 5,6-b. '] 3.5 mg of a yellow solid of dithiophene (Compound 18) was obtained (yield 10%).
  • the zinc reagent solution prepared above was added dropwise using a Teflon (registered trademark) cannula, and the mixture was stirred at room temperature for 5 hours.
  • the reaction mixture was ice-cooled, 1M hydrochloric acid was added, and then toluene was added to separate the phases.
  • the organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography (solvent; hexane).
  • the obtained solid was rinsed with methanol to obtain 15.1 mg of a yellow solid of 2- (2-phenylethyl) dithienobiphenylene (Compound 13) (yield 39%).
  • Synthesis Example 26 Synthesis of 2- (4-methylphenyl) ethylmagnesium bromide (B1 step) Under a nitrogen atmosphere, 228 mg (9.36 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., shavings) was added to a 50 mL two-necked flask, and the mixture was stirred under vacuum for 1 hour. Under a nitrogen atmosphere, add 20 mL of a solution of 1.60 g (8.02 mmol) of 1- (2-bromoethyl) -4-methylbenzene synthesized in Synthesis Example 25 in THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydration grade), and add 90 at room temperature. Stir for minutes. The solid was removed by filtration to give a 0.4M 2- (4-methylphenyl) ethylmagnesium bromide / THF solution.
  • Synthesis Example 27 Synthesis of 2-bromoanthra [1,2-b: 5,6-b'] dithiophene (Compound 22) (Step A-4) In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 481 mg (1.66 mmol) of anthra [1,2-b: 5,6-b'] dithiophene (Compound 19) synthesized in Synthesis Example 22, THF (Fujifilm Wako Pure Chemical Industries, Ltd.) , Dehydration grade) 57 ml was added.
  • Synthesis Example 28 Synthesis of 1,5-bis (trimethylsilylethynyl) -2,6-difluorobiphenylene (D1 step) 2,6-Difluoro-1,5-diiodobiphenylene 260 mg (0.591 mmol), bis (triphenylphosphine) dichloro synthesized in a 50 mL Schlenck reaction vessel under a nitrogen atmosphere using the method described in JP-A-2018-174322.
  • Example 20 (Preparation of a solution for forming an organic semiconductor layer) Organic semiconductor by the same method as in Example 2 except that 0.44 mg of 2,7-di (2- (4-propylphenyl) ethyl) dithienobiphenylene (Compound 4) synthesized in Example 5 was used. A layering solution was prepared. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 4 was 0.10% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Compound 4 2,7-di (2- (4-propylphenyl) ethyl) dithienobiphenylene
  • Example 21 (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor) Using the organic semiconductor layer forming solution obtained in Example 20, a bottom gate-bottom contact type p-type organic thin film transistor was produced using the materials and film forming methods of the constituent members shown in Example 3. Results were evaluated in the transfer characteristics of the transistor element, the carrier mobility of holes 1.86cm 2 / V ⁇ sec, the current on-off ratio was 1.1 ⁇ 10 6. Further, the electrical characteristics of this organic thin film transistor after being annealed at 130 ° C. for 10 minutes were measured. Carrier mobility of holes 1.70cm 2 / V ⁇ sec, the current on-off ratio was 1.0 ⁇ 10 6, was hardly observed performance degradation due to heat treatment.
  • Example 22 (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor) Add 0.87 mg of 2,7-di (2- (4-propylphenyl) ethyl) dithienobiphenylene (Compound 4) and 440 mg of anisole (Sigma-Aldrich) synthesized in Example 5 to a 10 ml sample tube under air. Then, the mixture was heated at 60 ° C. to prepare a 0.20% by weight solution of Compound 4. Using the obtained solution, a bottom gate-bottom contact type p-type organic thin film transistor was produced using the materials and film forming methods of the constituent members shown in Example 3.
  • Results were evaluated in the transfer characteristics of the transistor element, the carrier mobility of holes 2.48cm 2 / V ⁇ sec, the current on-off ratio was 1.6 ⁇ 10 6. Further, the electrical characteristics of this organic thin film transistor after being annealed at 130 ° C. for 10 minutes were measured. Carrier mobility of holes 2.40cm 2 / V ⁇ sec, the current on-off ratio was 1.4 ⁇ 10 6, was hardly observed performance degradation due to heat treatment.
  • Example 23 (Preparation of a solution for forming an organic semiconductor layer) Organic semiconductor by the same method as in Example 2 except that 1.74 mg of 2,7-di (2- (4-butylphenyl) ethyl) dithienobiphenylene (Compound 5) synthesized in Example 6 was used. A layer-forming solution was prepared. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 5 was 0.40% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Compound 5 2,7-di (2- (4-butylphenyl) ethyl) dithienobiphenylene
  • Example 24 (Preparation of Solution for Forming Organic Semiconductor Layer) Organic semiconductor by the same method as in Example 2 except that 0.87 mg of 2,7-di (2- (4-heptylphenyl) ethyl) dithienobiphenylene (Compound 6) synthesized in Example 7 was used. A layering solution was prepared. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 6 was 0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Compound 6 2,7-di (2- (4-heptylphenyl) ethyl) dithienobiphenylene
  • Example 25 (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor) Using the organic semiconductor layer forming solution obtained in Example 24, a bottom gate-bottom contact type p-type organic thin film transistor was produced using the materials and film forming methods of the constituent members shown in Example 3. Results were evaluated in the transfer characteristics of the transistor element, the carrier mobility of holes 1.19 cm 2 / V ⁇ sec, the current on-off ratio was 1.1 ⁇ 10 6. Further, the electrical characteristics of this organic thin film transistor after being annealed at 130 ° C. for 10 minutes were measured. Carrier mobility of holes 1.15cm 2 / V ⁇ sec, the current on-off ratio was 1.0 ⁇ 10 6, was hardly observed performance degradation due to heat treatment.
  • Example 26 (Preparation of Solution for Forming Organic Semiconductor Layer) Example 2 except that 0.87 mg of 2,8-di (2-phenylethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 10) synthesized in Example 10 was used. A solution for forming an organic semiconductor layer was prepared by the same method as in the above. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 10 was 0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Compound 10 2,8-di (2-phenylethyl) anthra [1,2-b: 5,6-b'] dithiophene synthesized in Example 10 was used.
  • a solution for forming an organic semiconductor layer was prepared by the same method as in the above. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 10 was 0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop
  • Example 27 (Preparation of Solution for Forming Organic Semiconductor Layer) A solution for forming an organic semiconductor layer was prepared by the same method as in Example 2 except that 4.35 mg of 2- (2-phenylethyl) dithienobiphenylene (Compound 13) synthesized in Example 16 was used. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 13 was 1.00% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Compound 13 2- (2-phenylethyl) dithienobiphenylene
  • Example 28 (Preparation of a solution for forming an organic semiconductor layer) For forming an organic semiconductor layer by the same method as in Example 2 except that 4.35 mg of 2- (2- (4-methylphenyl) ethyl) dithienobiphenylene (Compound 14) synthesized in Example 17 was used. The solution was prepared. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 14 was 1.00% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Example 29 (Preparation of a solution for forming an organic semiconductor layer) Same as in Example 2 except that 1.74 mg of 2- (2-phenylethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 15) synthesized in Example 11 was used. A solution for forming an organic semiconductor layer was prepared by the method. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 15 was 0.40% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Example 30 (Preparation of a solution for forming an organic semiconductor layer) This was carried out except that 2.18 mg of 2- (2- (4-methylphenyl) ethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 16) synthesized in Example 18 was used.
  • a solution for forming an organic semiconductor layer was prepared by the same method as in Example 2. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 16 was 0.50% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Example 31 (Preparation of a solution for forming an organic semiconductor layer) Except for using 4.35 mg of 2- (2- (4-normalbutylphenyl) ethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 17) synthesized in Example 13.
  • a solution for forming an organic semiconductor layer was prepared by the same method as in Example 2. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 17 was 1.00% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Example 32 (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor) Except for using 0.87 mg of 2- (2- (4-normalbutylphenyl) ethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 17) synthesized in Example 13.
  • a solution for forming an organic semiconductor layer was prepared by the same method as in Example 2 (concentration of compound 17 was 0.20% by weight). Using the obtained solution for forming an organic semiconductor layer, a bottom gate-bottom contact type p-type organic thin film transistor was produced using the materials and film forming methods of the constituent members shown in Example 3.
  • Results were evaluated in the transfer characteristics of the transistor element, the carrier mobility of holes 1.13 cm 2 / V ⁇ sec, the current on-off ratio was 8.1 ⁇ 10 7. Further, the electrical characteristics of this organic thin film transistor after being annealed at 130 ° C. for 10 minutes were measured. Carrier mobility of holes 1.10cm 2 / V ⁇ sec, the current on-off ratio was 8.0 ⁇ 10 7, was hardly observed performance degradation due to heat treatment.
  • Example 33 (Preparation of a solution for forming an organic semiconductor layer) Except for using 0.87 mg of 2- (2- (4-normal heptylphenyl) ethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 18) synthesized in Example 15.
  • a solution for forming an organic semiconductor layer was prepared by the same method as in Example 2. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 18 was 0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Synthesis Example 31 Synthesis of 4-propoxybenzene ethanol In a nitrogen atmosphere, in a 300 ml Schlenk reaction vessel, 4.51 g (21.0 mmol) of 1-bromo-4-propoxybenzene (Tokyo Chemical Industry) and THF (Fuji Film Wako Pure Chemical Industries, Ltd., dehydration) Grade) 80 ml was added. The mixture was cooled to ⁇ 78 ° C., 22.0 mL (35.0 mmol) of 1.6 M normal butyllithium (Tokyo Chemical Industry) was added, and the mixture was stirred at ⁇ 78 ° C. for 2 hours.
  • Synthesis Example 33 Synthesis of 2- (4-propoxyphenyl) ethylmagnesium bromide (B1 step) Under a nitrogen atmosphere, 172 mg (7.06 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., shavings) was added to a 20 mL two-necked flask, and the mixture was stirred under vacuum for 1 hour. Under a nitrogen atmosphere, add 15 mL of a solution of 1.46 g (6.00 mmol) of 1- (2-bromoethyl) -4-propoxybenzene synthesized in Synthesis Example 32 in THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydration grade), and add 1 at room temperature. Stirred for hours. The solid was removed by filtration to give a 0.4M 2- (4-propoxyphenyl) ethylmagnesium bromide / THF solution.
  • Example 36 (Preparation of a solution for forming an organic semiconductor layer) Except for using 4.35 mg of 2- (2- (4-propoxyphenyl) ethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 23) synthesized in Example 34.
  • a solution for forming an organic semiconductor layer was prepared by the same method as in Example 2. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 23 was 1.00% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Example 37 (Preparation of a solution for forming an organic semiconductor layer) Except for the use of 0.44 mg of 2- (2- (4-methoxyphenyl) ethyl) anthra [1,2-b: 5,6-b'] dithiophene (Compound 24) synthesized in Example 35.
  • a solution for forming an organic semiconductor layer was prepared by the same method as in Example 2. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 24 was 0.10% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Comparative Example 2 (Preparation of solution for forming organic semiconductor layer) Using 2,7-dioctyl [1] benzothiophene [3,2-b] [1] benzothiophene (Sigma-Aldrich) in a 10 ml sample tube under air, an organic semiconductor layer is formed by the same method as in Example 2. A solution was prepared. The solution state was maintained at 25 ° C. for 10 hours (0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Comparative Example 3 (Preparation of solution for forming organic semiconductor layer)
  • 2,7-di (normal octyl) dithienobiphenylene (Compound 3 in the publication) described in JP-A-2018-174322 was used, and an organic semiconductor layer was used in the same manner as in Example 2.
  • a forming solution was prepared. The solution state was maintained at 25 ° C. for 10 hours (0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • Comparative Example 4 (Preparation of solution for forming organic semiconductor layer)
  • 2,8-dioctyl anthra [1,2-b: 5,6-b'] dithiophene synthesized in Synthesis Example 6 was used, and an organic semiconductor layer was used in the same manner as in Example 2.
  • a forming solution was prepared. The solution state was maintained at 25 ° C. for 10 hours (0.20% by weight), and it was confirmed that the compound was suitable for film formation by drop casting and inkjet.
  • the aromatic compound of the present invention provides high carrier mobility and is excellent in heat resistance and solubility, so that it can be expected to be applied as a semiconductor device material represented by an organic thin film transistor.
  • A Bottom gate-top contact type organic thin film transistor
  • B Bottom gate-bottom contact type organic thin film transistor
  • C Top gate-top contact type organic thin film transistor
  • D Top gate-bottom contact type organic thin film transistor 1: Organic semiconductor layer 2: Substrate 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Thin Film Transistor (AREA)
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