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WO2016047391A1 - Organic semiconductor element, method for producing same, compound, composition for forming organic semiconductor film, and organic semiconductor film - Google Patents

Organic semiconductor element, method for producing same, compound, composition for forming organic semiconductor film, and organic semiconductor film Download PDF

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Publication number
WO2016047391A1
WO2016047391A1 PCT/JP2015/074800 JP2015074800W WO2016047391A1 WO 2016047391 A1 WO2016047391 A1 WO 2016047391A1 JP 2015074800 W JP2015074800 W JP 2015074800W WO 2016047391 A1 WO2016047391 A1 WO 2016047391A1
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group
formula
organic semiconductor
ring
represented
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PCT/JP2015/074800
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French (fr)
Japanese (ja)
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北村 哲
友樹 平井
健介 益居
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富士フイルム株式会社
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Priority to JP2016550080A priority Critical patent/JP6205074B2/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D487/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D495/00Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D495/00Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D495/00Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40Organic transistors

Definitions

  • the present invention relates to an organic semiconductor device and a method of manufacturing the same, a compound, a composition for forming an organic semiconductor film, and an organic semiconductor film.
  • FET Field Effect Transistor
  • RFID Radio Frequency Identifier, RF tag
  • liquid crystal display organic EL (organic electroluminescence) display
  • organic transistor having an organic semiconductor film (organic semiconductor layer) is used.
  • organic semiconductor layer organic semiconductor layer
  • the problem to be solved by the present invention is to provide an organic semiconductor device having high mobility, excellent thermal stability, and suppressed variation in mobility, and a method for manufacturing the same.
  • Another object of the present invention is to provide a novel compound suitable as an organic semiconductor.
  • another problem to be solved by the present invention is to preferably form an organic semiconductor film having high mobility, excellent thermal stability, and suppressed variation in mobility, and the above organic semiconductor film. It is to provide a composition for forming an organic semiconductor film that can
  • each X independently represents any of O, S, Se, and NR
  • each R independently represents a substituent
  • each ring A independently represents a 5- or 6-membered monocyclic aromatic ring.
  • Group hydrocarbon ring or aromatic heterocyclic ring m represents an integer of 1 to 5, and when m is 2 to 5, plural rings A may be the same or different, and n is an integer of 0 or more
  • m 1, at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when m is 4 or 5, three or more R's are an aromatic hydrocarbon group or an aromatic complex It can not be a ring group.
  • each ring A independently represents a benzene ring, a furan ring, a thiophene ring, a selenophen ring, or a pyrrole ring, and the symmetry of the partial structure from which R in the formula 1 is removed is C 2, C 2v, or a C 2h, the organic semiconductor device according to ⁇ 1>, ⁇ 3>
  • T represents any structure selected from the group consisting of T-1 to T-35 below, R ′ independently represents a substituent, n represents an integer of 0 to 6, and T represents When at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group when T is T-1 or T-2, and three when T is any of T-20 to T-35 The above R 'does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • X each independently represents any of O, S, Se, and NR '.
  • L is each independently a divalent linking group represented by any one of the following Formulas L-1 to L-12, or any of two or more of the following Formulas L-1 to L-12.
  • Z's independently represents a hydrogen atom, an alkyl group, or an oligooxyethylene group having a repeating number of oxyethylene units of 2 or more.
  • R L1 in Formula L-1, Formula L-2 and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.
  • ⁇ 6> a compound represented by the above formula 2, ⁇ 7> The compound according to ⁇ 6>, wherein R ′ is represented by the above formula 3, ⁇ 8> The compound according to ⁇ 6> or ⁇ 7>, wherein each X independently represents O or S, ⁇ 9> The compound according to any one of ⁇ 6> to ⁇ 8>, which is an organic semiconductor, ⁇ 10> A composition for forming an organic semiconductor film, comprising: an organic semiconductor represented by the above formula 1; and a solvent ⁇ 11>
  • ring A respectively independently represents a benzene ring, a furan ring, a thiophene ring, a selenophen ring, or a pyrrole ring, and the symmetry of the partial structure from which R in Formula 1 is removed is C 2, C 2v, or a C 2h, the organic semiconductor film forming composition as described in ⁇ 10>,
  • the composition for organic-semiconductor film formation as described in any one of ⁇ 10>- ⁇ 13> in which ⁇ 14> X respectively independently represents O or S, ⁇ 15> The organic semiconductor film according to any one of ⁇ 10> to ⁇ 14>, wherein the concentration of the organic semiconductor represented by the above formula 1 is 0.5 to 15% by mass with respect to the entire composition.
  • composition for forming ⁇ 16> the boiling point of the solvent is 100 ° C. or higher, ⁇ 10> - an organic semiconductor film forming composition according to any one of ⁇ 15>, ⁇ 17>
  • a method of manufacturing an organic semiconductor device comprising a coating step of coating the composition for forming an organic semiconductor film according to any one of ⁇ 10> to ⁇ 18> on a substrate,
  • an organic semiconductor device having high mobility, excellent thermal stability, and suppressed variation in mobility, and a method of manufacturing the same.
  • a novel compound suitable as an organic semiconductor can be provided.
  • an organic semiconductor film having high mobility, excellent thermal stability, and suppressed variation in mobility, and organic semiconductor film formation capable of suitably forming the above organic semiconductor film It was possible to provide a composition for use.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the chemical structural formula in this specification may be described by the simplified structural formula which abbreviate
  • mobility means carrier mobility and means either or both of electron mobility and hole mobility.
  • mass% and weight% are synonymous, and “mass part” and “part by weight” are synonymous.
  • a combination of preferred embodiments is more preferred.
  • organic semiconductor device and compound The organic semiconductor device of the present invention is characterized by having an organic semiconductor layer containing the organic semiconductor represented by the above-mentioned formula 1 (hereinafter, also referred to as “specific organic semiconductor compound” or “specific compound”).
  • the inventors of the present invention conducted intensive studies, and as a result, by containing the above specific organic semiconductor compound, the obtained organic semiconductor device or organic semiconductor film has high mobility, excellent thermal stability, and variation in mobility. It has been found that it is suppressed, and the present invention has been completed. Although the mechanism of expression of detailed effects is unknown, the above-mentioned specific organic semiconductor compounds are likely to have a large overlap of HOMO (Highest Occupied Molecular Orbital) between molecules, have high mobility, and have excellent thermal stability, and It is estimated that the variation in mobility is suppressed.
  • HOMO Highest Occupied Molecular Orbital
  • the specific organic semiconductor compound is represented by the following formula 1.
  • each X independently represents any of O, S, Se, and NR
  • each R independently represents a substituent
  • each ring A independently represents a 5- or 6-membered monocyclic aromatic ring.
  • Group hydrocarbon ring or aromatic heterocyclic ring m represents an integer of 1 to 5, and when m is 2 to 5, plural rings A may be the same or different, and n is an integer of 0 or more
  • m 1, at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when m is 4 or 5, three or more R's are an aromatic hydrocarbon group or an aromatic complex It can not be a ring group.
  • the specific organic semiconductor compound of the present invention is a novel compound. Also, certain organic semiconductor compounds of the present invention, the organic semiconductor element, an organic semiconductor film, and can be suitably used for the organic semiconductor film-forming composition.
  • the specific organic semiconductor compound of the present invention hetero atoms of the heteroaromatic ring present at both ends of ring A are arranged outward with respect to ring A.
  • each ring A independently represents a 5- or 6-membered monocyclic aromatic hydrocarbon ring or aromatic heterocycle.
  • a benzene ring is illustrated as an aromatic hydrocarbon ring.
  • the hetero atom of the heteroaromatic ring is not particularly limited, and examples thereof include S, O, N and Se.
  • Examples of the heteroaromatic ring include thiophene ring, furan ring, pyran ring, pyrrole ring, pyridine ring, pyrazine ring, A pyrimidine ring, a pyridazine ring, a selenophen ring, an imidazole ring, etc. are mentioned.
  • the ring A is preferably each independently a benzene ring, a thiophene ring, a selenophen ring or a pyrrole ring, more preferably a benzene ring, a thiophene ring or a furan ring, a benzene ring or a thiophene ring It is further preferred that When a plurality of rings A are present, that is, m is 2 or more, the plurality of rings A may be the same or different and is not particularly limited.
  • the specific organic semiconductor compound is a compound containing an aromatic hydrocarbon group or an aromatic heterocyclic group (condensed polycyclic aromatic group containing a condensed ring of 3 or more rings) containing a condensed ring of 3 to 7 rings.
  • the structure obtained by removing the substituent R from the specific organic semiconductor compound is also referred to as a “fused polycyclic aromatic group”.
  • m represents an integer of 1 to 5.
  • m is preferably 1 to 4, and more preferably 2 to 4. That is, the number of rings in the fused polycyclic aromatic group excluding the substituent R from the specific organic semiconductor compound is 3 to 7, preferably 3 to 6, from the viewpoint of mobility as an organic semiconductor. 6 is more preferable.
  • the partial structure obtained by removing R from the specific organic semiconductor compound that is, the symmetry of the fused polycyclic aromatic group obtained by removing R which is a substituent from the specific organic semiconductor is C 2 , C 2 v or C 2 h Is preferred.
  • the symmetry is C 2 , C 2 v or C 2 h, it is easy to form an ordered crystal structure and easily express high mobility.
  • the description of "Symmetry of molecules and group theory" (Nakazaki Masao, Tokyo Kagaku Dojin) is referred to.
  • R respectively independently represents a substituent.
  • n 2 or more, a plurality of R may be the same or different.
  • R represents a halogen atom, alkyl group (including cycloalkyl group, bicycloalkyl group and tricycloalkyl group), alkenyl group, alkynyl group, aryl group (aromatic hydrocarbon group), heterocyclic group (heterocyclic group (Including aromatic heterocyclic groups and aliphatic heterocyclic groups), cyano groups, hydroxy groups, nitro groups, carboxy groups, alkoxy groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino
  • R is preferably a halogen atom, an alkyl group, an alkoxy group, an alkynyl group, an acyl group, an acyloxy group, an aryl group or a heterocyclic group, and an alkyl group, an aryl group (aromatic hydrocarbon group) or An aromatic heterocyclic group is more preferred.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, and a fluorine atom is preferable.
  • the alkyl group is preferably an alkyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 3 to 15 carbon atoms, and still more preferably an alkyl group having 4 to 12 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, or may have a structure combining them, but is preferably a linear or branched alkyl group, and is a linear alkyl group Is more preferred.
  • the alkoxy group is preferably an alkoxy group having 2 to 18 carbon atoms, more preferably an alkoxy group having 3 to 15 carbon atoms, and still more preferably an alkoxy group having 4 to 12 carbon atoms.
  • the alkyl group portion of the alkoxy group may be linear, branched or cyclic, or may be a combination of these, but is preferably a linear or branched alkyl group.
  • the alkynyl group is preferably an alkynyl group having 2 to 18 carbon atoms, more preferably an alkynyl group having 3 to 15 carbon atoms, and still more preferably an alkynyl group having 4 to 12 carbon atoms.
  • aryl group aromatic hydrocarbon group
  • aromatic hydrocarbon group examples include groups in which one hydrogen is removed from benzene, naphthalene, anthracene or the like.
  • aromatic heterocyclic group groups in which one hydrogen atom has been removed from a thiophene ring, furan ring, pyran ring, pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, selenophen ring, imidazole ring, etc.
  • a group in which one hydrogen atom is removed from a thiophene ring, a selenophen ring, or a pyrrole ring more preferably a group in which one hydrogen atom is removed from a thiophene ring or a furan ring, More preferably, it is a group in which one hydrogen atom has been removed from the ring.
  • At least one of R represents an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • m 1, unless at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, sufficient mobility can not be obtained because the ⁇ conjugated system is small.
  • m 1, it is preferable that at least one of R is an aromatic hydrocarbon group or an aromatic heterocyclic group, and from the viewpoint of mobility, at least two are an aromatic hydrocarbon group or an aromatic heterocyclic group .
  • examples of the aromatic hydrocarbon group represented by R include groups in which one hydrogen atom has been removed from a benzene ring, a naphthalene ring, an anthracene ring or the like.
  • a group in which one hydrogen atom is removed from a benzene ring or a naphthalene ring is preferable, and a group in which one hydrogen atom is removed from a benzene ring is particularly preferable.
  • the aromatic heterocyclic group represented by R one hydrogen atom is removed from a thiophene ring, furan ring, pyran ring, pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, selenophen ring, imidazole ring, etc.
  • Preferred is a group in which one hydrogen atom is removed from a thiophene ring, a selenophen ring, or a pyrrole ring, and a group in which one hydrogen atom is removed from a thiophene ring or a furan ring More preferably, it is a group obtained by removing one hydrogen atom from a thiophene ring.
  • the aromatic hydrocarbon group or aromatic heterocyclic group represented by R is particularly preferably a group obtained by removing one hydrogen atom from a benzene ring or a thiophene ring.
  • 0 to 2 Rs are an aromatic hydrocarbon group or an aromatic heterocyclic group
  • 0 or 1 R is an aromatic hydrocarbon group or an aromatic heterocyclic group It is more preferable not to have R which represents an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • N represents an integer of 0 or more and means the number of substitution of R for a fused polycyclic aromatic group.
  • n is an integer of 1 or more, and when m is 2 to 5, n is an integer of 0 or more.
  • n is preferably 1 or more, and more preferably 2 or more.
  • the upper limit of n is not particularly limited, but is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less from the viewpoint of mobility and film formability.
  • the specific organic semiconductor compound includes a fused polycyclic aromatic group containing a ring A (fused polycyclic aromatic structure), and it is preferable that this group be included as a main component.
  • the main component means that the content of the molecular weight of the fused polycyclic aromatic group is 30% or more with respect to the total molecular weight of the specific organic semiconductor compound, and is preferably 40% or more.
  • the upper limit is not particularly limited, but is preferably 95% or less from the viewpoint of solubility.
  • the specific organic semiconductor compound is more preferably a compound represented by the following formula 2.
  • T represents any structure selected from the group consisting of T-1 to T-35 below, R ′ independently represents a substituent, n represents an integer of 0 to 6, and T represents When at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group when T is T-1 or T-2, and three when T is any of T-20 to T-35 The above R 'does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • X each independently represents any of O, S, Se, and NR '.
  • T is T-1, T-2, T-3, T-4, T-9, T-11, T-22, T-23, T-24, T-25 T-3, T-4, T-9, T-11 and T-22 are more preferable, and T-9 and T-11 are more preferable.
  • R ' is synonymous with R in Formula 1.
  • the preferable range of X is the same as the preferable range of X in Formula 1.
  • R ′ is preferably represented by Formula 3 below.
  • L is each independently a divalent linking group represented by any one of the following Formulas L-1 to L-12, or any of two or more of the following Formulas L-1 to L-12.
  • Z's independently represents a hydrogen atom, an alkyl group, or an oligooxyethylene group having a repeating number of oxyethylene units of 2 or more.
  • R L1 in Formula L-1, Formula L-2 and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.
  • the dashed line represents a bonding position to any structure selected from the group consisting of T-1 to T-35, and * represents a bonding position to Z, or It is preferable to represent the bonding position with a divalent linking group selected from the group consisting of other L-1 to L-12.
  • L represents a linking group to which a divalent linking group represented by any one of the above formulas L-1 to L-12 is bonded
  • the table is represented by any one of formulas L-1 to L-12.
  • the number of bonded bivalent linking groups is preferably 2 to 4, and more preferably 2 or 3.
  • L1, in L-2, L-10, L-11 and L-12, R L1 existing in plural numbers may be the same or different.
  • RL1 may be bonded to Z adjacent thereto to form a ring structure, or may form a fused ring as the above ring structure.
  • R L1 include a hydrogen atom, and various substituents exemplified as R in the above-mentioned formula 1.
  • the divalent linking group represented by the above formula L-10 is a divalent linking group represented by the following formula L-10A, formula L-10B, or formula L-10C, and the formula L-10A or
  • the divalent linking group represented by the formula L-10B is preferable, and the divalent linking group represented by the formula L-10B is more preferable.
  • the divalent linking group represented by the above formula L-12 is a divalent linking group represented by the following formula L-12A, L-12B or L-12C, and in the formula L-12A or L-12B
  • the divalent linking group represented is preferable, and the divalent linking group represented by the formula L-12B is more preferable.
  • L is a divalent linking group represented by any one of formulas L-1 to L-6, L-10, L-11 and L-12, or two or more of these divalent linking groups are bonded
  • a divalent linking group is preferable, and a divalent linking group represented by any one of formulas L-1 to L-5, L-10, L-11 and L-12, or a divalent thereof Is more preferably a divalent linking group in which two or more linking groups are linked, and from the viewpoint of obtaining chemical stability and high mobility, the formulas L-1, L-3, L-10, L-11 and More preferably, it is a divalent linking group represented by any one of L-12, or a divalent linking group in which two or more of these divalent linking groups are bonded, as represented by formulas L-1 and L-3.
  • L-10 and L-12 or a divalent linking group in which two or more of these divalent linking groups are bonded to each other.
  • a divalent linking group represented by the formula L-1 or L-3 or a divalent linking group in which two or more of these divalent linking groups are bonded.
  • Z is an alkyl group
  • it is not particularly limited as long as it is an alkyl group having 1 or more carbon atoms, but from the viewpoint of chemical stability and carrier transportability, the number of carbon atoms is preferably 2 to 18 and 3 to 12 more preferably, more preferably from 4 to 10, particularly preferably from 4 to 8, most preferably 4-6.
  • the carrier mobility becomes high when the alkyl group represented by Z is at least the lower limit value of the above range.
  • the alkyl group represented by Z may be linear, branched or cyclic, and is preferably a linear alkyl group from the viewpoint of enhancing carrier mobility, and is a linear alkyl group having 1 to 12 carbon atoms.
  • a halogen atom etc. can be mentioned as a substituent in case Z is an alkyl group which has a substituent, A fluorine atom is preferable.
  • Z is an alkyl group having a fluorine atom, all hydrogen atoms of the alkyl group may be substituted with a fluorine atom to form a perfluoroalkyl group.
  • the oxyethylene unit represented by Z is a group represented by-(OCH 2 CH 2 ) x OY in the present specification.
  • the repeating number x of the oxyethylene unit represents an integer of 2 or more, and the terminal Y represents a hydrogen atom or a substituent.
  • Y at the end of the oligooxyethylene group is a hydrogen atom, it is a hydroxy group.
  • the repeat number x of the oxyethylene unit is preferably 2 to 4, and more preferably 2 to 3. It is preferable that the terminal hydroxy group of the oligooxyethylene group is sealed, that is, Y represents a substituent.
  • the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. Is more preferable, and a methyl group is more preferable.
  • the number of repetition of the siloxane unit is preferably 2 to 4, and more preferably 2 to 3.
  • a hydrogen atom or an alkyl group is preferably bonded to the Si atom.
  • the carbon number of the alkyl group is preferably 1 to 3, and for example, a methyl group or an ethyl group is preferably bonded.
  • the same alkyl group may be bonded to the Si atom, or different alkyl groups or hydrogen atoms may be bonded.
  • Z can take a substituted or unsubstituted trialkylsilyl group.
  • the carbon number of the alkyl group bonded to the Si atom is preferably 1 to 3, and for example, a methyl group, an ethyl group or an isopropyl group is preferably bonded .
  • the same alkyl group may be bonded to a Si atom, or different alkyl groups may be bonded.
  • Z is a trialkylsilyl group having a substituent, the substituent is not particularly limited.
  • the fused polycyclic aromatic group organic semiconductor mother nucleus containing the ring A in the formula 1 or T in the formula 2
  • the fused polycyclic aromatic group t-1 to Although t-35
  • the present invention is not limited to these examples.
  • t-1, t-2, t-3, t-4, t-9, t-11, t-22, t-23, t-24 and t-25 are preferable, and t-3, t-4, t-9, t-11 and t-22 are more preferable, and t-9 and t-11 are more preferable.
  • the molecular weight of the specific organic semiconductor compound is not particularly limited, but it is preferably 1,500 or less, more preferably 1,000 or less, still more preferably 800 or less, and 700 or less. Is particularly preferred. By setting the molecular weight to the above upper limit or less, the solubility in a solvent can be enhanced. On the other hand, from the viewpoint of the film quality stability of the thin film, the molecular weight is preferably 400 or more, more preferably 450 or more, and still more preferably 500 or more. Even if only one specific organic semiconductor compound is contained in an organic semiconductor layer described later, an organic semiconductor film to be described later, or a composition for forming an organic semiconductor film, two or more specific organic semiconductor compounds are contained. Although it may be used, from the viewpoint of orientation, it is preferable to be only one kind.
  • the synthesis method of the specific organic semiconductor compound is not particularly limited, and can be synthesized with reference to known methods.
  • a synthesis method an organic semiconductor mother nucleus having a halogen atom as a substituent is synthesized, and various coupling reactions such as Stille coupling reaction, Suzuki-Miyaura coupling reaction, Negishi coupling reaction, and Kumada coupling reaction are performed. Can be mentioned.
  • the content of the specific organic semiconductor compound in the organic semiconductor layer of the organic semiconductor device of the present invention or the organic semiconductor film of the present invention described later is preferably 30 to 100% by mass, and is 50 to 100% by mass. More preferably, it is 70 to 100% by mass.
  • the content is preferably 90 to 100% by mass, and more preferably 95 to 100% by mass.
  • the organic-semiconductor layer of the organic-semiconductor element of this invention contains a binder polymer.
  • the organic semiconductor device of the present invention may be an organic semiconductor device having a layer containing the organic semiconductor layer and a binder polymer.
  • the type of binder polymer is not particularly limited, and known binder polymers can be used.
  • the binder polymer include polystyrene resin, acrylic resin, rubber, thermoplastic elastomer and the like. Among them, as the binder polymer, a polymer compound having a benzene ring (polymer having a monomer unit having a benzene ring) are preferred.
  • the content of the monomer unit having a benzene ring group is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more, based on all the monomer units. Although the upper limit in particular is not restrict
  • the binder polymer include polystyrene, poly ( ⁇ -methylstyrene), polyvinylcinnamate, poly (4-vinylphenyl), poly (4-methylstyrene) and the like.
  • the weight average molecular weight of the pinder polymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 3,000 to 1,000,000, and still more preferably 5,000 to 600,000. Moreover, when using the solvent mentioned later, it is preferable that a pinder polymer has the solubility to the solvent to be used higher than a specific compound. It is excellent by the mobility and thermal stability of the organic semiconductor obtained as it is the said aspect.
  • the content of the binder polymer in the organic semiconductor layer of the organic semiconductor element of the present invention is preferably 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the specific compound. Preferably, it is more preferably 20 to 120 parts by mass. It is excellent by the mobility and thermal stability of the organic semiconductor obtained as it is the said range.
  • the organic semiconductor layer in the organic semiconductor device of the present invention may contain other components other than the specific organic semiconductor compound and a binder polymer.
  • known additives and the like can be used.
  • the content of components other than the specific compound and the binder polymer in the organic semiconductor layer is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less. It is particularly preferable that the content be 0.1% by mass or less. It is excellent in film formation property as it is the said range, and it is excellent by the mobility and thermal stability of the organic semiconductor obtained.
  • the method for forming the organic semiconductor layer in the organic semiconductor device of the present invention is not particularly limited, and the composition for forming an organic semiconductor film of the present invention described later is applied onto the source electrode, the drain electrode, and the gate insulating film.
  • a desired organic semiconductor layer can be formed by subjecting it to drying treatment as necessary.
  • the organic semiconductor element of this invention is manufactured using the composition for organic semiconductor film formation of this invention mentioned later.
  • the method for producing an organic semiconductor film or an organic semiconductor element using the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted.
  • prescribed base material, performing a drying process as needed, and manufacturing an organic-semiconductor film is mentioned.
  • the method for applying the composition onto the substrate is not particularly limited, and any known method can be employed, such as inkjet printing, flexographic printing, bar coating, spin coating, knife coating, doctor blade method, etc. And ink jet printing and flexographic printing are preferred.
  • the composition can be printed on a substrate to easily form a pattern.
  • the method for producing an organic semiconductor device of the present invention preferably includes the step of applying the composition for forming an organic semiconductor film of the present invention on a substrate, and the composition for forming an organic semiconductor film of the present invention is a solvent It is more preferable to include an application step of applying the composition for forming an organic semiconductor film of the present invention on a substrate, and a removal step of removing a solvent from the applied composition.
  • the composition for organic-semiconductor film formation of this invention mentioned later contains a solvent, and it is more preferable that an organic solvent is included.
  • a well-known solvent can be used as a solvent.
  • hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin and 1-methylnaphthalene
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene and chlorotoluene, ester solvents such as ethyl acetate, butyl
  • the solvents may be used alone or in combination of two or more.
  • hydrocarbon solvents, halogenated hydrocarbon solvents and / or ether solvents are preferable, and toluene, xylene, mesitylene, tetralin, dichlorobenzene or anisole is more preferable.
  • the boiling point of the solvent is 100 ° C. or higher.
  • the boiling point of the solvent is more preferably 100 to 300 ° C., further preferably 125 to 250 ° C., and particularly preferably 150 to 225 ° C.
  • the boiling point of the solvent with most content is 100 degreeC or more, and it is more preferable that the boiling point of all the solvents is 100 degreeC or more.
  • the content of the specific compound in the composition for forming an organic semiconductor film of the present invention is preferably 0.05 to 50% by mass, and more preferably 0.1 to 25% by mass 0.25 to 15% by mass, more preferably 0.4 to 10% by mass, and the content of the binder polymer is preferably 0.01 to 50% by mass. And more preferably 0.1 to 10% by mass. It is excellent in applicability
  • the drying process in the removal step is a process carried out as necessary, and the optimum conditions are appropriately selected depending on the type of the specific compound and the solvent used.
  • the heating temperature is preferably 30 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C., and the heating time is more excellent in mobility and thermal stability of the obtained organic semiconductor and excellent in productivity. 10 to 300 minutes are preferable, and 30 to 180 minutes are more preferable.
  • the thickness of the organic semiconductor layer to be formed is not particularly limited, but is preferably 10 to 500 nm, more preferably 30 to 200 nm, from the viewpoint of the mobility and thermal stability of the obtained organic semiconductor.
  • the organic semiconductor device is not particularly limited, but is preferably an organic semiconductor device of 2 to 5 terminals, and more preferably an organic semiconductor device of 2 or 3 terminals.
  • the organic semiconductor element is preferably not a photoelectric conversion element.
  • the organic-semiconductor element of this invention is a nonluminous organic-semiconductor element.
  • the two-terminal element include a rectifying diode, a constant voltage diode, a PIN diode, a Schottky barrier diode, a diode for surge protection, a diac, a varistor, a tunnel diode and the like.
  • three-terminal devices include bipolar transistors, Darlington transistors, field effect transistors, insulated gate bipolar transistors, unijunction transistors, electrostatic induction transistors, gate turn thyristors, triacs, electrostatic induction thyristors, and the like.
  • rectifying diodes and transistors are preferably mentioned, and field effect transistors are more preferably mentioned.
  • field effect transistor an organic thin film transistor is preferably mentioned.
  • FIG. 1 is a schematic cross-sectional view of one embodiment of the organic semiconductor device (organic thin film transistor (organic TFT)) of the present invention.
  • the organic thin film transistor 100 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and the gate insulating film 30 on the opposite side to the gate electrode 20 side.
  • the organic thin film transistor 100 is a bottom gate-bottom contact type organic thin film transistor.
  • the organic semiconductor film 50 corresponds to the film
  • the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and the formation method of each will be described in detail.
  • the substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode and the like described later.
  • the type of substrate is not particularly limited, and examples thereof include plastic substrates, glass substrates, ceramic substrates, and the like. Among them, a glass substrate or a plastic substrate is preferable from the viewpoint of the applicability to each device and the cost.
  • thermosetting resin for example, epoxy resin, phenol resin, polyimide resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.) or thermoplastic resin (for example, phenoxy) Resin, polyether sulfone, polysulfone, polyphenylene sulfone and the like).
  • thermoplastic resin for example, phenoxy
  • the material of the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide and the like.
  • the material of the glass substrate include soda glass, potash glass, borosilicate glass, quartz glass, aluminum silicate glass, lead glass and the like.
  • the material of the gate electrode, the source electrode, and the drain electrode include, for example, gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum, magnesium, calcium, barium, sodium, etc.
  • metal is preferable, and silver or aluminum is more preferable.
  • the thickness of the gate electrode, the source electrode, and the drain electrode is not particularly limited, but is preferably 20 to 200 nm.
  • the method for forming the gate electrode, the source electrode, and the drain electrode is not particularly limited, and examples thereof include a method of vacuum depositing or sputtering an electrode material on a substrate, and a method of applying or printing a composition for electrode formation.
  • a method of patterning printing methods, such as a photolithographic method; inkjet printing, screen printing, offset printing, letterpress printing, mask vapor deposition etc. are mentioned, for example.
  • ⁇ Gate insulating film Materials for the gate insulating film include polymethyl methacrylate, polystyrene, polyvinyl phenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin, phenol resin, etc. And polymers such as silicon dioxide, aluminum oxide, oxides such as titanium oxide, and nitrides such as silicon nitride. Among these materials, a polymer is preferable in view of compatibility with the organic semiconductor film.
  • the material of the gate insulating film When a polymer is used as the material of the gate insulating film, it is preferable to use a crosslinking agent (for example, melamine) in combination. By using the crosslinking agent in combination, the polymer is crosslinked to improve the durability of the formed gate insulating film.
  • the thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1,000 nm.
  • the method for forming the gate insulating film is not particularly limited, for example, a method for applying a composition for forming a gate insulating film on a substrate on which a gate electrode is formed, a method for depositing or sputtering a gate insulating film material, etc.
  • the method for applying the composition for forming a gate insulating film is not particularly limited, and known methods (bar coating method, spin coating method, knife coating method, doctor blade method) can be used.
  • heating may be performed after application for the purpose of solvent removal, crosslinking, and the like.
  • the organic semiconductor device of the present invention preferably has the binder polymer layer between the organic semiconductor layer and the insulating film, and more preferably has the binder polymer layer between the organic semiconductor layer and the gate insulating film.
  • the thickness of the binder polymer layer is not particularly limited, but is preferably 20 to 500 nm.
  • the said binder polymer layer should just be a layer containing the said polymer, it is preferable that it is a layer which consists of the said binder polymer.
  • the method for forming the binder polymer layer is not particularly limited, but known methods (bar coating method, spin coating method, knife coating method, doctor blade method, ink jet method) can be used.
  • heating may be performed after application for the purpose of solvent removal, crosslinking, and the like.
  • the organic semiconductor element of this invention equips an outermost layer with a sealing layer from a durable viewpoint.
  • a well-known sealing agent can be used for a sealing layer.
  • the thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 ⁇ m.
  • the method for forming the sealing layer is not particularly limited, for example, the composition for forming a sealing layer is applied on a substrate on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed. Methods etc.
  • coating the composition for sealing layer formation is the same as the method of apply
  • heating may be performed after application for the purpose of solvent removal, crosslinking, and the like.
  • FIG. 2 is a cross-sectional schematic diagram of another one aspect
  • the organic thin film transistor 200 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and an organic semiconductor film 50 disposed on the gate insulating film 30.
  • the source electrode 40 and the drain electrode 42 are formed using the composition of the present invention described above.
  • the organic thin film transistor 200 is a top contact type organic thin film transistor.
  • the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer are as described above.
  • the organic semiconductor device of the present invention is a top gate bottom
  • the present invention can also be suitably used for a contact type organic thin film transistor and a top gate-top contact type organic thin film transistor.
  • the organic thin film transistor described above can be suitably used for electronic paper, a display device, and the like.
  • composition for forming an organic semiconductor film of the present invention is characterized by containing a specific organic semiconductor compound and a solvent. Moreover, it is preferable that the composition for organic-semiconductor film formation of this invention contains a binder polymer.
  • the specific compound, the binder polymer, and the solvent in the composition for forming an organic semiconductor film of the present invention have the same meanings as the specific compound, the binder polymer, and the solvent described above, and preferred embodiments are also the same.
  • the composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific compound and the binder polymer. As other components, known additives and the like can be used.
  • the content of components other than the specific compound and the binder polymer in the composition for forming an organic semiconductor film of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content.
  • the content is more preferably 1% by mass or less and particularly preferably 0.1% by mass or less. It is excellent in film formation property as it is the said range, and it is excellent by the mobility and thermal stability of the organic semiconductor obtained.
  • solid content is the quantity of the component except volatile components, such as a solvent.
  • the viscosity of the composition for forming an organic semiconductor film of the present invention is not particularly limited, but it is preferably 3 to 100 mPa ⁇ s, more preferably 5 to 50 mPa ⁇ s, and still more preferably 9 to 40 mPa ⁇ s, from the viewpoint of more excellent coatability. More preferable.
  • the viscosity in this invention is a viscosity in 25 degreeC. It is preferable that it is a measuring method based on JISZ8803 as a measuring method of a viscosity.
  • the method for producing the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted.
  • a desired composition can be obtained by adding a predetermined amount of a specific compound to a solvent and appropriately performing a stirring process.
  • a specific compound and a binder polymer can be added simultaneously or sequentially, and a composition can be suitably produced.
  • the organic semiconductor film of the present invention is characterized by containing a specific organic semiconductor.
  • the organic semiconductor film of the present invention preferably contains a binder polymer.
  • the specific compound in the organic semiconductor film of the present invention, the polymer and oligomer obtained by polymerizing the specific compound, and the binder polymer are obtained by polymerizing the specific compound and the specific compound described above in the organic semiconductor device of the present invention It is synonymous with the said polymer and oligomer, and a binder polymer, and its preferable aspect is also the same.
  • the composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific compound, the polymer and the oligomer obtained by polymerizing the specific compound, and the binder polymer.
  • known additives and the like can be used.
  • the content of the specific compound, the polymer and the oligomer obtained by polymerizing the specific compound, and the component other than the binder polymer in the organic semiconductor film of the present invention is preferably 10% by mass or less, and 5% by mass or less Is more preferably, 1% by mass or less is more preferable, and 0.1% by mass or less is particularly preferable. It is excellent in film formation property as it is the said range, and it is excellent by the mobility and thermal stability of the organic semiconductor obtained.
  • solid content is the quantity of the component except volatile components, such as a solvent.
  • the thickness of the organic semiconductor film of the present invention is not particularly limited, but is preferably 10 to 500 nm, and more preferably 30 to 200 nm, from the viewpoint of the mobility and thermal stability of the obtained organic semiconductor.
  • the organic semiconductor film of the present invention can be suitably used for an organic semiconductor element, and can be particularly suitably used for an organic transistor (organic thin film transistor).
  • the organic semiconductor film of the present invention can be suitably produced using the composition for forming an organic semiconductor film of the present invention.
  • Compound 2 was synthesized by the synthetic scheme shown below. Specifically, Chem. Commun. 2013, 49, 5354.
  • the synthetic intermediate 3 is synthesized according to the method described in J. Mater. Chem. S, 2014, 2, 3972.
  • the synthetic intermediate 4 was synthesized by the method described in 4. and the compound 2 was obtained by the Stille coupling reaction of both.
  • the compounds 3 to 15 were also synthesized according to the above method.
  • the comparative compound 1 is the exemplified compound (II-5) described in JP-A-7-228865.
  • Comparative compound 2 is the exemplified compound (II-2) described in JP-A-5-158260.
  • the comparison compound 3 and the comparison compound 4 are the illustration compound 71 and the illustration compound 120 which are described in Unexamined-Japanese-Patent No. 2010-177643.
  • Comparative compound 5 is Exemplified compound 3 described in JP-A-2010-205984.
  • Comparative compound 6 is described in J.I. Am. Chem. Soc. , 1998, 120, 664. And the compound 7a described in All of them were confirmed to be 99.8% or more in purity (a ratio of absorption intensity area at 254 nm) by high performance liquid chromatography (TSKgel ODS-100Z, manufactured by Tosoh Corp.).
  • 1,2,3,4-Tetramethylbenzene used for the synthesis of Compound 1 was purchased from Alpha Acer.
  • 3,4-dibromo-thiophene was used for the synthesis of Compound 2 were purchased from Wako Pure Chemical Industries, Ltd..
  • binders The polymers used as binders are shown below.
  • P ⁇ MS poly- ⁇ -methylstyrene, weight average molecular weight 437,000, manufactured by Sigma Aldrich
  • PTAA poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine], number average molecular weight 7,000 to 10,000
  • PCPDTBT poly [2,6- (4,4-bis (2-ethylhexyl) -4H cyclopenta [2,1-b; 3,4-b '] dithiophene) -alto-4 , 7- (2,1,3-benzothiadiazole)], weight average molecular weight of 7,000 to 20,000, manufactured by sigma-Aldrich
  • silver ink (H-1, manufactured by Mitsubishi Materials Corporation) is formed into a source electrode and a drain electrode (channel length 40 ⁇ m, channel width 200 ⁇ m) using an inkjet device DMP-2831 (manufactured by Fujifilm Dimatics Co., Ltd.) I drew it. After that, baking was performed at 180 ° C. for 30 minutes in an oven and sintering was performed to form a source electrode and a drain electrode, whereby an element substrate for TFT characteristic evaluation was obtained. After spin-coating each coating solution for organic semiconductor film formation on the element substrate for TFT characteristic evaluation (1,000 rpm for 30 seconds after 500 rpm for 10 seconds), the organic semiconductor layer is formed by drying at 50 ° C for 10 minutes on a hot plate. Then, a bottom gate-bottom contact type organic TFT element was obtained.
  • a semiconductor characteristic evaluation apparatus B2900A manufactured by Agilent Technologies Inc.
  • the performance was evaluated in the following in the air.
  • the carrier mobility ⁇ was calculated using the following equation representing the current I d .
  • I d (w / 2 L) ⁇ C i (V g -V th ) 2
  • L represents a gate length
  • W represents a gate width
  • C i represents a capacity per unit area of the insulating layer
  • V g represents a gate voltage
  • V th represents a threshold voltage.
  • the carrier mobility values shown in Table 1 are average values of 10 elements.
  • the carrier mobility ⁇ is preferably as high as possible, and for practical use is preferably 1 ⁇ 10 ⁇ 2 cm 2 / Vs or more, and more preferably 1 ⁇ 10 ⁇ 1 cm 2 / Vs or more.
  • the characteristic evaluation is not performed, and “-” is described in the corresponding column of Table 1.
  • the variation coefficient calculated by the following formula with respect to the carrier mobility of 10 elements was evaluated in the following five steps, and was used as an index of mobility variation. The smaller this value is, the smaller the variation in mobility between elements is. Practically, A or B is preferable, and A is more preferable.
  • Coefficient of variation standard deviation / mean value ⁇ 100 A: less than 15% B: 15% or more and less than 30% C: 30% or more and less than 50% D: 50% or more
  • Carrier mobility maintenance rate after heating (%) mobility (after heating) / mobility (before heating) A: 80% or more B: 60% or more and less than 80% C: 40% or more and less than 60% D: less than 40%

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Abstract

The purpose of the present invention is to provide: an organic semiconductor element which has high mobility and excellent thermal stability, while being suppressed in variation of the mobility; a method for producing the organic semiconductor element; a novel compound which is suitable as an organic semiconductor; an organic semiconductor film which has high mobility and excellent thermal stability, while being suppressed in variation of the mobility; and a composition for forming an organic semiconductor film, which is capable of suitably forming the organic semiconductor film. An organic semiconductor element according to the present invention is characterized by comprising an organic semiconductor layer that contains an organic semiconductor represented by formula 1. In formula 1, each X independently represents O, S, Se or NR; each ring A independently represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring; m represents an integer of 1-5; in cases where m is 1, at least one of R moieties represents an aromatic hydrocarbon group or an aromatic heterocyclic group; and in cases where m is 4 or 5, it is not possible that three or more R moieties represent aromatic hydrocarbon groups or aromatic heterocyclic groups.

Description

有機半導体素子及びその製造方法、化合物、有機半導体膜形成用組成物、並びに、有機半導体膜Organic semiconductor device and method for manufacturing the same, compound, composition for forming organic semiconductor film, and organic semiconductor film
 本発明は、有機半導体素子及びその製造方法、化合物、有機半導体膜形成用組成物、並びに、有機半導体膜に関する。 The present invention relates to an organic semiconductor device and a method of manufacturing the same, a compound, a composition for forming an organic semiconductor film, and an organic semiconductor film.
 軽量化、低コスト化、柔軟化が可能であることから、液晶ディスプレイや有機EL(有機エレクトロルミネッセンス)ディスプレイに用いられるFET(Field effect transistor、電界効果トランジスタ)、RFID(Radio Frequency Identifier、RFタグ)等に、有機半導体膜(有機半導体層)を有する有機トランジスタが利用されている。
 従来の有機半導体としては、特許文献1に記載されたものが知られている。
Since weight reduction, cost reduction, and flexibility can be achieved, FET (Field Effect Transistor) or RFID (Radio Frequency Identifier, RF tag) used for liquid crystal display or organic EL (organic electroluminescence) display For example, an organic transistor having an organic semiconductor film (organic semiconductor layer) is used.
As a conventional organic semiconductor, what was described in patent document 1 is known.
特開2010-177643号公報Unexamined-Japanese-Patent No. 2010-177643
 本発明が解決しようとする課題は、高移動度であり、熱安定性に優れ、移動度のバラツキが抑制された有機半導体素子及びその製造方法を提供することである。
 また、本発明が解決しようとする他の課題は、有機半導体として好適な新規な化合物を提供することである。
 更に、本発明が解決しようとする他の課題は、高移動度であり、熱安定性に優れ、移動度のバラツキが抑制された有機半導体膜、及び、上記有機半導体膜を好適に形成することができる有機半導体膜形成用組成物を提供することである。
The problem to be solved by the present invention is to provide an organic semiconductor device having high mobility, excellent thermal stability, and suppressed variation in mobility, and a method for manufacturing the same.
Another object of the present invention is to provide a novel compound suitable as an organic semiconductor.
Furthermore, another problem to be solved by the present invention is to preferably form an organic semiconductor film having high mobility, excellent thermal stability, and suppressed variation in mobility, and the above organic semiconductor film. It is to provide a composition for forming an organic semiconductor film that can
 本発明の上記課題は、以下の<1>、<6>、<10>、<19>、又は、<20>に記載の手段により解決された。好ましい実施態様である<2>~<5>、<7>~<9>、<11>~<18>、及び、<21>~<25>とともに以下に記載する。
 <1> 下記式1で表される有機半導体を含有する有機半導体層を有することを特徴とする、有機半導体素子、
The above-mentioned subject of the present invention is solved by the means as described in the following <1>, <6>, <10>, <19>, or <20>. They are described below together with <2> to <5>, <7> to <9>, <11> to <18>, and <21> to <25>, which are preferred embodiments.
<1> An organic semiconductor device comprising an organic semiconductor layer containing an organic semiconductor represented by the following formula 1:
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
 式1中、Xはそれぞれ独立に、O、S、Se、NRのいずれかを表し、Rはそれぞれ独立に置換基を表し、環Aはそれぞれ独立に、5員又は6員の単環の芳香族炭化水素環又は芳香族複素環を表し、mは1~5の整数を表し、mが2~5の場合は複数の環Aはそれぞれ同一でも異なってもよく、nは0以上の整数を表し、mが1の場合はRの少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、mが4又は5の場合は3つ以上のRが芳香族炭化水素基又は芳香族複素環基になることはない。 In Formula 1, each X independently represents any of O, S, Se, and NR, each R independently represents a substituent, and each ring A independently represents a 5- or 6-membered monocyclic aromatic ring. Group hydrocarbon ring or aromatic heterocyclic ring, m represents an integer of 1 to 5, and when m is 2 to 5, plural rings A may be the same or different, and n is an integer of 0 or more When m is 1, at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when m is 4 or 5, three or more R's are an aromatic hydrocarbon group or an aromatic complex It can not be a ring group.
 <2> 式1中、環Aがそれぞれ独立に、ベンゼン環、フラン環、チオフェン環、セレノフェン環、又はピロール環を表し、かつ、式1中のRを取り去った部分構造の対称性が、C2、C2v、又は、C2hである、<1>に記載の有機半導体素子、
 <3> 式1で表される有機半導体が、下記式2で表される有機半導体である、<1>又は<2>に記載の有機半導体素子、
<2> In the formula 1, each ring A independently represents a benzene ring, a furan ring, a thiophene ring, a selenophen ring, or a pyrrole ring, and the symmetry of the partial structure from which R in the formula 1 is removed is C 2, C 2v, or a C 2h, the organic semiconductor device according to <1>,
<3> The organic semiconductor of the formula 1, an organic semiconductor represented by the following formula 2, the organic semiconductor device according to <1> or <2>,
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
 式2中、Tは下記T-1~T-35よりなる群から選択されるいずれかの構造を表し、R’はそれぞれ独立に置換基を表し、nは0~6の整数を表し、TがT-1又はT-2である場合、R’の少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、TがT-20~T-35のいずれかである場合、3つ以上のR’が芳香族炭化水素基又は芳香族複素環基になることはない。 In Formula 2, T represents any structure selected from the group consisting of T-1 to T-35 below, R ′ independently represents a substituent, n represents an integer of 0 to 6, and T represents When at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group when T is T-1 or T-2, and three when T is any of T-20 to T-35 The above R 'does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
 T-1~T-35中、Xはそれぞれ独立に、O、S、Se、NR’のいずれかを表す。 In T-1 to T-35, X each independently represents any of O, S, Se, and NR '.
 <4> R’が下記式3で表される、<3>に記載の有機半導体素子、 The organic-semiconductor element as described in <3> by which <4> R 'is represented by following formula 3,
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
 式3中、Lはそれぞれ独立に、下記式L-1~式L-12のいずれかで表される2価の連結基、又は、2以上の下記式L-1~式L-12のいずれかで表される2価の連結基が2つ以上結合した2価の連結基を表し、Zはそれぞれ独立に、水素原子、アルキル基、オキシエチレン単位の繰り返し数が2以上のオリゴオキシエチレン基、ケイ素原子数が2以上のオリゴシロキサン基、又は、トリアルキルシリル基を表し、ただし、Zがトリアルキルシリル基を表すのは、Zに隣接するLが下記式L-3で表される連結基である場合に限り、水素原子を表すのは、Zに隣接するLが下記式L-1、L-2、L-3、L-10、L-11、又は、L-12で表される連結基である場合に限る。 In Formula 3, L is each independently a divalent linking group represented by any one of the following Formulas L-1 to L-12, or any of two or more of the following Formulas L-1 to L-12. And each of Z's independently represents a hydrogen atom, an alkyl group, or an oligooxyethylene group having a repeating number of oxyethylene units of 2 or more. And an oligosiloxane group having a silicon atom number of 2 or more, or a trialkylsilyl group, provided that Z represents a trialkylsilyl group, and a linkage in which L adjacent to Z is represented by the following formula L-3 Only when it is a group, it means that L adjacent to Z is represented by the following formula L-1, L-2, L-3, L-10, L-11 or L-12. Limited if it is a
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
 式L-1~式L-12中、*及び波線部分は他の構造との結合位置を表し、式L-1、式L-2及び式L-10~式L-12におけるRL1はそれぞれ独立に、水素原子又は置換基を表す。 In Formula L-1 to Formula L-12, * and a wavy line portion indicate bonding positions with other structures, and R L1 in Formula L-1, Formula L-2 and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.
 <5> Xがそれぞれ独立に、O又はSを表す、<1>~<4>のいずれか1つに記載の有機半導体素子、 <5> The organic semiconductor device according to any one of <1> to <4>, wherein each X independently represents O or S,
 <6> 上記式2で表されることを特徴とする化合物、
 <7> R’が上記式3で表される、<6>に記載の化合物、
 <8> Xがそれぞれ独立に、O又はSを表す、<6>又は<7>に記載の化合物、
 <9> 有機半導体である、<6>~<8>のいずれか1つに記載の化合物、
 <10> 上記式1で表される有機半導体と、溶媒とを含有することを特徴とする、有機半導体膜形成用組成物、
 <11> 式1中、環Aがそれぞれ独立に、ベンゼン環、フラン環、チオフェン環、セレノフェン環、又は、ピロール環を表し、かつ、式1中のRを取り去った部分構造の対称性が、C2、C2v、又は、C2hである、<10>に記載の有機半導体膜形成用組成物、
<6> a compound represented by the above formula 2,
<7> The compound according to <6>, wherein R ′ is represented by the above formula 3,
<8> The compound according to <6> or <7>, wherein each X independently represents O or S,
<9> The compound according to any one of <6> to <8>, which is an organic semiconductor,
<10> A composition for forming an organic semiconductor film, comprising: an organic semiconductor represented by the above formula 1; and a solvent
<11> In Formula 1, ring A respectively independently represents a benzene ring, a furan ring, a thiophene ring, a selenophen ring, or a pyrrole ring, and the symmetry of the partial structure from which R in Formula 1 is removed is C 2, C 2v, or a C 2h, the organic semiconductor film forming composition as described in <10>,
 <12> 式1で表される有機半導体が、上記式2で表される有機半導体である、<10>又は<11>に記載の有機半導体膜形成用組成物、
 <13> R’が上記式3で表される、<12>に記載の有機半導体膜形成用組成物、
 <14> Xがそれぞれ独立に、O又はSを表す、<10>~<13>のいずれか1つに記載の有機半導体膜形成用組成物、
 <15> 上記式1で表される有機半導体の濃度が、組成物全体に対して0.5~15質量%である、<10>~<14>のいずれか1つに記載の有機半導体膜形成用組成物、
 <16> 溶媒の沸点が100℃以上である、<10>~<15>のいずれか1つに記載の有機半導体膜形成用組成物、
 <17> ポリマーバインダーを更に含有する、<10>~<16>のいずれか1つに記載の有機半導体膜形成用組成物、
 <18> 組成物の粘度が5mPa・s~50mPa・sである、<10>~<17>のいずれか1つに記載の有機半導体膜形成用組成物、
 <19> <10>~<18>のいずれか1つに記載の有機半導体膜形成用組成物を基板上に塗布する塗布工程を含む、有機半導体素子の製造方法、
The composition for organic-semiconductor film formation as described in <10> or <11> whose organic semiconductor represented by <12> Formula 1 is an organic semiconductor represented by the said Formula 2,
<13> The composition for forming an organic semiconductor film according to <12>, wherein R ′ is represented by the above formula 3.
The composition for organic-semiconductor film formation as described in any one of <10>-<13> in which <14> X respectively independently represents O or S,
<15> The organic semiconductor film according to any one of <10> to <14>, wherein the concentration of the organic semiconductor represented by the above formula 1 is 0.5 to 15% by mass with respect to the entire composition. Composition for forming,
<16> the boiling point of the solvent is 100 ° C. or higher, <10> - an organic semiconductor film forming composition according to any one of <15>,
<17> The composition for forming an organic semiconductor film according to any one of <10> to <16>, further comprising a polymer binder,
<18> The composition for forming an organic semiconductor film according to any one of <10> to <17>, wherein the viscosity of the composition is 5 mPa · s to 50 mPa · s.
<19> A method of manufacturing an organic semiconductor device, comprising a coating step of coating the composition for forming an organic semiconductor film according to any one of <10> to <18> on a substrate,
 <20> 上記式1で表される有機半導体を含有することを特徴とする、有機半導体膜、
 <21> 上記式1中、環Aがそれぞれ独立に、ベンゼン環、フラン環、チオフェン環、セレノフェン環、又は、ピロール環を表し、かつ、式1中のRを取り去った部分構造の対称性が、C2、C2v、又は、C2hである、<20>に記載の有機半導体膜、
 <22> 上記式1で表される有機半導体が、上記式2で表される有機半導体である、<20>又は<21>に記載の有機半導体膜、
 <23> R’が上記式3で表される、<22>に記載の有機半導体膜、
 <24> Xがそれぞれ独立に、O又はSを表す、<20>~<23>のいずれか1つに記載の有機半導体膜、
 <25> 溶液塗布法により製膜された、<20>~<24>のいずれか1つに記載の有機半導体膜。
<20> An organic semiconductor film characterized by containing the organic semiconductor represented by the above formula 1
<21> In the above formula 1, the ring A independently represents a benzene ring, a furan ring, a thiophene ring, a selenophen ring or a pyrrole ring, and the symmetry of the partial structure from which R in the formula 1 is removed is , C 2, C 2v, or a C 2h, the organic semiconductor film according to <20>,
<22> The organic semiconductor film according to <20> or <21>, wherein the organic semiconductor represented by Formula 1 is an organic semiconductor represented by Formula 2;
The organic semiconductor film as described in <22> by which <23> R 'is represented by the said Formula 3,
<24> The organic semiconductor film according to any one of <20> to <23>, wherein each X independently represents O or S,
<25> The organic semiconductor film according to any one of <20> to <24>, which is formed by a solution coating method.
 本発明によれば、高移動度であり、熱安定性に優れ、移動度のバラツキが抑制された有機半導体素子及びその製造方法を提供することができた。
 また、本発明によれば、有機半導体として好適な新規な化合物を提供することができた。
 更に、本発明によれば、高移動度であり、熱安定性に優れ、移動度のバラツキが抑制された有機半導体膜、及び、上記有機半導体膜を好適に形成することができる有機半導体膜形成用組成物を提供することができた。
According to the present invention, it has been possible to provide an organic semiconductor device having high mobility, excellent thermal stability, and suppressed variation in mobility, and a method of manufacturing the same.
Moreover, according to the present invention, a novel compound suitable as an organic semiconductor can be provided.
Furthermore, according to the present invention, an organic semiconductor film having high mobility, excellent thermal stability, and suppressed variation in mobility, and organic semiconductor film formation capable of suitably forming the above organic semiconductor film It was possible to provide a composition for use.
本発明の有機半導体素子の一態様の断面模式図である。It is a cross-sectional schematic diagram of the one aspect | mode of the organic-semiconductor element of this invention. 本発明の有機半導体素子の別の一態様の断面模式図である。It is a cross-sectional schematic diagram of another one aspect | mode of the organic-semiconductor element of this invention.
 以下において、本発明の内容について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。なお、本願明細書において「~」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。また、本発明における有機EL素子とは、有機エレクトロルミネッセンス素子のことをいう。
 本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有さないものとともに置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
 また、本明細書における化学構造式は、水素原子を省略した簡略構造式で記載する場合もある。
 本発明において、「移動度」との記載は、キャリア移動度を意味し、電子移動度及びホール移動度のいずれか、又は、双方を意味する。
 また、本発明において、「質量%」と「重量%」とは同義であり、「質量部」と「重量部」とは同義である。
 また、本発明において、好ましい態様の組み合わせは、より好ましい。
Hereinafter, the contents of the present invention will be described in detail. Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments. In this specification a "~" is the numerical values described before and after thereof in the sense of including as a lower limit and an upper limit. Moreover, the organic EL element in this invention means the thing of an organic electroluminescent element.
In the notation of groups (atomic groups) in the present specification, notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Moreover, the chemical structural formula in this specification may be described by the simplified structural formula which abbreviate | omitted the hydrogen atom.
In the present invention, the term "mobility" means carrier mobility and means either or both of electron mobility and hole mobility.
Moreover, in the present invention, “mass%” and “weight%” are synonymous, and “mass part” and “part by weight” are synonymous.
Moreover, in the present invention, a combination of preferred embodiments is more preferred.
(有機半導体素子、及び、化合物)
 本発明の有機半導体素子は、上記式1で表される有機半導体(以下、「特定有機半導体化合物」又は「特定化合物」ともいう。)を含有する有機半導体層を有することを特徴とする。
(Organic semiconductor device and compound)
The organic semiconductor device of the present invention is characterized by having an organic semiconductor layer containing the organic semiconductor represented by the above-mentioned formula 1 (hereinafter, also referred to as “specific organic semiconductor compound” or “specific compound”).
 本発明者らは鋭意検討を重ねた結果、上記特定有機半導体化合物を含有することにより、得られる有機半導体素子や有機半導体膜が高移動度であり、熱安定性に優れ、移動度のバラツキが抑制されることを見いだし、本発明を完成するに至ったものである。
 詳細な効果の発現機構については不明であるが、上記特定有機半導体化合物は、分子間でHOMO(Highest Occupied Molecular Orbital)の重なりが大きくなりやすく、高移動度であり、熱安定性に優れ、また、移動度のバラツキが抑制されると推定される。
The inventors of the present invention conducted intensive studies, and as a result, by containing the above specific organic semiconductor compound, the obtained organic semiconductor device or organic semiconductor film has high mobility, excellent thermal stability, and variation in mobility. It has been found that it is suppressed, and the present invention has been completed.
Although the mechanism of expression of detailed effects is unknown, the above-mentioned specific organic semiconductor compounds are likely to have a large overlap of HOMO (Highest Occupied Molecular Orbital) between molecules, have high mobility, and have excellent thermal stability, and It is estimated that the variation in mobility is suppressed.
<特定有機半導体化合物>
 本発明において、特定有機半導体化合物は、下記式1で表される。
<Specific organic semiconductor compound>
In the present invention, the specific organic semiconductor compound is represented by the following formula 1.
Figure JPOXMLDOC01-appb-C000030
 式1中、Xはそれぞれ独立に、O、S、Se、NRのいずれかを表し、Rはそれぞれ独立に置換基を表し、環Aはそれぞれ独立に、5員又は6員の単環の芳香族炭化水素環又は芳香族複素環を表し、mは1~5の整数を表し、mが2~5の場合は複数の環Aはそれぞれ同一でも異なってもよく、nは0以上の整数を表し、mが1の場合はRの少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、mが4又は5の場合は3つ以上のRが芳香族炭化水素基又は芳香族複素環基になることはない。
Figure JPOXMLDOC01-appb-C000030
In Formula 1, each X independently represents any of O, S, Se, and NR, each R independently represents a substituent, and each ring A independently represents a 5- or 6-membered monocyclic aromatic ring. Group hydrocarbon ring or aromatic heterocyclic ring, m represents an integer of 1 to 5, and when m is 2 to 5, plural rings A may be the same or different, and n is an integer of 0 or more When m is 1, at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when m is 4 or 5, three or more R's are an aromatic hydrocarbon group or an aromatic complex It can not be a ring group.
 本発明の特定有機半導体化合物は、新規な化合物である。
 また、本発明の特定有機半導体化合物は、有機半導体素子、有機半導体膜、及び、有機半導体膜形成用組成物に好適に用いることができる。
 本発明の特定有機半導体化合物は、環Aの両端に存在する複素芳香環の複素原子が、環Aに対して外向きに配置している。このような特定の構造を有することにより、有機半導体層や膜として高移動度であり、熱安定性に優れ、移動度のバラツキが抑制されたものが得られると推定している。
The specific organic semiconductor compound of the present invention is a novel compound.
Also, certain organic semiconductor compounds of the present invention, the organic semiconductor element, an organic semiconductor film, and can be suitably used for the organic semiconductor film-forming composition.
In the specific organic semiconductor compound of the present invention, hetero atoms of the heteroaromatic ring present at both ends of ring A are arranged outward with respect to ring A. By having such a specific structure, it is estimated that the organic semiconductor layer or the film has high mobility, is excellent in thermal stability, and has a variation in mobility suppressed.
 式1中、環Aはそれぞれ独立に、5員又は6員の単環の芳香族炭化水素環又は芳香族複素環を表す。芳香族炭化水素環としては、ベンゼン環が例示される。芳香族複素環の複素原子としては特に限定されないが、S、O、N、Seが例示され、芳香族複素環としては、チオフェン環、フラン環、ピラン環、ピロール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、セレノフェン環、イミダゾール環等が挙げられる。
 これらの中でも、環Aはそれぞれ独立に、ベンゼン環、チオフェン環、セレノフェン環、又は、ピロール環であることが好ましく、ベンゼン環、チオフェン環又はフラン環であることがより好ましく、ベンゼン環又はチオフェン環であることが更に好ましい。
 なお、環Aが複数存在する場合、すなわち、mが2以上である場合、複数存在する環Aは同一でも異なっていてもよく、特に限定されない。
In Formula 1, each ring A independently represents a 5- or 6-membered monocyclic aromatic hydrocarbon ring or aromatic heterocycle. A benzene ring is illustrated as an aromatic hydrocarbon ring. The hetero atom of the heteroaromatic ring is not particularly limited, and examples thereof include S, O, N and Se. Examples of the heteroaromatic ring include thiophene ring, furan ring, pyran ring, pyrrole ring, pyridine ring, pyrazine ring, A pyrimidine ring, a pyridazine ring, a selenophen ring, an imidazole ring, etc. are mentioned.
Among them, the ring A is preferably each independently a benzene ring, a thiophene ring, a selenophen ring or a pyrrole ring, more preferably a benzene ring, a thiophene ring or a furan ring, a benzene ring or a thiophene ring It is further preferred that
When a plurality of rings A are present, that is, m is 2 or more, the plurality of rings A may be the same or different and is not particularly limited.
 特定有機半導体化合物は、3環以上7環以下の縮環を含む芳香族炭化水素基又は芳香族ヘテロ環基(3環以上の縮環を含む縮合多環芳香族基)を含む化合物である。なお、特定有機半導体化合物から置換基Rを除いた構造を、「縮合多環芳香族基」ともいうこととする。
 式1中、mは1~5の整数を表す。mは、1~4であることが好ましく、2~4であることがより好ましい。すなわち、特定有機半導体化合物から、置換基Rを除いた縮合多環芳香族基中の環数は、有機半導体としての移動度の観点から、3~7であり、3~6が好ましく、4~6がより好ましい。
The specific organic semiconductor compound is a compound containing an aromatic hydrocarbon group or an aromatic heterocyclic group (condensed polycyclic aromatic group containing a condensed ring of 3 or more rings) containing a condensed ring of 3 to 7 rings. The structure obtained by removing the substituent R from the specific organic semiconductor compound is also referred to as a “fused polycyclic aromatic group”.
In formula 1, m represents an integer of 1 to 5. m is preferably 1 to 4, and more preferably 2 to 4. That is, the number of rings in the fused polycyclic aromatic group excluding the substituent R from the specific organic semiconductor compound is 3 to 7, preferably 3 to 6, from the viewpoint of mobility as an organic semiconductor. 6 is more preferable.
 特定有機半導体化合物からRを取り去った部分構造、すなわち、特定有機半導体から置換基であるRを除いた縮合多環芳香族基の対称性が、C2、C2v、又は、C2hであることが好ましい。対称性がC2、C2v、又は、C2hであると、規則正しい結晶構造をとりやすく、高移動度を発現しやすいためである。
 なお、縮環構造の対称性については、『分子の対称と群論』(中崎昌雄著、東京化学同人)の記載が参酌される。
The partial structure obtained by removing R from the specific organic semiconductor compound, that is, the symmetry of the fused polycyclic aromatic group obtained by removing R which is a substituent from the specific organic semiconductor is C 2 , C 2 v or C 2 h Is preferred. When the symmetry is C 2 , C 2 v or C 2 h, it is easy to form an ordered crystal structure and easily express high mobility.
As for the symmetry of the condensed ring structure, the description of "Symmetry of molecules and group theory" (Nakazaki Masao, Tokyo Kagaku Dojin) is referred to.
 式1中、Rはそれぞれ独立に置換基を表す。nが2以上の場合、複数存在するRは同一でも異なっていてもよい。
 Rとしては、ハロゲン原子、アルキル基(シクロアルキル基、ビシクロアルキル基、トリシクロアルキル基を含む。)、アルケニル基、アルキニル基、アリール基(芳香族炭化水素基)、複素環基(ヘテロ環基といってもよい。芳香族複素環基、及び、脂肪族複素環基を含む。)、シアノ基、ヒドロキシ基、ニトロ基、カルボキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基(アニリノ基を含む。)、アンモニオ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキル及びアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、スルホ基、アルキル及びアリールスルフィニル基、アルキル及びアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリール及びヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、ホスホノ基、シリル基(モノ-、ジ-、トリアルキルシリル基を含む。)、ヒドラジノ基、ウレイド基、ボロン酸基(-B(OH)2)、ホスファト基(-OPO(OH)2)、スルファト基(-OSO3H)、その他の公知の置換基が挙げられる。また、Rが更に置換基により置換されていてもよい。置換基としては、Rで例示した基が例示される。
In Formula 1, R respectively independently represents a substituent. When n is 2 or more, a plurality of R may be the same or different.
R represents a halogen atom, alkyl group (including cycloalkyl group, bicycloalkyl group and tricycloalkyl group), alkenyl group, alkynyl group, aryl group (aromatic hydrocarbon group), heterocyclic group (heterocyclic group (Including aromatic heterocyclic groups and aliphatic heterocyclic groups), cyano groups, hydroxy groups, nitro groups, carboxy groups, alkoxy groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group , Sulfamoylamino group, alkyl and aryls Phononylamino, mercapto, alkylthio, arylthio, heterocyclic thio, sulfamoyl, sulfo, alkyl and arylsulfinyl, alkyl and arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, Aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyl oxy groups, phosphinyl amino groups, phosphono groups, silyl groups (including mono-, di- and trialkylsilyl groups), hydrazino Groups, ureido groups, boronic acid groups (-B (OH) 2 ), phosphato groups (-OPO (OH) 2 ), sulfato groups (-OSO 3 H), and other known substituents. In addition, R may be further substituted by a substituent. Examples of the substituent include the groups exemplified for R.
 これらの中でも、Rとしては、ハロゲン原子、アルキル基、アルコキシ基、アルキニル基、アシル基、アシルオキシ基、アリール基、複素環基が好ましく、アルキル基、アリール基(芳香族炭化水素基)、又は、芳香族複素環基がより好ましい。
 ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示され、フッ素原子が好ましい。
 アルキル基としては、炭素数2~18のアルキル基が好ましく、炭素数3~15のアルキル基がより好ましく、炭素数4~12のアルキル基が更に好ましい。上記アルキル基は、直鎖状、分岐状又は環状のいずれでもよく、これらを組み合わせた構造でもよいが、直鎖状又は分岐状のアルキル基であることが好ましく、直鎖状のアルキル基であることがより好ましい。
 アルコキシ基としては、炭素数2~18のアルコキシ基であることが好ましく、炭素数3~15のアルコキシ基であることがより好ましく、炭素数4~12のアルコキシ基であることが更に好ましい。アルコキシ基のアルキル基部分は、直鎖状、分岐状又は環状のいずれでもよく、これらを組み合わせた構造でもよいが、直鎖状又は分岐状のアルキル基であることが好ましい。
 アルキニル基としては、炭素数2~18のアルキニル基が好ましく、炭素数3~15のアルキニル基がより好ましく、炭素数4~12のアルキニル基が更に好ましい。
 アシル基(R-C(=O)-)としては、炭素数2~18のアシル基が好ましく、炭素数3~15のアシル基がより好ましく、炭素数4~12のアシル基がより好ましい。
 アシルオキシ基(R-(=O)-O-)としては、炭素数2~18のアシルオキシ基が好ましく、炭素数3~15のアシルオキシ基がより好ましく、炭素数4~12のアシルオキシ基が更に好ましい。
Among these, R is preferably a halogen atom, an alkyl group, an alkoxy group, an alkynyl group, an acyl group, an acyloxy group, an aryl group or a heterocyclic group, and an alkyl group, an aryl group (aromatic hydrocarbon group) or An aromatic heterocyclic group is more preferred.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, and a fluorine atom is preferable.
The alkyl group is preferably an alkyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 3 to 15 carbon atoms, and still more preferably an alkyl group having 4 to 12 carbon atoms. The alkyl group may be linear, branched or cyclic, or may have a structure combining them, but is preferably a linear or branched alkyl group, and is a linear alkyl group Is more preferred.
The alkoxy group is preferably an alkoxy group having 2 to 18 carbon atoms, more preferably an alkoxy group having 3 to 15 carbon atoms, and still more preferably an alkoxy group having 4 to 12 carbon atoms. The alkyl group portion of the alkoxy group may be linear, branched or cyclic, or may be a combination of these, but is preferably a linear or branched alkyl group.
The alkynyl group is preferably an alkynyl group having 2 to 18 carbon atoms, more preferably an alkynyl group having 3 to 15 carbon atoms, and still more preferably an alkynyl group having 4 to 12 carbon atoms.
The acyl group (R—C (= O) —) is preferably an acyl group having 2 to 18 carbon atoms, more preferably an acyl group having 3 to 15 carbon atoms, and still more preferably an acyl group having 4 to 12 carbon atoms.
The acyloxy group (R-(= O) -O-) is preferably an acyloxy group having 2 to 18 carbon atoms, more preferably an acyloxy group having 3 to 15 carbon atoms, still more preferably an acyloxy group having 4 to 12 carbon atoms .
 アリール基(芳香族炭化水素基)としては、ベンゼン、ナフタレン、アントラセン等から水素を1つ除いた基が例示される。
 また、芳香族複素環基としては、チオフェン環、フラン環、ピラン環、ピロール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、セレノフェン環、イミダゾール環等から水素原子を1つ除いた基が挙げられ、チオフェン環、セレノフェン環、又は、ピロール環から水素原子を1つ除いた基であることが好ましく、チオフェン環又はフラン環から水素原子を1つ除いた基であることがより好ましく、チオフェン環から水素原子を1つ除いた基であることが更に好ましい。
Examples of the aryl group (aromatic hydrocarbon group) include groups in which one hydrogen is removed from benzene, naphthalene, anthracene or the like.
Further, as the aromatic heterocyclic group, groups in which one hydrogen atom has been removed from a thiophene ring, furan ring, pyran ring, pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, selenophen ring, imidazole ring, etc. Preferably a group in which one hydrogen atom is removed from a thiophene ring, a selenophen ring, or a pyrrole ring, more preferably a group in which one hydrogen atom is removed from a thiophene ring or a furan ring, More preferably, it is a group in which one hydrogen atom has been removed from the ring.
 mが1の場合、Rの少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表す。mが1の時、Rの少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表さないと、π共役系が小さいため十分な移動度が得られない。
 mが1の時、Rの少なくとも1つが芳香族炭化水素基又は芳香族複素環基であり、移動度の観点から、少なくとも2つが芳香族炭化水素基又は芳香族複素環基であることが好ましい。
 mが1の場合、Rが表す芳香族炭化水素基としては、ベンゼン環、ナフタレン環、アントラセン環等から水素原子を1つ除いた基が例示される。これらの中でも、ベンゼン環又はナフタレン環から水素原子を1つ除いた基が好ましく、ベンゼン環から水素原子を1つ除いた基が特に好ましい。
 また、Rが表す芳香族複素環基としては、チオフェン環、フラン環、ピラン環、ピロール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、セレノフェン環、イミダゾール環等から水素原子を1つ除いた基が挙げられ、チオフェン環、セレノフェン環、又は、ピロール環から水素原子を1つ除いた基であることが好ましく、チオフェン環又はフラン環から水素原子を1つ除いた基であることがより好ましく、チオフェン環から水素原子を1つ除いた基であることが更に好ましい。
 Rが表す芳香族炭化水素基又は芳香族複素環基は、ベンゼン環又はチオフェン環から水素原子を1つ除いた基であることが特に好ましい。
 なお、Rの少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表すとは、環Aを含む縮合多環芳香族基に、直接芳香族炭化水素基又は芳香族複素環基が結合していることを意味する。
When m is 1, at least one of R represents an aromatic hydrocarbon group or an aromatic heterocyclic group. When m is 1, unless at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, sufficient mobility can not be obtained because the π conjugated system is small.
When m is 1, it is preferable that at least one of R is an aromatic hydrocarbon group or an aromatic heterocyclic group, and from the viewpoint of mobility, at least two are an aromatic hydrocarbon group or an aromatic heterocyclic group .
When m is 1, examples of the aromatic hydrocarbon group represented by R include groups in which one hydrogen atom has been removed from a benzene ring, a naphthalene ring, an anthracene ring or the like. Among these, a group in which one hydrogen atom is removed from a benzene ring or a naphthalene ring is preferable, and a group in which one hydrogen atom is removed from a benzene ring is particularly preferable.
Further, as the aromatic heterocyclic group represented by R, one hydrogen atom is removed from a thiophene ring, furan ring, pyran ring, pyrrole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, selenophen ring, imidazole ring, etc. Preferred is a group in which one hydrogen atom is removed from a thiophene ring, a selenophen ring, or a pyrrole ring, and a group in which one hydrogen atom is removed from a thiophene ring or a furan ring More preferably, it is a group obtained by removing one hydrogen atom from a thiophene ring.
The aromatic hydrocarbon group or aromatic heterocyclic group represented by R is particularly preferably a group obtained by removing one hydrogen atom from a benzene ring or a thiophene ring.
When at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, it means that an aromatic hydrocarbon group or an aromatic heterocyclic group is directly bonded to a fused polycyclic aromatic group containing ring A. Means that
 また、mが4又は5の場合は3つ以上のRが芳香族炭化水素基又は芳香族複素環基になることはない。mが4又は5の場合に、3つ以上のRが芳香族炭化水素基又は芳香族複素環基であると、π共役系が大きくなり過ぎることにより、溶解度が非常に低く、また昇華温度は非常に高くなる。そのため、塗布製膜時には膜質不良で性能が悪化しやすくなり、蒸着製膜時には熱分解物を生じるため性能が悪化しやすくなる。
 mが4又は5である場合、0~2つのRが芳香族炭化水素基又は芳香族複素環基であり、0又は1つのRが芳香族炭化水素基又は芳香族複素環基であることが好ましく、芳香族炭化水素基又は芳香族複素環基を表すRを有しないことがより好ましい。
In addition, when m is 4 or 5, three or more of R do not become an aromatic hydrocarbon group or an aromatic heterocyclic group. When m is 4 or 5, and the three or more Rs are aromatic hydrocarbon groups or aromatic heterocyclic groups, the solubility is very low because the π conjugated system becomes too large, and the sublimation temperature is It will be very expensive. Therefore, the performance tends to deteriorate due to poor film quality at the time of coating film formation, and the thermal decomposition product is generated at the time of deposition film formation, so that the performance tends to deteriorate.
When m is 4 or 5, 0 to 2 Rs are an aromatic hydrocarbon group or an aromatic heterocyclic group, and 0 or 1 R is an aromatic hydrocarbon group or an aromatic heterocyclic group It is more preferable not to have R which represents an aromatic hydrocarbon group or an aromatic heterocyclic group.
 nは、0以上の整数を表し、縮合多環芳香族基に対するRの置換数を意味する。なお、mが1の場合、nは1以上の整数を表し、mが2~5の場合、nは0以上の整数を表す。nは、1以上であることが好ましく、2以上であることがより好ましい。nの上限は特に限定されないが、移動度及び製膜性の観点から、8以下であることが好ましく、6以下であることがより好ましく、4以下であることが更に好ましい。 N represents an integer of 0 or more and means the number of substitution of R for a fused polycyclic aromatic group. When m is 1, n is an integer of 1 or more, and when m is 2 to 5, n is an integer of 0 or more. n is preferably 1 or more, and more preferably 2 or more. The upper limit of n is not particularly limited, but is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less from the viewpoint of mobility and film formability.
 特定有機半導体化合物中には、環Aを含む縮合多環芳香族基(縮合多環芳香族構造)が含まれるが、この基が主成分として含まれることが好ましい。ここで主成分とは、縮合多環芳香族基の分子量の含有量が、特定有機半導体化合物の全分子量に対して、30%以上であることを意味し、40%以上であることが好ましい。上限は特に制限されないが、溶解性の点から、95%以下であることが好ましい。 The specific organic semiconductor compound includes a fused polycyclic aromatic group containing a ring A (fused polycyclic aromatic structure), and it is preferable that this group be included as a main component. Here, the main component means that the content of the molecular weight of the fused polycyclic aromatic group is 30% or more with respect to the total molecular weight of the specific organic semiconductor compound, and is preferably 40% or more. The upper limit is not particularly limited, but is preferably 95% or less from the viewpoint of solubility.
 特定有機半導体化合物は、下記式2で表される化合物であることがより好ましい。 The specific organic semiconductor compound is more preferably a compound represented by the following formula 2.
Figure JPOXMLDOC01-appb-C000031
 式2中、Tは下記T-1~T-35よりなる群から選択されるいずれかの構造を表し、R’はそれぞれ独立に置換基を表し、nは0~6の整数を表し、TがT-1又はT-2である場合、R’の少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、TがT-20~T-35のいずれかである場合、3つ以上のR’が芳香族炭化水素基又は芳香族複素環基になることはない。
Figure JPOXMLDOC01-appb-C000031
In Formula 2, T represents any structure selected from the group consisting of T-1 to T-35 below, R ′ independently represents a substituent, n represents an integer of 0 to 6, and T represents When at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group when T is T-1 or T-2, and three when T is any of T-20 to T-35 The above R 'does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
 T-1~T-35中、Xはそれぞれ独立に、O、S、Se、NR’のいずれかを表す。
Figure JPOXMLDOC01-appb-C000033
In T-1 to T-35, X each independently represents any of O, S, Se, and NR '.
 式2中、Tは、T-1、T-2、T-3、T-4、T-9、T-11、T-22、T-23、T-24、T-25であることが好ましく、T-3、T-4、T-9、T-11、T-22であることがより好ましく、T-9、T-11が更に好ましい。 In Formula 2, T is T-1, T-2, T-3, T-4, T-9, T-11, T-22, T-23, T-24, T-25 T-3, T-4, T-9, T-11 and T-22 are more preferable, and T-9 and T-11 are more preferable.
 式2中、R’は式1中のRと同義である。
 また、式2中、Xの好ましい範囲は、式1中のXの好ましい範囲と同様である。
 式2中、R’は下記式3で表されることが好ましい。
In Formula 2, R 'is synonymous with R in Formula 1.
Moreover, in Formula 2, the preferable range of X is the same as the preferable range of X in Formula 1.
In Formula 2, R ′ is preferably represented by Formula 3 below.
Figure JPOXMLDOC01-appb-C000034
 式3中、Lはそれぞれ独立に、下記式L-1~式L-12のいずれかで表される2価の連結基、又は、2以上の下記式L-1~式L-12のいずれかで表される2価の連結基が2つ以上結合した2価の連結基を表し、Zはそれぞれ独立に、水素原子、アルキル基、オキシエチレン単位の繰り返し数が2以上のオリゴオキシエチレン基、ケイ素原子数が2以上のオリゴシロキサン基、又は、トリアルキルシリル基を表し、ただし、Zがトリアルキルシリル基を表すのは、Zに隣接するLが下記式L-3で表される連結基である場合に限り、水素原子を表すのは、Zに隣接するLが下記式L-1、L-2、L-3、L-10、L-11、又は、L-12で表される連結基である場合に限る。
Figure JPOXMLDOC01-appb-C000034
In Formula 3, L is each independently a divalent linking group represented by any one of the following Formulas L-1 to L-12, or any of two or more of the following Formulas L-1 to L-12. And each of Z's independently represents a hydrogen atom, an alkyl group, or an oligooxyethylene group having a repeating number of oxyethylene units of 2 or more. And an oligosiloxane group having a silicon atom number of 2 or more, or a trialkylsilyl group, provided that Z represents a trialkylsilyl group, and a linkage in which L adjacent to Z is represented by the following formula L-3 Only when it is a group, it means that L adjacent to Z is represented by the following formula L-1, L-2, L-3, L-10, L-11 or L-12. Limited if it is a
Figure JPOXMLDOC01-appb-C000035
 式L-1~式L-12中、*及び波線部分は他の構造との結合位置を表し、式L-1、式L-2及び式L-10~式L-12におけるRL1はそれぞれ独立に、水素原子又は置換基を表す。
Figure JPOXMLDOC01-appb-C000035
In Formula L-1 to Formula L-12, * and a wavy line portion indicate bonding positions with other structures, and R L1 in Formula L-1, Formula L-2 and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.
 式L-1~式L-12中、波線部分がT-1~T-35よりなる群から選択されるいずれかの構造との結合位置を表し、*は、Zとの結合位置、又は、他のL-1~L-12よりなる群から選択される2価の連結基との結合位置を表すことが好ましい。
 なお、Lが、上記式L-1~式L-12のいずれかで表される2価の連結基が結合した連結基を表す場合、式L-1~式L-12のいずれかで表される2価の連結基の結合数は、2~4であることが好ましく、2又は3であることがより好ましい。
 L-1、L-2、L-10、L-11及びL-12中、複数存在するRL1は同一でも異なっていてもよい。また、L-1及びL-2中、RL1は、それぞれ隣接するZと結合して環構造を形成してもよく、上記環構造として、縮合環を形成していてもよい。
 RL1としては、水素原子、又は、上記式1におけるRとして例示した各種の置換基が例示される。
In formulas L-1 to L-12, the dashed line represents a bonding position to any structure selected from the group consisting of T-1 to T-35, and * represents a bonding position to Z, or It is preferable to represent the bonding position with a divalent linking group selected from the group consisting of other L-1 to L-12.
When L represents a linking group to which a divalent linking group represented by any one of the above formulas L-1 to L-12 is bonded, the table is represented by any one of formulas L-1 to L-12. The number of bonded bivalent linking groups is preferably 2 to 4, and more preferably 2 or 3.
L1, in L-2, L-10, L-11 and L-12, R L1 existing in plural numbers may be the same or different. In L-1 and L-2, RL1 may be bonded to Z adjacent thereto to form a ring structure, or may form a fused ring as the above ring structure.
Examples of R L1 include a hydrogen atom, and various substituents exemplified as R in the above-mentioned formula 1.
 上記式L-10で表される2価の連結基は、下記式L-10A、式L-10B、又は、式L-10Cで表される2価の連結基であり、式L-10A又は式L-10Bで表される2価の連結基であることが好ましく、式L-10Bで表される2価の連結基であることがより好ましい。 The divalent linking group represented by the above formula L-10 is a divalent linking group represented by the following formula L-10A, formula L-10B, or formula L-10C, and the formula L-10A or The divalent linking group represented by the formula L-10B is preferable, and the divalent linking group represented by the formula L-10B is more preferable.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
 上記式L-12で表される2価の連結基は、下記式L-12A、L-12B又はL-12Cで表される2価の連結基であり、式L-12A又はL-12Bで表される2価の連結基であることが好ましく、式L-12Bで表される2価の連結基であることがより好ましい。 The divalent linking group represented by the above formula L-12 is a divalent linking group represented by the following formula L-12A, L-12B or L-12C, and in the formula L-12A or L-12B The divalent linking group represented is preferable, and the divalent linking group represented by the formula L-12B is more preferable.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
 上記Lは式L-1~L-6、L-10、L-11及びL-12のいずれかで表される2価の連結基、又は、これらの2価の連結基が2以上結合した2価の連結基であることが好ましく、式L-1~L-5、L-10、L-11及びL-12のいずれかで表される2価の連結基、又は、これらの2価の連結基が2以上結合した2価の連結基であることがより好ましく、化学的安定性、高い移動度が得られる観点から式L-1、L-3、L-10、L-11及びL-12のいずれかで表される2価の連結基、又は、これらの2価の連結基が2以上結合した2価の連結基であることが更に好ましく、式L-1、L-3、L-10、及び、L-12のいずれかで表される2価の連結基、又は、これらの2価の連結基が2以上結合した2価の連結基であることが特に好ましく、式L-1若しくは又はL-3で表される2価の連結基、又は、これらの2価の連結基が2以上結合した2価の連結基であることが最も好ましい。 L is a divalent linking group represented by any one of formulas L-1 to L-6, L-10, L-11 and L-12, or two or more of these divalent linking groups are bonded A divalent linking group is preferable, and a divalent linking group represented by any one of formulas L-1 to L-5, L-10, L-11 and L-12, or a divalent thereof Is more preferably a divalent linking group in which two or more linking groups are linked, and from the viewpoint of obtaining chemical stability and high mobility, the formulas L-1, L-3, L-10, L-11 and More preferably, it is a divalent linking group represented by any one of L-12, or a divalent linking group in which two or more of these divalent linking groups are bonded, as represented by formulas L-1 and L-3. , L-10 and L-12, or a divalent linking group in which two or more of these divalent linking groups are bonded to each other. Are most preferably a divalent linking group represented by the formula L-1 or L-3, or a divalent linking group in which two or more of these divalent linking groups are bonded. .
 Zがアルキル基である場合、炭素数1以上のアルキル基であれば特に限定されないが、化学的安定性、キャリア輸送性の観点から、炭素数は2~18であることが好ましく、3~12であることがより好ましく、4~10であることが更に好ましく、4~8であることが特に好ましく、4~6であることが最も好ましい。
 特定有機半導体化合物は、上記-L-Zにアルキル基が含まれる場合、Zが表すアルキル基が上記範囲の下限値以上であるとキャリア移動度が高くなる。また、LがZに隣接する式L-1を含む場合は、式L-1で表されるアルキレン基及びZで表されるアルキル基が結合して形成されるアルキル基の炭素数が上記範囲の下限値以上であるとキャリア移動度が高くなる。
 Zが表すアルキル基は、直鎖状、分岐状、環状のいずれであってもよく、直鎖アルキル基であることがキャリア移動度を高める観点から好ましく、炭素数1~12の直鎖アルキル基であることがより好ましく、炭素数3~12の直鎖アルキル基であることが更に好ましく、炭素数4~10の直鎖アルキル基であることが特に好ましく、炭素数4~8の直鎖アルキル基であることが更に特に好ましく、炭素数4~6の直鎖アルキル基であることが最も好ましい。Zが置換基を有するアルキル基である場合の置換基としては、ハロゲン原子などを挙げることができ、フッ素原子が好ましい。なお、Zがフッ素原子を有するアルキル基である場合はアルキル基の水素原子が全てフッ素原子で置換されてパーフルオロアルキル基を形成してもよい。
When Z is an alkyl group, it is not particularly limited as long as it is an alkyl group having 1 or more carbon atoms, but from the viewpoint of chemical stability and carrier transportability, the number of carbon atoms is preferably 2 to 18 and 3 to 12 more preferably, more preferably from 4 to 10, particularly preferably from 4 to 8, most preferably 4-6.
In the specific organic semiconductor compound, when an alkyl group is contained in the above-mentioned -LZ, the carrier mobility becomes high when the alkyl group represented by Z is at least the lower limit value of the above range. Moreover, when L contains Formula L-1 which adjoins Z, carbon number of the alkyl group formed when the alkylene group represented by Formula L-1 and the alkyl group represented by Z couple | bonds the said range Carrier mobility will become it high that it is more than the lower limit of.
The alkyl group represented by Z may be linear, branched or cyclic, and is preferably a linear alkyl group from the viewpoint of enhancing carrier mobility, and is a linear alkyl group having 1 to 12 carbon atoms. Is more preferably a linear alkyl group having 3 to 12 carbon atoms, and particularly preferably a linear alkyl group having 4 to 10 carbon atoms, a linear alkyl group having 4 to 8 carbon atoms More preferably, it is a group, and most preferably a linear alkyl group of 4 to 6 carbon atoms. A halogen atom etc. can be mentioned as a substituent in case Z is an alkyl group which has a substituent, A fluorine atom is preferable. When Z is an alkyl group having a fluorine atom, all hydrogen atoms of the alkyl group may be substituted with a fluorine atom to form a perfluoroalkyl group.
 上記Zがオキシエチレン単位の繰り返し数が2以上のオリゴオキシエチレン基を表す場合、Zが表すオキシエチレン単位とは本明細書中、-(OCH2CH2xOYで表される基のことをいう(オキシエチレン単位の繰り返し数xは2以上の整数を表し、末端のYは水素原子又は置換基を表す。)。なお、オリゴオキシエチレン基の末端のYが水素原子である場合はヒドロキシ基となる。オキシエチレン単位の繰り返し数xは2~4であることが好ましく、2~3であることがより好ましい。オリゴオキシエチレン基の末端のヒドロキシ基は封止されていること、すなわちYが置換基を表すことが好ましい。この場合、ヒドロキシ基は、炭素数が1~3のアルキル基で封止されること、すなわちYが炭素数1~3のアルキル基であることが好ましく、Yがメチル基やエチル基であることがより好ましく、メチル基であることが更に好ましい。 When Z represents an oligooxyethylene group in which the number of repeating oxyethylene units is 2 or more, the oxyethylene unit represented by Z is a group represented by-(OCH 2 CH 2 ) x OY in the present specification. (The repeating number x of the oxyethylene unit represents an integer of 2 or more, and the terminal Y represents a hydrogen atom or a substituent.). When Y at the end of the oligooxyethylene group is a hydrogen atom, it is a hydroxy group. The repeat number x of the oxyethylene unit is preferably 2 to 4, and more preferably 2 to 3. It is preferable that the terminal hydroxy group of the oligooxyethylene group is sealed, that is, Y represents a substituent. In this case, the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. Is more preferable, and a methyl group is more preferable.
 上記Zが、ケイ素原子数が2以上のオリゴシロキサン基の場合、シロキサン単位の繰り返し数は2~4であることが好ましく、2~3であることがより好ましい。また、Si原子には、水素原子やアルキル基が結合することが好ましい。Si原子にアルキル基が結合する場合、アルキル基の炭素数は1~3であることが好ましく、例えば、メチル基やエチル基が結合することが好ましい。Si原子には、同一のアルキル基が結合してもよく、異なるアルキル基又は水素原子が結合してもよい。また、オリゴシロキサン基を構成するシロキサン単位はすべて同一であっても異なっていてもよいが、すべて同一であることが好ましい。
 Zに隣接するLが上記式L-3で表される2価の連結基である場合に限り、Zが置換又は無置換のトリアルキルシリル基をとり得る。Zが置換又は無置換のトリアルキルシリル基の場合、Si原子に結合するアルキル基の炭素数は1~3であることが好ましく、例えば、メチル基やエチル基やイソプロピル基が結合することが好ましい。
 Si原子には、同一のアルキル基が結合してもよく、異なるアルキル基が結合してもよい。Zが置換基を有するトリアルキルシリル基である場合の置換基としては、特に制限はない。
When Z is an oligosiloxane group having 2 or more silicon atoms, the number of repetition of the siloxane unit is preferably 2 to 4, and more preferably 2 to 3. Further, a hydrogen atom or an alkyl group is preferably bonded to the Si atom. When an alkyl group is bonded to a Si atom, the carbon number of the alkyl group is preferably 1 to 3, and for example, a methyl group or an ethyl group is preferably bonded. The same alkyl group may be bonded to the Si atom, or different alkyl groups or hydrogen atoms may be bonded. Moreover, although all the siloxane units which comprise an oligo siloxane group may be same or different, it is preferable that all are the same.
Only when L adjacent to Z is a divalent linking group represented by the above formula L-3, Z can take a substituted or unsubstituted trialkylsilyl group. When Z is a substituted or unsubstituted trialkylsilyl group, the carbon number of the alkyl group bonded to the Si atom is preferably 1 to 3, and for example, a methyl group, an ethyl group or an isopropyl group is preferably bonded .
The same alkyl group may be bonded to a Si atom, or different alkyl groups may be bonded. When Z is a trialkylsilyl group having a substituent, the substituent is not particularly limited.
 本発明において、式1における環Aを含む縮合多環芳香族基(有機半導体母核)、又は、式2におけるTの具体例としては、下記に示す縮合多環芳香族基(t-1~t-35)が好ましく例示されるが、本発明はこれらの例に限定されるものではない。 In the present invention, as a specific example of the fused polycyclic aromatic group (organic semiconductor mother nucleus) containing the ring A in the formula 1 or T in the formula 2, the fused polycyclic aromatic group (t-1 to Although t-35) is preferably exemplified, the present invention is not limited to these examples.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
 これらの中でも、t-1、t-2、t-3、t-4、t-9、t-11、t-22、t-23、t-24、t-25が好ましく、t-3、t-4、t-9、t-11、t-22がより好ましく、t-9、t-11が更に好ましい。 Among these, t-1, t-2, t-3, t-4, t-9, t-11, t-22, t-23, t-24 and t-25 are preferable, and t-3, t-4, t-9, t-11 and t-22 are more preferable, and t-9 and t-11 are more preferable.
 特定有機半導体化合物の分子量は、特に制限されないが、分子量が1,500以下であることが好ましく、1,000以下であることがより好ましく、800以下であることが更に好ましく、700以下であることが特に好ましい。分子量を上記上限値以下とすることにより、溶媒への溶解性を高めることができる。一方で、薄膜の膜質安定性の観点からは、分子量は400以上であることが好ましく、450以上であることがより好ましく、500以上であることが更に好ましい。
 後述する有機半導体層、後述する有機半導体膜又は有機半導体膜形成用組成物中には、1種のみの特定有機半導体化合物が含まれていても、2種以上の特定有機半導体化合物が含まれていてもよいが、配向性の観点から、1種のみであることが好ましい。
The molecular weight of the specific organic semiconductor compound is not particularly limited, but it is preferably 1,500 or less, more preferably 1,000 or less, still more preferably 800 or less, and 700 or less. Is particularly preferred. By setting the molecular weight to the above upper limit or less, the solubility in a solvent can be enhanced. On the other hand, from the viewpoint of the film quality stability of the thin film, the molecular weight is preferably 400 or more, more preferably 450 or more, and still more preferably 500 or more.
Even if only one specific organic semiconductor compound is contained in an organic semiconductor layer described later, an organic semiconductor film to be described later, or a composition for forming an organic semiconductor film, two or more specific organic semiconductor compounds are contained. Although it may be used, from the viewpoint of orientation, it is preferable to be only one kind.
 特定有機半導体化合物の合成方法は、特に制限されず、公知の方法を参照して合成できる。合成方法としては、置換基としてハロゲン原子を有する有機半導体母核を合成し、Stilleカップリング反応、鈴木-宮浦カップリング反応、根岸カップリング反応、熊田カップリング反応等の各種カップリング反応を行う方法が挙げられる。 The synthesis method of the specific organic semiconductor compound is not particularly limited, and can be synthesized with reference to known methods. As a synthesis method, an organic semiconductor mother nucleus having a halogen atom as a substituent is synthesized, and various coupling reactions such as Stille coupling reaction, Suzuki-Miyaura coupling reaction, Negishi coupling reaction, and Kumada coupling reaction are performed. Can be mentioned.
 以下に特定有機半導体化合物の好ましい具体例を示すが、これらに限定されないことはいうまでもない。 Although the preferable specific example of a specific organic-semiconductor compound is shown below, it can not be overemphasized that it is not limited to these.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
 本発明の有機半導体素子の有機半導体層又は後述する本発明の有機半導体膜における、特定有機半導体化合物の含有量は、30~100質量%であることが好ましく、50~100質量%であることがより好ましく、70~100質量%であることが更に好ましい。また、後述するバインダーポリマーを含有しない場合は、上記含有量が、90~100質量%であることが好ましく、95~100質量%であることがより好ましい。 The content of the specific organic semiconductor compound in the organic semiconductor layer of the organic semiconductor device of the present invention or the organic semiconductor film of the present invention described later is preferably 30 to 100% by mass, and is 50 to 100% by mass. More preferably, it is 70 to 100% by mass. When the binder polymer described later is not contained, the content is preferably 90 to 100% by mass, and more preferably 95 to 100% by mass.
<バインダーポリマー>
 本発明の有機半導体素子の有機半導体層は、バインダーポリマーを含有することが好ましい。
 また、本発明の有機半導体素子は、上記有機半導体層とバインダーポリマーを含む層を有する有機半導体素子であってもよい。
 バインダーポリマーの種類は特に制限されず、公知のバインダーポリマーを用いることができる。
 バインダーポリマーとしては、ポリスチレン樹脂、アクリル樹脂、ゴム、熱可塑性エラストマー等が挙げられる。
 中でも、バインダーポリマーとしては、ベンゼン環を有する高分子化合物(ベンゼン環基を有する単量体単位を有する高分子)が好ましい。ベンゼン環基を有する単量体単位の含有量は特に制限されないが、全単量体単位中、50モル%以上が好ましく、70モル%以上がより好ましく、90モル%以上が更に好ましい。上限は特に制限されないが、100モル%が挙げられる。
 上記バインダーポリマーとしては、例えば、ポリスチレン、ポリ(α-メチルスチレン)、ポリビニルシンナメート、ポリ(4-ビニルフェニル)、ポリ(4-メチルスチレン)などが挙げられる。
<Binder polymer>
It is preferable that the organic-semiconductor layer of the organic-semiconductor element of this invention contains a binder polymer.
The organic semiconductor device of the present invention may be an organic semiconductor device having a layer containing the organic semiconductor layer and a binder polymer.
The type of binder polymer is not particularly limited, and known binder polymers can be used.
Examples of the binder polymer include polystyrene resin, acrylic resin, rubber, thermoplastic elastomer and the like.
Among them, as the binder polymer, a polymer compound having a benzene ring (polymer having a monomer unit having a benzene ring) are preferred. The content of the monomer unit having a benzene ring group is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more, based on all the monomer units. Although the upper limit in particular is not restrict | limited, 100 mol% is mentioned.
Examples of the binder polymer include polystyrene, poly (α-methylstyrene), polyvinylcinnamate, poly (4-vinylphenyl), poly (4-methylstyrene) and the like.
 パインダーポリマーの重量平均分子量は、特に制限されないが、1,000~200万が好ましく、3,000~100万がより好ましく、5,000~60万が更に好ましい。
 また、後述する溶媒を用いる場合、パインダーポリマーは、使用する溶媒への溶解度が、特定化合物よりも高いことが好ましい。上記態様であると、得られる有機半導体の移動度及び熱安定性により優れる。
 本発明の有機半導体素子の有機半導体層におけるバインダーポリマーの含有量は、特定化合物の含有量100質量部に対し、1~200質量部であることが好ましく、10~150質量部であることがより好ましく、20~120質量部であることが更に好ましい。上記範囲であると、得られる有機半導体の移動度及び熱安定性により優れる。
The weight average molecular weight of the pinder polymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 3,000 to 1,000,000, and still more preferably 5,000 to 600,000.
Moreover, when using the solvent mentioned later, it is preferable that a pinder polymer has the solubility to the solvent to be used higher than a specific compound. It is excellent by the mobility and thermal stability of the organic semiconductor obtained as it is the said aspect.
The content of the binder polymer in the organic semiconductor layer of the organic semiconductor element of the present invention is preferably 1 to 200 parts by mass, and more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the specific compound. Preferably, it is more preferably 20 to 120 parts by mass. It is excellent by the mobility and thermal stability of the organic semiconductor obtained as it is the said range.
<その他の成分>
 本発明の有機半導体素子における有機半導体層には、特定有機半導体化合物及びバインダーポリマー以外に他の成分が含まれていてもよい。
 その他の成分としては、公知の添加剤等を用いることができる。
 上記有機半導体層における特定化合物及びバインダーポリマー以外の成分の含有量は、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、1質量%以下であることが更に好ましく、0.1質量%以下であることが特に好ましい。上記範囲であると、膜形成性に優れ、得られる有機半導体の移動度及び熱安定性により優れる。
<Other ingredients>
The organic semiconductor layer in the organic semiconductor device of the present invention may contain other components other than the specific organic semiconductor compound and a binder polymer.
As other components, known additives and the like can be used.
The content of components other than the specific compound and the binder polymer in the organic semiconductor layer is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less. It is particularly preferable that the content be 0.1% by mass or less. It is excellent in film formation property as it is the said range, and it is excellent by the mobility and thermal stability of the organic semiconductor obtained.
 本発明の有機半導体素子における有機半導体層の形成方法は特に制限されず、後述する本発明の有機半導体膜形成用組成物を、ソース電極、ドレイン電極、及び、ゲート絶縁膜上に付与して、必要に応じて乾燥処理を施すことにより、所望の有機半導体層を形成することができる。 The method for forming the organic semiconductor layer in the organic semiconductor device of the present invention is not particularly limited, and the composition for forming an organic semiconductor film of the present invention described later is applied onto the source electrode, the drain electrode, and the gate insulating film. A desired organic semiconductor layer can be formed by subjecting it to drying treatment as necessary.
 本発明の有機半導体素子は、後述する本発明の有機半導体膜形成用組成物を用いて製造されたものであることが好ましい。
 本発明の有機半導体膜形成用組成物を用いて有機半導体膜や有機半導体素子を製造する方法は、特に制限されず、公知の方法を採用できる。例えば、組成物を所定の基材上に付与して、必要に応じて乾燥処理を施して、有機半導体膜を製造する方法が挙げられる。
 基材上に組成物を付与する方法は特に制限されず、公知の方法を採用でき、例えば、インクジェット印刷法、フレキソ印刷法、バーコート法、スピンコート法、ナイフコート法、ドクターブレード法などが挙げられ、インクジェット印刷法、フレキソ印刷法が好ましい。
 なお、フレキソ印刷法としては、フレキソ印刷版として感光性樹脂版を用いる態様が好適に挙げられる。態様によって、組成物を基板上に印刷して、パターンを容易に形成することができる。
 中でも、本発明の有機半導体素子の製造方法は、本発明の有機半導体膜形成用組成物を基板上に塗布する塗布工程、を含むことが好ましく、本発明の有機半導体膜形成用組成物が溶媒を含み、本発明の有機半導体膜形成用組成物を基板上に塗布する塗布工程、及び、塗布された組成物から溶媒を除去する除去工程を含むことがより好ましい。
It is preferable that the organic semiconductor element of this invention is manufactured using the composition for organic semiconductor film formation of this invention mentioned later.
The method for producing an organic semiconductor film or an organic semiconductor element using the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted. For example, the method of apply | coating a composition on a predetermined | prescribed base material, performing a drying process as needed, and manufacturing an organic-semiconductor film is mentioned.
The method for applying the composition onto the substrate is not particularly limited, and any known method can be employed, such as inkjet printing, flexographic printing, bar coating, spin coating, knife coating, doctor blade method, etc. And ink jet printing and flexographic printing are preferred.
In addition, as a flexographic printing method, the aspect which uses a photosensitive resin plate as a flexographic printing plate is mentioned suitably. In an embodiment, the composition can be printed on a substrate to easily form a pattern.
Among them, the method for producing an organic semiconductor device of the present invention preferably includes the step of applying the composition for forming an organic semiconductor film of the present invention on a substrate, and the composition for forming an organic semiconductor film of the present invention is a solvent It is more preferable to include an application step of applying the composition for forming an organic semiconductor film of the present invention on a substrate, and a removal step of removing a solvent from the applied composition.
 後述する本発明の有機半導体膜形成用組成物は、溶媒を含むことが好ましく、有機溶媒を含むことがより好ましい。
 溶媒としては、公知の溶媒を用いることができる。
 具体的には、例えば、ヘキサン、オクタン、デカン、トルエン、キシレン、メシチレン、エチルベンゼン、デカリン、1-メチルナフタレンなどの炭化水素系溶媒、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン系溶媒、ジクロロメタン、クロロホルム、テトラクロロメタン、ジクロロエタン、トリクロロエタン、テトラクロロエタン、クロロベンゼン、ジクロロベンゼン、クロロトルエンなどのハロゲン化炭化水素系溶媒、酢酸エチル、酢酸ブチル、酢酸アミルなどのエステル系溶媒、メタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、メチルセロソルブ、エチルセロソルブ、エチレングリコールなどのアルコール系溶媒、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソールなどのエーテル系溶媒、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のアミド系溶媒、1-メチル-2-ピロリドン、1-メチル-2-イミダゾリジノン等のイミド系溶媒、ジメチルスルフォキサイドなどのスルホキシド系溶媒、アセトニトリルなどのニトリル系溶媒が挙げられる。
It is preferable that the composition for organic-semiconductor film formation of this invention mentioned later contains a solvent, and it is more preferable that an organic solvent is included.
A well-known solvent can be used as a solvent.
Specifically, for example, hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin and 1-methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene and chlorotoluene, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, methanol, propanol, Alcohol solvents such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, dibutyl ether Ether solvents such as tetrahydrofuran, dioxane, anisole, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, imides such as 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone Examples thereof include system solvents, sulfoxide solvents such as dimethyl sulfoxide, and nitrile solvents such as acetonitrile.
 溶媒は、1種単独で用いてもよく、複数組み合わせて用いてもよい。
 これらの中でも、炭化水素系溶媒、ハロゲン化炭化水素系溶媒及び/又はエーテル系溶媒が好ましく、トルエン、キシレン、メシチレン、テトラリン、ジクロロベンゼン又はアニソールがより好ましい。
The solvents may be used alone or in combination of two or more.
Among these, hydrocarbon solvents, halogenated hydrocarbon solvents and / or ether solvents are preferable, and toluene, xylene, mesitylene, tetralin, dichlorobenzene or anisole is more preferable.
 溶媒の沸点が100℃以上であることが、製膜性の観点から好ましい。溶媒の沸点は、100~300℃であることがより好ましく、125~250℃であることが更に好ましく、150~225℃であることが特に好ましい。
 なお、最も含有量の多い溶媒の沸点が100℃以上であることが好ましく、全ての溶媒の沸点が100℃以上であることがより好ましい。
It is preferable from the viewpoint of film formability that the boiling point of the solvent is 100 ° C. or higher. The boiling point of the solvent is more preferably 100 to 300 ° C., further preferably 125 to 250 ° C., and particularly preferably 150 to 225 ° C.
In addition, it is preferable that the boiling point of the solvent with most content is 100 degreeC or more, and it is more preferable that the boiling point of all the solvents is 100 degreeC or more.
 溶媒を含有する場合、本発明の有機半導体膜形成用組成物における特定化合物の含有量は、0.05~50質量%であることが好ましく、0.1~25質量%であることがより好ましく、0.25~15質量%であることが更に好ましく、0.4~10質量%であることが特に好ましく、また、バインダーポリマーの含有量は、0.01~50質量%であることが好ましく、0.05~25質量%であることがより好ましく、0.1~10質量%であることが更に好ましい。上記範囲であると、塗布性に優れ、容易に有機半導体膜を形成することができる。 When the solvent is contained, the content of the specific compound in the composition for forming an organic semiconductor film of the present invention is preferably 0.05 to 50% by mass, and more preferably 0.1 to 25% by mass 0.25 to 15% by mass, more preferably 0.4 to 10% by mass, and the content of the binder polymer is preferably 0.01 to 50% by mass. And more preferably 0.1 to 10% by mass. It is excellent in applicability | paintability as it is the said range, and an organic-semiconductor film can be formed easily.
 上記除去工程における乾燥処理は、必要に応じて実施される処理であり、使用される特定化合物及び溶媒の種類により適宜最適な条件が選択される。中でも、得られる有機半導体の移動度及び熱安定性により優れ、また、生産性に優れる点で、加熱温度としては30℃~100℃が好ましく、40℃~80℃がより好ましく、加熱時間としては10~300分が好ましく、30~180分がより好ましい。 The drying process in the removal step is a process carried out as necessary, and the optimum conditions are appropriately selected depending on the type of the specific compound and the solvent used. Among them, the heating temperature is preferably 30 ° C. to 100 ° C., more preferably 40 ° C. to 80 ° C., and the heating time is more excellent in mobility and thermal stability of the obtained organic semiconductor and excellent in productivity. 10 to 300 minutes are preferable, and 30 to 180 minutes are more preferable.
 形成される有機半導体層の厚さは、特に制限されないが、得られる有機半導体の移動度及び熱安定性の観点から、10~500nmが好ましく、30~200nmがより好ましい。 The thickness of the organic semiconductor layer to be formed is not particularly limited, but is preferably 10 to 500 nm, more preferably 30 to 200 nm, from the viewpoint of the mobility and thermal stability of the obtained organic semiconductor.
 有機半導体素子としては、特に制限はないが、2~5端子の有機半導体素子であることが好ましく、2又は3端子の有機半導体素子であることがより好ましい。
 また、有機半導体素子としては、光電変換素子でないことが好ましい。
 更に、本発明の有機半導体素子は、非発光性有機半導体素子であることが好ましい。
 2端子素子としては、整流用ダイオード、定電圧ダイオード、PINダイオード、ショットキーバリアダイオード、サージ保護用ダイオード、ダイアック、バリスタ、トンネルダイオード等が挙げられる。
 3端子素子としては、バイポーラトランジスタ、ダーリントントランジスタ、電界効果トランジスタ、絶縁ゲートバイポーラトランジスタ、ユニジャンクショントランジスタ、静電誘導トランジスタ、ゲートターンサイリスタ、トライアック、静電誘導サイリスタ等が挙げられる。
 これらの中でも、整流用ダイオード、及び、トランジスタ類が好ましく挙げられ、電界効果トランジスタがより好ましく挙げられる。
 電界効果トランジスタとしては、有機薄膜トランジスタが好ましく挙げられる。
The organic semiconductor device is not particularly limited, but is preferably an organic semiconductor device of 2 to 5 terminals, and more preferably an organic semiconductor device of 2 or 3 terminals.
The organic semiconductor element is preferably not a photoelectric conversion element.
Furthermore, it is preferable that the organic-semiconductor element of this invention is a nonluminous organic-semiconductor element.
Examples of the two-terminal element include a rectifying diode, a constant voltage diode, a PIN diode, a Schottky barrier diode, a diode for surge protection, a diac, a varistor, a tunnel diode and the like.
Examples of three-terminal devices include bipolar transistors, Darlington transistors, field effect transistors, insulated gate bipolar transistors, unijunction transistors, electrostatic induction transistors, gate turn thyristors, triacs, electrostatic induction thyristors, and the like.
Among these, rectifying diodes and transistors are preferably mentioned, and field effect transistors are more preferably mentioned.
As a field effect transistor, an organic thin film transistor is preferably mentioned.
 本発明の有機薄膜トランジスタの一態様について図面を参照して説明する。
 図1は、本発明の有機半導体素子(有機薄膜トランジスタ(有機TFT))の一態様の断面模式図である。
 図1において、有機薄膜トランジスタ100は、基板10と、基板10上に配置されたゲート電極20と、ゲート電極20を覆うゲート絶縁膜30と、ゲート絶縁膜30のゲート電極20側とは反対側の表面に接するソース電極40及びドレイン電極42と、ソース電極40とドレイン電極42との間のゲート絶縁膜30の表面を覆う有機半導体膜50と、各部材を覆う封止層60とを備える。有機薄膜トランジスタ100は、ボトムゲート-ボトムコンタクト型の有機薄膜トランジスタである。
 なお、図1においては、有機半導体膜50が、上述した組成物より形成される膜に該当する。
 以下、基板、ゲート電極、ゲート絶縁膜、ソース電極、ドレイン電極、有機半導体膜及び封止層並びにそれぞれの形成方法について詳述する。
One aspect of the organic thin film transistor of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of one embodiment of the organic semiconductor device (organic thin film transistor (organic TFT)) of the present invention.
In FIG. 1, the organic thin film transistor 100 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and the gate insulating film 30 on the opposite side to the gate electrode 20 side. A source electrode 40 and a drain electrode 42 in contact with the surface, an organic semiconductor film 50 covering the surface of the gate insulating film 30 between the source electrode 40 and the drain electrode 42, and a sealing layer 60 covering each member. The organic thin film transistor 100 is a bottom gate-bottom contact type organic thin film transistor.
In addition, in FIG. 1, the organic semiconductor film 50 corresponds to the film | membrane formed from the composition mentioned above.
Hereinafter, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and the formation method of each will be described in detail.
<基板>
 基板は、後述するゲート電極、ソース電極、ドレイン電極などを支持する役割を果たす。
 基板の種類は特に制限されず、例えば、プラスチック基板、ガラス基板、セラミック基板などが挙げられる。中でも、各デバイスへの適用性及びコストの観点から、ガラス基板又はプラスチック基板であることが好ましい。
 プラスチック基板の材料としては、熱硬化性樹脂(例えば、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂、ポリエステル樹脂(例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)など)又は熱可塑性樹脂(例えば、フェノキシ樹脂、ポリエーテルスルフォン、ポリスルフォン、ポリフェニレンスルフォンなど)が挙げられる。
 セラミック基板の材料としては、例えば、アルミナ、窒化アルミニウム、ジルコニア、シリコン、窒化シリコン、シリコンカーバイドなどが挙げられる。
 ガラス基板の材料としては、例えば、ソーダガラス、カリガラス、ホウケイ酸ガラス、石英ガラス、アルミケイ酸ガラス、鉛ガラスなどが挙げられる。
<Board>
The substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode and the like described later.
The type of substrate is not particularly limited, and examples thereof include plastic substrates, glass substrates, ceramic substrates, and the like. Among them, a glass substrate or a plastic substrate is preferable from the viewpoint of the applicability to each device and the cost.
As a material of the plastic substrate, thermosetting resin (for example, epoxy resin, phenol resin, polyimide resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.) or thermoplastic resin (for example, phenoxy) Resin, polyether sulfone, polysulfone, polyphenylene sulfone and the like).
Examples of the material of the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide and the like.
Examples of the material of the glass substrate include soda glass, potash glass, borosilicate glass, quartz glass, aluminum silicate glass, lead glass and the like.
<ゲート電極、ソース電極、ドレイン電極>
 ゲート電極、ソース電極、ドレイン電極の材料としては、例えば、金(Au)、銀、アルミニウム(Al)、銅、クロム、ニッケル、コバルト、チタン、白金、タンタル、マグネシウム、カルシウム、バリウム、ナトリウム等の金属;InO2、SnO2、酸化インジウムスズ(ITO)等の導電性の酸化物;ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリジアセチレン等の導電性高分子;シリコン、ゲルマニウム、ガリウム砒素等の半導体;フラーレン、カーボンナノチューブ、グラファイト等の炭素材料などが挙げられる。中でも、金属であることが好ましく、銀又はアルミニウムであることがより好ましい。
 ゲート電極、ソース電極、ドレイン電極の厚みは特に制限されないが、20~200nmであることが好ましい。
<Gate electrode, source electrode, drain electrode>
Examples of the material of the gate electrode, the source electrode, and the drain electrode include, for example, gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum, magnesium, calcium, barium, sodium, etc. Metals; conductive oxides such as InO 2 , SnO 2 , indium tin oxide (ITO); conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, polydiacetylene; semiconductors such as silicon, germanium, gallium arsenide; And carbon materials such as carbon nanotubes and graphite. Among them, metal is preferable, and silver or aluminum is more preferable.
The thickness of the gate electrode, the source electrode, and the drain electrode is not particularly limited, but is preferably 20 to 200 nm.
 ゲート電極、ソース電極、ドレイン電極を形成する方法は特に制限されないが、例えば、基板上に、電極材料を真空蒸着又はスパッタする方法、電極形成用組成物を塗布又は印刷する方法などが挙げられる。また、電極をパターニングする場合、パターニングする方法としては、例えば、フォトリソグラフィー法;インクジェット印刷、スクリーン印刷、オフセット印刷、凸版印刷等の印刷法;マスク蒸着法などが挙げられる。 The method for forming the gate electrode, the source electrode, and the drain electrode is not particularly limited, and examples thereof include a method of vacuum depositing or sputtering an electrode material on a substrate, and a method of applying or printing a composition for electrode formation. Moreover, when patterning an electrode, as a method of patterning, printing methods, such as a photolithographic method; inkjet printing, screen printing, offset printing, letterpress printing, mask vapor deposition etc. are mentioned, for example.
<ゲート絶縁膜>
 ゲート絶縁膜の材料としては、ポリメチルメタクリレート、ポリスチレン、ポリビニルフェノール、ポリイミド、ポリカーボネート、ポリエステル、ポリビニルアルコール、ポリ酢酸ビニル、ポリウレタン、ポリスルホン、ポリベンゾオキサゾール、ポリシルセスキオキサン、エポキシ樹脂、フェノール樹脂等のポリマー;二酸化珪素、酸化アルミニウム、酸化チタン等の酸化物;窒化珪素等の窒化物などが挙げられる。これらの材料のうち、有機半導体膜との相性から、ポリマーであることが好ましい。
 ゲート絶縁膜の材料としてポリマーを用いる場合、架橋剤(例えば、メラミン)を併用することが好ましい。架橋剤を併用することで、ポリマーが架橋されて、形成されるゲート絶縁膜の耐久性が向上する。
 ゲート絶縁膜の膜厚は特に制限されないが、100~1,000nmであることが好ましい。
<Gate insulating film>
Materials for the gate insulating film include polymethyl methacrylate, polystyrene, polyvinyl phenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin, phenol resin, etc. And polymers such as silicon dioxide, aluminum oxide, oxides such as titanium oxide, and nitrides such as silicon nitride. Among these materials, a polymer is preferable in view of compatibility with the organic semiconductor film.
When a polymer is used as the material of the gate insulating film, it is preferable to use a crosslinking agent (for example, melamine) in combination. By using the crosslinking agent in combination, the polymer is crosslinked to improve the durability of the formed gate insulating film.
The thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1,000 nm.
 ゲート絶縁膜を形成する方法は特に制限されないが、例えば、ゲート電極が形成された基板上に、ゲート絶縁膜形成用組成物を塗布する方法、ゲート絶縁膜材料を蒸着又はスパッタする方法などが挙げられる。ゲート絶縁膜形成用組成物を塗布する方法は特に制限されず、公知の方法(バーコート法、スピンコート法、ナイフコート法、ドクターブレード法)を使用することができる。
 ゲート絶縁膜形成用組成物を塗布してゲート絶縁膜を形成する場合、溶媒除去、架橋などを目的として、塗布後に加熱(ベーク)してもよい。
Although the method for forming the gate insulating film is not particularly limited, for example, a method for applying a composition for forming a gate insulating film on a substrate on which a gate electrode is formed, a method for depositing or sputtering a gate insulating film material, etc. Be The method for applying the composition for forming a gate insulating film is not particularly limited, and known methods (bar coating method, spin coating method, knife coating method, doctor blade method) can be used.
When a gate insulating film is formed by applying a composition for forming a gate insulating film, heating (baking) may be performed after application for the purpose of solvent removal, crosslinking, and the like.
<バインダーポリマー層>
 本発明の有機半導体素子は、上記有機半導体層と絶縁膜との間に上記バインダーポリマー層を有することが好ましく、上記有機半導体層とゲート絶縁膜との間に上記バインダーポリマー層を有することがより好ましい。上記バインダーポリマー層の膜厚は特に制限されないが、20~500nmであることが好ましい。上記バインダーポリマー層は、上記ポリマーを含む層であればよいが、上記バインダーポリマーからなる層であることが好ましい。
<Binder polymer layer>
The organic semiconductor device of the present invention preferably has the binder polymer layer between the organic semiconductor layer and the insulating film, and more preferably has the binder polymer layer between the organic semiconductor layer and the gate insulating film. preferable. The thickness of the binder polymer layer is not particularly limited, but is preferably 20 to 500 nm. Although the said binder polymer layer should just be a layer containing the said polymer, it is preferable that it is a layer which consists of the said binder polymer.
 バインダーポリマー層を形成する方法は特に制限されないが、公知の方法(バーコート法、スピンコート法、ナイフコート法、ドクターブレード法、インクジェット法)を使用することができる。
 バインダーポリマー層形成用組成物を塗布してバインダーポリマー層を形成する場合、溶媒除去、架橋などを目的として、塗布後に加熱(ベーク)してもよい。
The method for forming the binder polymer layer is not particularly limited, but known methods (bar coating method, spin coating method, knife coating method, doctor blade method, ink jet method) can be used.
When the binder polymer layer forming composition is applied to form a binder polymer layer, heating (baking) may be performed after application for the purpose of solvent removal, crosslinking, and the like.
<封止層>
 本発明の有機半導体素子は、耐久性の観点から、最外層に封止層を備えることが好ましい。封止層には公知の封止剤を用いることができる。
 封止層の厚さは特に制限されないが、0.2~10μmであることが好ましい。
<Sealing layer>
It is preferable that the organic semiconductor element of this invention equips an outermost layer with a sealing layer from a durable viewpoint. A well-known sealing agent can be used for a sealing layer.
The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.
 封止層を形成する方法は特に制限されないが、例えば、ゲート電極とゲート絶縁膜とソース電極とドレイン電極と有機半導体膜とが形成された基板上に、封止層形成用組成物を塗布する方法などが挙げられる。封止層形成用組成物を塗布する方法の具体例は、ゲート絶縁膜形成用組成物を塗布する方法と同じである。封止層形成用組成物を塗布して有機半導体膜を形成する場合、溶媒除去、架橋などを目的として、塗布後に加熱(ベーク)してもよい。 Although the method for forming the sealing layer is not particularly limited, for example, the composition for forming a sealing layer is applied on a substrate on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed. Methods etc. The specific example of the method of apply | coating the composition for sealing layer formation is the same as the method of apply | coating the composition for gate insulating film formation. When the composition for forming a sealing layer is applied to form an organic semiconductor film, heating (baking) may be performed after application for the purpose of solvent removal, crosslinking, and the like.
 また、図2は、本発明の有機半導体素子(有機薄膜トランジスタ)の別の一態様の断面模式図である。
 図2において、有機薄膜トランジスタ200は、基板10と、基板10上に配置されたゲート電極20と、ゲート電極20を覆うゲート絶縁膜30と、ゲート絶縁膜30上に配置された有機半導体膜50と、有機半導体膜50上に配置されたソース電極40及びドレイン電極42と、各部材を覆う封止層60を備える。ここで、ソース電極40及びドレイン電極42は、上述した本発明の組成物を用いて形成されたものである。有機薄膜トランジスタ200は、トップコンタクト型の有機薄膜トランジスタである。
 基板、ゲート電極、ゲート絶縁膜、ソース電極、ドレイン電極、有機半導体膜及び封止層については、上述のとおりである。
Moreover, FIG. 2 is a cross-sectional schematic diagram of another one aspect | mode of the organic-semiconductor element (organic thin-film transistor) of this invention.
In FIG. 2, the organic thin film transistor 200 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and an organic semiconductor film 50 disposed on the gate insulating film 30. A source electrode 40 and a drain electrode 42 disposed on the organic semiconductor film 50, and a sealing layer 60 covering each member. Here, the source electrode 40 and the drain electrode 42 are formed using the composition of the present invention described above. The organic thin film transistor 200 is a top contact type organic thin film transistor.
The substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer are as described above.
 上記では図1及び図2において、ボトムゲート-ボトムコンタクト型の有機薄膜トランジスタ、及び、ボトムゲート-トップコンタクト型の有機薄膜トランジスタの態様について詳述したが、本発明の有機半導体素子は、トップゲート-ボトムコンタクト型の有機薄膜トランジスタ、及び、トップゲート-トップコンタクト型の有機薄膜トランジスタにも好適に使用できる。
 なお、上述した有機薄膜トランジスタは、電子ペーパー、ディスプレイデバイスなどに好適に使用できる。
Although the embodiments of the bottom gate-bottom contact type organic thin film transistor and the bottom gate / top contact type organic thin film transistor have been described above in detail in FIGS. 1 and 2, the organic semiconductor device of the present invention is a top gate bottom The present invention can also be suitably used for a contact type organic thin film transistor and a top gate-top contact type organic thin film transistor.
The organic thin film transistor described above can be suitably used for electronic paper, a display device, and the like.
(有機半導体膜形成用組成物)
 本発明の有機半導体膜形成用組成物は、特定有機半導体化合物、及び、溶媒を含有することを特徴とする。
 また、本発明の有機半導体膜形成用組成物は、バインダーポリマーを含有することが好ましい。
 本発明の有機半導体膜形成用組成物における特定化合物、バインダーポリマー及び溶媒は、上述した特定化合物、バインダーポリマー及び溶媒と同義であり、好ましい態様も同様である。
(Composition for forming an organic semiconductor film)
The composition for forming an organic semiconductor film of the present invention is characterized by containing a specific organic semiconductor compound and a solvent.
Moreover, it is preferable that the composition for organic-semiconductor film formation of this invention contains a binder polymer.
The specific compound, the binder polymer, and the solvent in the composition for forming an organic semiconductor film of the present invention have the same meanings as the specific compound, the binder polymer, and the solvent described above, and preferred embodiments are also the same.
 本発明の有機半導体膜形成用組成物は、特定化合物及びバインダーポリマー以外に他の成分を含んでいてもよい。
 その他の成分としては、公知の添加剤等を用いることができる。
 本発明の有機半導体膜形成用組成物における特定化合物及びバインダーポリマー以外の成分の含有量は、全固形分に対し、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、1質量%以下であることが更に好ましく、0.1質量%以下であることが特に好ましい。上記範囲であると、膜形成性に優れ、得られる有機半導体の移動度及び熱安定性により優れる。なお、固形分とは、溶媒等の揮発性成分を除いた成分の量である。
The composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific compound and the binder polymer.
As other components, known additives and the like can be used.
The content of components other than the specific compound and the binder polymer in the composition for forming an organic semiconductor film of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content. The content is more preferably 1% by mass or less and particularly preferably 0.1% by mass or less. It is excellent in film formation property as it is the said range, and it is excellent by the mobility and thermal stability of the organic semiconductor obtained. In addition, solid content is the quantity of the component except volatile components, such as a solvent.
 本発明の有機半導体膜形成用組成物の粘度は、特に制限されないが、塗布性がより優れる点で、3~100mPa・sが好ましく、5~50mPa・sがより好ましく、9~40mPa・sが更に好ましい。なお、本発明における粘度は、25℃での粘度である。
 粘度の測定方法としては、JIS Z8803に準拠した測定方法であることが好ましい。
The viscosity of the composition for forming an organic semiconductor film of the present invention is not particularly limited, but it is preferably 3 to 100 mPa · s, more preferably 5 to 50 mPa · s, and still more preferably 9 to 40 mPa · s, from the viewpoint of more excellent coatability. More preferable. In addition, the viscosity in this invention is a viscosity in 25 degreeC.
It is preferable that it is a measuring method based on JISZ8803 as a measuring method of a viscosity.
 本発明の有機半導体膜形成用組成物の製造方法は、特に制限されず、公知の方法を採用できる。例えば、溶媒中に所定量の特定化合物を添加して、適宜撹拌処理を施すことにより、所望の組成物を得ることができる。また、バインダーポリマーを用いる場合は、特定化合物及びバインダーポリマーを同時又は逐次に添加して好適に組成物を作製することができる。 The method for producing the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted. For example, a desired composition can be obtained by adding a predetermined amount of a specific compound to a solvent and appropriately performing a stirring process. Moreover, when using a binder polymer, a specific compound and a binder polymer can be added simultaneously or sequentially, and a composition can be suitably produced.
(有機半導体膜)
 本発明の有機半導体膜は、特定有機半導体を含有することを特徴とする。
 また、本発明の有機半導体膜は、バインダーポリマーを含有することが好ましい。
 本発明の有機半導体膜における特定化合物、特定化合物を重合することにより得られたポリマー及びオリゴマー、並びに、バインダーポリマーは、本発明の有機半導体素子において上述した特定化合物、特定化合物を重合することにより得られたポリマー及びオリゴマー、並びに、バインダーポリマーと同義であり、好ましい態様も同様である。
(Organic semiconductor film)
The organic semiconductor film of the present invention is characterized by containing a specific organic semiconductor.
In addition, the organic semiconductor film of the present invention preferably contains a binder polymer.
The specific compound in the organic semiconductor film of the present invention, the polymer and oligomer obtained by polymerizing the specific compound, and the binder polymer are obtained by polymerizing the specific compound and the specific compound described above in the organic semiconductor device of the present invention It is synonymous with the said polymer and oligomer, and a binder polymer, and its preferable aspect is also the same.
 本発明の有機半導体膜形成用組成物は、特定化合物、特定化合物を重合することにより得られたポリマー及びオリゴマー、並びに、バインダーポリマー以外に他の成分を含んでいてもよい。
 その他の成分としては、公知の添加剤等を用いることができる。
 本発明の有機半導体膜における特定化合物、特定化合物を重合することにより得られたポリマー及びオリゴマー、並びに、バインダーポリマー以外の成分の含有量は、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、1質量%以下であることが更に好ましく、0.1質量%以下であることが特に好ましい。上記範囲であると、膜形成性に優れ、得られる有機半導体の移動度及び熱安定性により優れる。なお、固形分とは、溶媒等の揮発性成分を除いた成分の量である。
The composition for forming an organic semiconductor film of the present invention may contain other components in addition to the specific compound, the polymer and the oligomer obtained by polymerizing the specific compound, and the binder polymer.
As other components, known additives and the like can be used.
The content of the specific compound, the polymer and the oligomer obtained by polymerizing the specific compound, and the component other than the binder polymer in the organic semiconductor film of the present invention is preferably 10% by mass or less, and 5% by mass or less Is more preferably, 1% by mass or less is more preferable, and 0.1% by mass or less is particularly preferable. It is excellent in film formation property as it is the said range, and it is excellent by the mobility and thermal stability of the organic semiconductor obtained. In addition, solid content is the quantity of the component except volatile components, such as a solvent.
 本発明の有機半導体膜の膜厚は、特に制限されないが、得られる有機半導体の移動度及び熱安定性の観点から、10~500nmが好ましく、30~200nmがより好ましい。
 本発明の有機半導体膜は、有機半導体素子に好適に使用することができ、有機トランジスタ(有機薄膜トランジスタ)に特に好適に使用することができる。
 本発明の有機半導体膜は、本発明の有機半導体膜形成用組成物を用いて好適に作製することができる。
The thickness of the organic semiconductor film of the present invention is not particularly limited, but is preferably 10 to 500 nm, and more preferably 30 to 200 nm, from the viewpoint of the mobility and thermal stability of the obtained organic semiconductor.
The organic semiconductor film of the present invention can be suitably used for an organic semiconductor element, and can be particularly suitably used for an organic transistor (organic thin film transistor).
The organic semiconductor film of the present invention can be suitably produced using the composition for forming an organic semiconductor film of the present invention.
 以下に実施例を挙げて本発明を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「部」、「%」は質量基準である。 Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references.
(有機半導体化合物)
 有機半導体層に用いた有機半導体化合物である、化合物1~15、及び、比較化合物1~6の構造を以下に示す。
(Organic semiconductor compounds)
The structures of Compounds 1 to 15 and Comparative Compounds 1 to 6, which are organic semiconductor compounds used in the organic semiconductor layer, are shown below.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
 化合物1は以下に示す合成スキームで合成した。具体的には、J.Org.Chem.1984,49,1027.記載の方法に従って合成中間体1を合成し、特開2009-200028号公報に記載の方法に従って合成中間体2を合成し、両者のStilleカップリング反応により化合物1を得た。 Compound 1 was synthesized by the synthetic scheme shown below. Specifically, J.J. Org. Chem. 1984, 49, 1027. Synthesis Intermediate 1 was synthesized according to the method described, and Synthesis Intermediate 2 was synthesized according to the method described in JP2009-200028A, and Compound 1 was obtained by the Stille coupling reaction of both.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
 化合物2は以下に示す合成スキームで合成した。具体的には、Chem.Commun.2013,49,5354.に記載の方法に従って合成中間体3を合成し、J.Mater.Chem.S,2014,2,3972.に記載の方法で合成中間体4を合成し、両者のStilleカップリング反応により化合物2を得た。 Compound 2 was synthesized by the synthetic scheme shown below. Specifically, Chem. Commun. 2013, 49, 5354. The synthetic intermediate 3 is synthesized according to the method described in J. Mater. Chem. S, 2014, 2, 3972. The synthetic intermediate 4 was synthesized by the method described in 4. and the compound 2 was obtained by the Stille coupling reaction of both.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
 化合物3~化合物15に関しても、上記の方法に準じて合成した。
 比較化合物1は特開平7-228865号公報に記載の例示化合物(II-5)である。比較化合物2は特開平5-158260号公報に記載の例示化合物(II-2)である。比較化合物3及び比較化合物4は特開2010-177643号公報に記載の例示化合物71及び例示化合物120である。比較化合物5は特開2010-205984号公報に記載の例示化合物3である。比較化合物6はJ.Am.Chem.Soc.,1998,120,664.に記載の化合物7aである。
 いずれも、高速液体クロマトグラフィー(東ソー(株)製、TSKgel ODS-100Z)により純度(254nmの吸収強度面積比)が99.8%以上であることを確認した。
The compounds 3 to 15 were also synthesized according to the above method.
The comparative compound 1 is the exemplified compound (II-5) described in JP-A-7-228865. Comparative compound 2 is the exemplified compound (II-2) described in JP-A-5-158260. The comparison compound 3 and the comparison compound 4 are the illustration compound 71 and the illustration compound 120 which are described in Unexamined-Japanese-Patent No. 2010-177643. Comparative compound 5 is Exemplified compound 3 described in JP-A-2010-205984. Comparative compound 6 is described in J.I. Am. Chem. Soc. , 1998, 120, 664. And the compound 7a described in
All of them were confirmed to be 99.8% or more in purity (a ratio of absorption intensity area at 254 nm) by high performance liquid chromatography (TSKgel ODS-100Z, manufactured by Tosoh Corp.).
<使用した出発原料>
 化合物1の合成に使用した1,2,3,4-テトラメチルベンゼンは、アルファ・エイサー社より購入した。
 化合物2の合成に使用した3,4-ジブロモチオフェンは、和光純薬工業(株)より購入した。
<Starting material used>
1,2,3,4-Tetramethylbenzene used for the synthesis of Compound 1 was purchased from Alpha Acer.
3,4-dibromo-thiophene was used for the synthesis of Compound 2 were purchased from Wako Pure Chemical Industries, Ltd..
 なお、上述した以外の上記スキームで使用した化合物は、以下の通りである。
 Br2:臭素(和光純薬工業(株)製)
 Na2S:硫化ナトリウム(和光純薬工業(株)製)
 NaIO4:過ヨウ素酸ナトリウム(和光純薬工業(株)製)
 Al23:酸化アルミニウム(和光純薬工業(株)製)
 NBS:N-ブロモスクシンイミド(和光純薬工業(株)製)
 Pd(PPh34:テトラキス(トリフェニルホスフィン)パラジウム(0)(東京化成工業(株)製)
 n-BuLi:n-ブチルリチウム(東京化成工業(株)製)
 (PhSO22S:ビス(フェニルスルホニル)スルフィド(Tetrahedron Lett.,2002,43,1553.に記載の方法で調製した。)
 Me3SnSnMe3:ヘキサメチルジスタナン(東京化成工業(株)製)
 LDA:リチウムジイソプロピルアミド(東京化成工業(株)製)
 TMSCl:クロロトリメチルシラン(東京化成工業(株)製)
 ICl:一塩化ヨウ素(和光純薬工業(株)製)
In addition, the compound used by the said scheme except having mentioned above is as follows.
Br 2 : Bromine (manufactured by Wako Pure Chemical Industries, Ltd.)
Na 2 S: Sodium sulfide (manufactured by Wako Pure Chemical Industries, Ltd.)
NaIO 4 : sodium periodate (manufactured by Wako Pure Chemical Industries, Ltd.)
Al 2 O 3 : Aluminum oxide (manufactured by Wako Pure Chemical Industries, Ltd.)
NBS: N-bromosuccinimide (manufactured by Wako Pure Chemical Industries, Ltd.)
Pd (PPh 3 ) 4 : tetrakis (triphenylphosphine) palladium (0) (manufactured by Tokyo Chemical Industry Co., Ltd.)
n-BuLi: n-butyllithium (manufactured by Tokyo Chemical Industry Co., Ltd.)
(PhSO 2 ) 2 S: bis (phenylsulfonyl) sulfide (prepared by the method described in Tetrahedron Lett., 2002, 43, 1553.)
Me 3 SnSnMe 3: hexamethyl register Nan (Tokyo Kasei Kogyo Co., Ltd.)
LDA: lithium diisopropylamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
TMSCl: chlorotrimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
ICl: iodine monochloride (manufactured by Wako Pure Chemical Industries, Ltd.)
<バインダーポリマー>
 バインダーとして用いたポリマーを以下に示す。
 PαMS:ポリ-α-メチルスチレン、重量平均分子量437,000、シグマアルドリッチ社製
 PTAA:ポリ[ビス(4-フェニル)(2,4,6-トリメチルフェニル)アミン]、数平均分子量7,000~10,000、シグマアルドリッチ社製
 PCPDTBT:ポリ[2,6-(4,4-ビス(2-エチルヘキシル)-4Hシクロペンタ[2,1-b;3,4-b’]ジチオフェン)-アルト-4,7-(2,1,3-ベンゾチアジアゾール)]、重量平均分子量7,000~20,000、シグマアルドリッチ社製
<Binder polymer>
The polymers used as binders are shown below.
P α MS: poly-α-methylstyrene, weight average molecular weight 437,000, manufactured by Sigma Aldrich PTAA: poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine], number average molecular weight 7,000 to 10,000, Sigma-Aldrich PCPDTBT: poly [2,6- (4,4-bis (2-ethylhexyl) -4H cyclopenta [2,1-b; 3,4-b '] dithiophene) -alto-4 , 7- (2,1,3-benzothiadiazole)], weight average molecular weight of 7,000 to 20,000, manufactured by sigma-Aldrich
<有機半導体膜形成用塗布液の調製>
 表1に記載の有機半導体化合物(0.5質量%)/バインダーポリマー(表1に記載の濃度)/アニソール(沸点154℃)を硝子バイヤルに秤量し、ミックスローター(アズワン(株)製)で10分間撹拌混合した後、0.5μmメンブレンフィルターでろ過することで、有機半導体膜形成用塗布液(有機半導体膜形成用組成物)を得た。表1中、バインダーポリマーの欄に「-」と記載されているものはバインダーポリマーを添加していないことを示す。
 なお、バインダーポリマーの濃度は、塗布液中の質量%である。
<Preparation of Coating Liquid for Forming Organic Semiconductor Film>
The organic semiconductor compound (0.5 mass%) / binder polymer (concentration shown in Table 1) / anisole (boiling point 154 ° C) listed in Table 1 are weighed on a glass vial, and mixed rotor (made by As One Corp.) After stirring and mixing for 10 minutes, the coating liquid for organic-semiconductor film formation (composition for organic-semiconductor film formation) was obtained by filtering with a 0.5 micrometer membrane filter. In Table 1, what is described as "-" in the column of the binder polymer shows that the binder polymer is not added.
The concentration of the binder polymer is mass% in the coating solution.
<TFT素子作製>
 ガラス基板(イーグルXG:コーニング社製)上に、ゲート電極となるAlを蒸着した(厚み:50nm)。その上にゲート絶縁膜形成用組成物(ポリビニルフェノール/メラミン=1質量部/1質量部(w/w)のPGMEA(プロピレングリコールモノメチルエーテルアセテート)溶液(固形分濃度:2質量%))をスピンコートし、150℃で60分間ベークを行うことで膜厚400nmのゲート絶縁膜を形成した。その上に銀インク(H-1、三菱マテリアル(株)製)をインクジェット装置DMP-2831(富士フイルムダイマティクス社製)を用いてソース電極及びドレイン電極状(チャネル長40μm、チャネル幅200μm)に描画した。その後オーブンにて180℃、30分間ベークを行い、焼結して、ソース電極及びドレイン電極を形成することでTFT特性評価用素子基板を得た。
 TFT特性評価用素子基板の上に各有機半導体膜形成用塗布液をスピンコート(500rpm10秒間の後1,000rpm30秒間)した後、ホットプレート上で50℃10分間乾燥することで有機半導体層を形成し、ボトムゲート-ボトムコンタクト型の有機TFT素子を得た。
<TFT element fabrication>
On a glass substrate (Eagle XG: manufactured by Corning), Al serving as a gate electrode was vapor-deposited (thickness: 50 nm). A composition for gate insulating film formation (polyvinylphenol / melamine = 1 mass part / 1 mass part (w / w) solution of PGMEA (propylene glycol monomethyl ether acetate) solution (solid content concentration: 2 mass%)) is spin-coated thereon. The resultant was coated and baked at 150 ° C. for 60 minutes to form a gate insulating film having a thickness of 400 nm. Furthermore, silver ink (H-1, manufactured by Mitsubishi Materials Corporation) is formed into a source electrode and a drain electrode (channel length 40 μm, channel width 200 μm) using an inkjet device DMP-2831 (manufactured by Fujifilm Dimatics Co., Ltd.) I drew it. After that, baking was performed at 180 ° C. for 30 minutes in an oven and sintering was performed to form a source electrode and a drain electrode, whereby an element substrate for TFT characteristic evaluation was obtained.
After spin-coating each coating solution for organic semiconductor film formation on the element substrate for TFT characteristic evaluation (1,000 rpm for 30 seconds after 500 rpm for 10 seconds), the organic semiconductor layer is formed by drying at 50 ° C for 10 minutes on a hot plate. Then, a bottom gate-bottom contact type organic TFT element was obtained.
<特性評価>
 半導体特性評価装置B2900A(アジレント・テクノロジー(株)製)を用い、大気下で以下の性能評価を行った。
(a)キャリア移動度、及び、(b)移動度バラツキ
 各有機TFT素子のソース電極-ドレイン電極間に、-60Vの電圧を印加し、ゲート電圧を+10V~-60Vの範囲で変化させ、ドレイン電流Idを表わす下記式を用いてキャリア移動度μを算出した。
 Id=(w/2L)μCi(Vg-Vth2
 式中、Lはゲート長、Wはゲート幅、Ciは絶縁層の単位面積当たりの容量、Vgはゲート電圧、Vthは閾値電圧を表す。
 表1中に示すキャリア移動度の値は、10素子の平均値である。キャリア移動度μは高いほど好ましく、実用上は1×10-2cm2/Vs以上であることが好ましく、1×10-1cm2/Vs以上であることがより好ましい。なお、移動度が1×10-5cm2/Vsを下回るものに関しては特性が低すぎるため、特性評価は行わず、表1の該当する欄には「-」を記載した。
 また、10素子のキャリア移動度に対して以下の式で計算した変異係数を、以下の5段階で評価し、移動度バラツキの指標として用いた。この値は小さいほど素子間の移動度バラツキが小さいことを示す。実用上、A又はBであることが好ましく、Aであることがより好ましい。
 変異係数=標準偏差÷平均値×100
  A:15%未満
  B:15%以上30%未満
  C:30%以上50%未満
  D:50%以上
<Characteristics evaluation>
A semiconductor characteristic evaluation apparatus B2900A (manufactured by Agilent Technologies Inc.), the performance was evaluated in the following in the air.
(A) Carrier mobility, and (b) Mobility variation: A voltage of -60 V is applied between the source electrode and the drain electrode of each organic TFT element, and the gate voltage is changed in the range of +10 V to -60 V, the drain The carrier mobility μ was calculated using the following equation representing the current I d .
I d = (w / 2 L) μC i (V g -V th ) 2
In the equation, L represents a gate length, W represents a gate width, C i represents a capacity per unit area of the insulating layer, V g represents a gate voltage, and V th represents a threshold voltage.
The carrier mobility values shown in Table 1 are average values of 10 elements. The carrier mobility μ is preferably as high as possible, and for practical use is preferably 1 × 10 −2 cm 2 / Vs or more, and more preferably 1 × 10 −1 cm 2 / Vs or more. In addition, since the characteristic is too low for the mobility lower than 1 × 10 −5 cm 2 / Vs, the characteristic evaluation is not performed, and “-” is described in the corresponding column of Table 1.
Moreover, the variation coefficient calculated by the following formula with respect to the carrier mobility of 10 elements was evaluated in the following five steps, and was used as an index of mobility variation. The smaller this value is, the smaller the variation in mobility between elements is. Practically, A or B is preferable, and A is more preferable.
Coefficient of variation = standard deviation / mean value × 100
A: less than 15% B: 15% or more and less than 30% C: 30% or more and less than 50% D: 50% or more
(c)耐熱性
 作製した各有機薄膜トランジスタ素子を、窒素グローブボックス中にて150℃1時間加熱した後に、(a)と同様の方法でキャリア移動度を測定し、下記式で計算される加熱後のキャリア移動度維持率を以下の4段階で評価し、耐熱性の指標とした。この値が大きいほど耐熱性が高く、実用上、Aであることが好ましい。
 加熱後のキャリア移動度維持率(%)=移動度(加熱後)/移動度(加熱前)
  A:80%以上
  B:60%以上80%未満
  C:40%以上60%未満
  D:40%未満
(C) Heat resistance After heating each produced organic thin film transistor element in a nitrogen glove box at 150 ° C. for 1 hour, the carrier mobility is measured by the same method as (a), and after heating calculated by the following equation The carrier mobility maintenance rate of was evaluated in the following four stages, and was used as an index of heat resistance. As the value is larger, the heat resistance is higher, and in practice, A is preferable.
Carrier mobility maintenance rate after heating (%) = mobility (after heating) / mobility (before heating)
A: 80% or more B: 60% or more and less than 80% C: 40% or more and less than 60% D: less than 40%
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
 10:基板、20:ゲート電極、30:ゲート絶縁膜、40:ソース電極、42:ドレイン電極、50:有機半導体膜、60:封止層、100、200:有機薄膜トランジスタ 10: substrate, 20: gate electrode, 30: gate insulating film, 40: source electrode, 42: drain electrode, 50: organic semiconductor film, 60: sealing layer, 100, 200: organic thin film transistor

Claims (25)

  1.  下記式1で表される有機半導体を含有する有機半導体層を有することを特徴とする、
     有機半導体素子。
    Figure JPOXMLDOC01-appb-C000001
     式1中、Xはそれぞれ独立に、O、S、Se、NRのいずれかを表し、Rはそれぞれ独立に置換基を表し、環Aはそれぞれ独立に、5員又は6員の単環の芳香族炭化水素環又は芳香族複素環を表し、mは1~5の整数を表し、mが2~5の場合は複数の環Aはそれぞれ同一でも異なってもよく、nは0以上の整数を表し、mが1の場合はRの少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、mが4又は5の場合は3つ以上のRが芳香族炭化水素基又は芳香族複素環基になることはない。
    Characterized by having an organic semiconductor layer containing an organic semiconductor represented by the following formula 1;
    Organic semiconductor device.
    Figure JPOXMLDOC01-appb-C000001
    In Formula 1, each X independently represents any of O, S, Se, and NR, each R independently represents a substituent, and each ring A independently represents a 5- or 6-membered monocyclic aromatic ring. Group hydrocarbon ring or aromatic heterocyclic ring, m represents an integer of 1 to 5, and when m is 2 to 5, plural rings A may be the same or different, and n is an integer of 0 or more When m is 1, at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when m is 4 or 5, three or more R's are an aromatic hydrocarbon group or an aromatic complex It can not be a ring group.
  2.  式1中、環Aがそれぞれ独立に、ベンゼン環、フラン環、チオフェン環、セレノフェン環、又は、ピロール環を表し、かつ、式1中のRを取り去った部分構造の対称性が、C2、C2v、又は、C2hである、請求項1に記載の有機半導体素子。 In Formula 1, the ring A each independently represents a benzene ring, a furan ring, a thiophene ring, a selenophen ring, or a pyrrole ring, and the symmetry of the partial structure from which R in Formula 1 is removed is C 2 , C 2v, or a C 2h, the organic semiconductor device according to claim 1.
  3.  式1で表される有機半導体が、下記式2で表される有機半導体である、請求項1又は2に記載の有機半導体素子。
    Figure JPOXMLDOC01-appb-C000002
     式2中、Tは下記T-1~T-35よりなる群から選択されるいずれかの構造を表し、R’はそれぞれ独立に置換基を表し、nは0~6の整数を表し、TがT-1又はT-2である場合、R’の少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、TがT-20~T-35のいずれかである場合、3つ以上のR’が芳香族炭化水素基又は芳香族複素環基になることはない。
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
     T-1~T-35中、Xはそれぞれ独立に、O、S、Se、NR’のいずれかを表す。
    The organic-semiconductor element of Claim 1 or 2 whose organic semiconductor represented by Formula 1 is an organic semiconductor represented by following formula 2.
    Figure JPOXMLDOC01-appb-C000002
    In Formula 2, T represents any structure selected from the group consisting of T-1 to T-35 below, R ′ independently represents a substituent, n represents an integer of 0 to 6, and T represents When at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group when T is T-1 or T-2, and three when T is any of T-20 to T-35 The above R 'does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
    In T-1 to T-35, X each independently represents any of O, S, Se, and NR '.
  4.  R’が下記式3で表される、請求項3に記載の有機半導体素子。
    Figure JPOXMLDOC01-appb-C000005
     式3中、Lはそれぞれ独立に、下記式L-1~式L-12のいずれかで表される2価の連結基、又は、2以上の下記式L-1~式L-12のいずれかで表される2価の連結基が2つ以上結合した2価の連結基を表し、Zはそれぞれ独立に、水素原子、アルキル基、オキシエチレン単位の繰り返し数が2以上のオリゴオキシエチレン基、ケイ素原子数が2以上のオリゴシロキサン基、又は、トリアルキルシリル基を表し、ただし、Zがトリアルキルシリル基を表すのは、Zに隣接するLが下記式L-3で表される連結基である場合に限り、水素原子を表すのは、Zに隣接するLが下記式L-1、L-2、L-3、L-10、L-11、又は、L-12で表される連結基である場合に限る。
    Figure JPOXMLDOC01-appb-C000006
     式L-1~式L-12中、*及び波線部分は他の構造との結合位置を表し、式L-1、式L-2及び式L-10~式L-12におけるRL1はそれぞれ独立に、水素原子又は置換基を表す。
    The organic semiconductor device according to claim 3, wherein R 'is represented by the following formula 3.
    Figure JPOXMLDOC01-appb-C000005
    In Formula 3, L is each independently a divalent linking group represented by any one of the following Formulas L-1 to L-12, or any of two or more of the following Formulas L-1 to L-12. And each of Z's independently represents a hydrogen atom, an alkyl group, or an oligooxyethylene group having a repeating number of oxyethylene units of 2 or more. And an oligosiloxane group having a silicon atom number of 2 or more, or a trialkylsilyl group, provided that Z represents a trialkylsilyl group, and a linkage in which L adjacent to Z is represented by the following formula L-3 Only when it is a group, it means that L adjacent to Z is represented by the following formula L-1, L-2, L-3, L-10, L-11 or L-12. Limited if it is a
    Figure JPOXMLDOC01-appb-C000006
    In Formula L-1 to Formula L-12, * and a wavy line portion indicate bonding positions with other structures, and R L1 in Formula L-1, Formula L-2 and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.
  5.  Xがそれぞれ独立に、O又はSを表す、請求項1~4のいずれか1項に記載の有機半導体素子。 The organic semiconductor device according to any one of claims 1 to 4, wherein each X independently represents O or S.
  6.  下記式2で表されることを特徴とする化合物。
    Figure JPOXMLDOC01-appb-C000007
     式2中、Tは下記T-1~T-35よりなる群から選択されるいずれかの構造を表し、R’はそれぞれ独立に置換基を表し、nは0~6の整数を表し、TがT-1又はT-2である場合、R’の少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、TがT-20~T-35のいずれかである場合、3つ以上のR’が芳香族炭化水素基又は芳香族複素環基になることはない。
    Figure JPOXMLDOC01-appb-C000008
    Figure JPOXMLDOC01-appb-C000009
     T-1~T-35中、Xはそれぞれ独立に、O、S、Se、NR’のいずれかを表す。
    A compound represented by the following formula 2.
    Figure JPOXMLDOC01-appb-C000007
    In Formula 2, T represents any structure selected from the group consisting of T-1 to T-35 below, R ′ independently represents a substituent, n represents an integer of 0 to 6, and T represents When at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group when T is T-1 or T-2, and three when T is any of T-20 to T-35 The above R 'does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.
    Figure JPOXMLDOC01-appb-C000008
    Figure JPOXMLDOC01-appb-C000009
    In T-1 to T-35, X each independently represents any of O, S, Se, and NR '.
  7.  R’が下記式3で表される、請求項6に記載の化合物。
    Figure JPOXMLDOC01-appb-C000010
     式3中、Lはそれぞれ独立に、下記式L-1~式L-12のいずれかで表される2価の連結基、又は、2以上の下記式L-1~式L-12のいずれかで表される2価の連結基が2つ以上結合した2価の連結基を表し、Zはそれぞれ独立に、水素原子、アルキル基、オキシエチレン単位の繰り返し数が2以上のオリゴオキシエチレン基、ケイ素原子数が2以上のオリゴシロキサン基、又は、トリアルキルシリル基を表し、ただし、Zがトリアルキルシリル基を表すのは、Zに隣接するLが下記式L-3で表される連結基である場合に限り、水素原子を表すのは、Zに隣接するLが下記式L-1、L-2、L-3、L-10、L-11、又は、L-12で表される連結基である場合に限る。
    Figure JPOXMLDOC01-appb-C000011
     式L-1~式L-12中、*及び波線部分は他の構造との結合位置を表し、式L-1、式L-2及び式L-10~式L-12におけるRL1はそれぞれ独立に、水素原子又は置換基を表す。
    The compound according to claim 6, wherein R 'is represented by the following formula 3.
    Figure JPOXMLDOC01-appb-C000010
    In Formula 3, L is each independently a divalent linking group represented by any one of the following Formulas L-1 to L-12, or any of two or more of the following Formulas L-1 to L-12. And each of Z's independently represents a hydrogen atom, an alkyl group, or an oligooxyethylene group having a repeating number of oxyethylene units of 2 or more. And an oligosiloxane group having a silicon atom number of 2 or more, or a trialkylsilyl group, provided that Z represents a trialkylsilyl group, and a linkage in which L adjacent to Z is represented by the following formula L-3 Only when it is a group, it means that L adjacent to Z is represented by the following formula L-1, L-2, L-3, L-10, L-11 or L-12. Limited if it is a
    Figure JPOXMLDOC01-appb-C000011
    In Formula L-1 to Formula L-12, * and a wavy line portion indicate bonding positions with other structures, and R L1 in Formula L-1, Formula L-2 and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.
  8.  Xがそれぞれ独立に、O又はSを表す、請求項6又は7に記載の化合物。 8. The compound according to claim 6 or 7, wherein each X independently represents O or S.
  9.  有機半導体である、請求項6~8のいずれか1項に記載の化合物。 The compound according to any one of claims 6 to 8, which is an organic semiconductor.
  10.  式1で表される有機半導体と、溶媒とを含有することを特徴とする、有機半導体膜形成用組成物。
    Figure JPOXMLDOC01-appb-C000012
     式1中、Xはそれぞれ独立に、O、S、Se、NRのいずれかを表し、Rはそれぞれ独立に置換基を表し、環Aはそれぞれ独立に、5員又は6員の単環の芳香族炭化水素環又は芳香族複素環を表し、mは1~5の整数を表し、mが2~5の場合は複数の環Aはそれぞれ同一でも異なってもよく、nは0以上の整数を表し、mが1の場合はRの少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、mが4又は5の場合は3つ以上のRが芳香族炭化水素基又は芳香族複素環基になることはない。
    What is claimed is: 1. A composition for forming an organic semiconductor film, comprising: an organic semiconductor represented by Formula 1; and a solvent.
    Figure JPOXMLDOC01-appb-C000012
    In Formula 1, each X independently represents any of O, S, Se, and NR, each R independently represents a substituent, and each ring A independently represents a 5- or 6-membered monocyclic aromatic ring. Group hydrocarbon ring or aromatic heterocyclic ring, m represents an integer of 1 to 5, and when m is 2 to 5, plural rings A may be the same or different, and n is an integer of 0 or more When m is 1, at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when m is 4 or 5, three or more R's are an aromatic hydrocarbon group or an aromatic complex It can not be a ring group.
  11.  式1中、環Aがそれぞれ独立に、ベンゼン環、フラン環、チオフェン環、セレノフェン環、又は、ピロール環を表し、かつ、式1中のRを取り去った部分構造の対称性が、C2、C2v、又は、C2hである、請求項10に記載の有機半導体膜形成用組成物。 In Formula 1, the ring A each independently represents a benzene ring, a furan ring, a thiophene ring, a selenophen ring, or a pyrrole ring, and the symmetry of the partial structure from which R in Formula 1 is removed is C 2 , C 2v, or a C 2h, the organic semiconductor film forming composition according to claim 10.
  12.  式1で表される有機半導体が、下記式2で表される有機半導体である、請求項10又は11に記載の有機半導体膜形成用組成物。
    Figure JPOXMLDOC01-appb-C000013
     式2中、Tは下記T-1~T-35よりなる群から選択されるいずれかの構造を表し、R’はそれぞれ独立に置換基を表し、nは0~6の整数を表し、TがT-1又はT-2である場合、R’の少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、TがT-20~T-35のいずれかである場合、3つ以上のR’が芳香族炭化水素基又は芳香族複素環基になることはない。
    Figure JPOXMLDOC01-appb-C000014
    Figure JPOXMLDOC01-appb-C000015
     T-1~T-35中、Xはそれぞれ独立に、O、S、Se、NR’のいずれかを表す。
    The composition for organic-semiconductor film formation of Claim 10 or 11 whose organic semiconductor represented by Formula 1 is an organic semiconductor represented by following formula 2.
    Figure JPOXMLDOC01-appb-C000013
    In Formula 2, T represents any structure selected from the group consisting of T-1 to T-35 below, R ′ independently represents a substituent, n represents an integer of 0 to 6, and T represents When at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group when T is T-1 or T-2, and three when T is any of T-20 to T-35 The above R 'does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.
    Figure JPOXMLDOC01-appb-C000014
    Figure JPOXMLDOC01-appb-C000015
    In T-1 to T-35, X each independently represents any of O, S, Se, and NR '.
  13.  R’が下記式3で表される、請求項12に記載の有機半導体膜形成用組成物。
    Figure JPOXMLDOC01-appb-C000016
     式3中、Lはそれぞれ独立に、下記式L-1~式L-12のいずれかで表される2価の連結基、又は、2以上の下記式L-1~式L-12のいずれかで表される2価の連結基が2つ以上結合した2価の連結基を表し、Zはそれぞれ独立に、水素原子、アルキル基、オキシエチレン単位の繰り返し数が2以上のオリゴオキシエチレン基、ケイ素原子数が2以上のオリゴシロキサン基、又は、トリアルキルシリル基を表し、ただし、Zがトリアルキルシリル基を表すのは、Zに隣接するLが下記式L-3で表される連結基である場合に限り、水素原子を表すのは、Zに隣接するLが下記式L-1、L-2、L-3、L-10、L-11、又は、L-12で表される連結基である場合に限る。
    Figure JPOXMLDOC01-appb-C000017
     式L-1~式L-12中、*及び波線部分は他の構造との結合位置を表し、式L-1、式L-2及び式L-10~式L-12におけるRL1はそれぞれ独立に、水素原子又は置換基を表す。
    The composition for organic-semiconductor film formation of Claim 12 to which R 'is represented by following formula 3.
    Figure JPOXMLDOC01-appb-C000016
    In Formula 3, L is each independently a divalent linking group represented by any one of the following Formulas L-1 to L-12, or any of two or more of the following Formulas L-1 to L-12. And each of Z's independently represents a hydrogen atom, an alkyl group, or an oligooxyethylene group having a repeating number of oxyethylene units of 2 or more. And an oligosiloxane group having a silicon atom number of 2 or more, or a trialkylsilyl group, provided that Z represents a trialkylsilyl group, and a linkage in which L adjacent to Z is represented by the following formula L-3 Only when it is a group, it means that L adjacent to Z is represented by the following formula L-1, L-2, L-3, L-10, L-11 or L-12. Limited if it is a
    Figure JPOXMLDOC01-appb-C000017
    In Formula L-1 to Formula L-12, * and a wavy line portion indicate bonding positions with other structures, and R L1 in Formula L-1, Formula L-2 and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.
  14.  Xがそれぞれ独立に、O又はSを表す、請求項10~13のいずれか1項に記載の有機半導体膜形成用組成物。 The composition for forming an organic semiconductor film according to any one of claims 10 to 13, wherein each X independently represents O or S.
  15.  式1で表される有機半導体の濃度が、組成物全体に対して0.1~15質量%である、請求項10~14のいずれか1項に記載の有機半導体膜形成用組成物。 The composition for forming an organic semiconductor film according to any one of claims 10 to 14, wherein the concentration of the organic semiconductor represented by the formula 1 is 0.1 to 15% by mass with respect to the whole composition.
  16.  溶媒の沸点が100℃以上である、請求項10~15のいずれか1項に記載の有機半導体膜形成用組成物。 The composition for forming an organic semiconductor film according to any one of claims 10 to 15, wherein the boiling point of the solvent is 100 属 C or more.
  17.  ポリマーバインダーを更に含有する、請求項10~16のいずれか1項に記載の有機半導体膜形成用組成物。 The composition for forming an organic semiconductor film according to any one of claims 10 to 16, further comprising a polymer binder.
  18.  組成物の粘度が5mPa・s~50mPa・sである、請求項10~17のいずれか1項に記載の有機半導体膜形成用組成物。 The composition for forming an organic semiconductor film according to any one of claims 10 to 17, wherein the viscosity of the composition is 5 mPa · s to 50 mPa · s.
  19.  請求項10~18のいずれか1項に記載の有機半導体膜形成用組成物を基板上に塗布する塗布工程を含む、有機半導体素子の製造方法。 A method of manufacturing an organic semiconductor device, comprising a coating step of coating the composition for forming an organic semiconductor film according to any one of claims 10 to 18 on a substrate.
  20.  下記式1で表される有機半導体を含有することを特徴とする、有機半導体膜。
    Figure JPOXMLDOC01-appb-C000018
     式1中、Xはそれぞれ独立に、O、S、Se、NRのいずれかを表し、Rはそれぞれ独立に置換基を表し、環Aはそれぞれ独立に、5員又は6員の単環の芳香族炭化水素環又は芳香族複素環を表し、mは1~5の整数を表し、mが2~5の場合は複数の環Aはそれぞれ同一でも異なってもよく、nは0以上の整数を表し、mが1の場合はRの少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、mが4又は5の場合は3つ以上のRが芳香族炭化水素基又は芳香族複素環基になることはない。
    An organic semiconductor film comprising an organic semiconductor represented by the following formula 1.
    Figure JPOXMLDOC01-appb-C000018
    In Formula 1, each X independently represents any of O, S, Se, and NR, each R independently represents a substituent, and each ring A independently represents a 5- or 6-membered monocyclic aromatic ring. Group hydrocarbon ring or aromatic heterocyclic ring, m represents an integer of 1 to 5, and when m is 2 to 5, plural rings A may be the same or different, and n is an integer of 0 or more When m is 1, at least one of R's represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and when m is 4 or 5, three or more R's are an aromatic hydrocarbon group or an aromatic complex It can not be a ring group.
  21.  式1中、環Aがそれぞれ独立に、ベンゼン環、フラン環、チオフェン環、セレノフェン環、又は、ピロール環を表し、かつ、式1中のRを取り去った部分構造の対称性が、C2、C2v、又は、C2hである、請求項20に記載の有機半導体膜。 In Formula 1, the ring A each independently represents a benzene ring, a furan ring, a thiophene ring, a selenophen ring, or a pyrrole ring, and the symmetry of the partial structure from which R in Formula 1 is removed is C 2 , C 2v, or a C 2h, the organic semiconductor film according to claim 20.
  22.  式1で表される有機半導体が、下記式2で表される有機半導体である、請求項20又は21に記載の有機半導体膜。
    Figure JPOXMLDOC01-appb-C000019
     式2中、Tは下記T-1~T-35よりなる群から選択されるいずれかの構造を表し、R’はそれぞれ独立に置換基を表し、nは0~6の整数を表し、TがT-1又はT-2である場合、R’の少なくとも1つが芳香族炭化水素基又は芳香族複素環基を表し、TがT-20~T-35のいずれかである場合、3つ以上のR’が芳香族炭化水素基又は芳香族複素環基になることはない。
    Figure JPOXMLDOC01-appb-C000020
    Figure JPOXMLDOC01-appb-C000021
     T-1~T-35中、Xはそれぞれ独立に、O、S、Se、NR’のいずれかを表す。
    The organic-semiconductor film of Claim 20 or 21 whose organic semiconductor represented by Formula 1 is an organic semiconductor represented by following formula 2.
    Figure JPOXMLDOC01-appb-C000019
    In Formula 2, T represents any structure selected from the group consisting of T-1 to T-35 below, R ′ independently represents a substituent, n represents an integer of 0 to 6, and T represents When at least one of R ′ represents an aromatic hydrocarbon group or an aromatic heterocyclic group when T is T-1 or T-2, and three when T is any of T-20 to T-35 The above R 'does not become an aromatic hydrocarbon group or an aromatic heterocyclic group.
    Figure JPOXMLDOC01-appb-C000020
    Figure JPOXMLDOC01-appb-C000021
    In T-1 to T-35, X each independently represents any of O, S, Se, and NR '.
  23.  R’が下記式3で表される、請求項22に記載の有機半導体膜。
    Figure JPOXMLDOC01-appb-C000022
     式3中、Lはそれぞれ独立に、下記式L-1~式L-12のいずれかで表される2価の連結基、又は、2以上の下記式L-1~式L-12のいずれかで表される2価の連結基が2つ以上結合した2価の連結基を表し、Zはそれぞれ独立に、水素原子、アルキル基、オキシエチレン単位の繰り返し数が2以上のオリゴオキシエチレン基、ケイ素原子数が2以上のオリゴシロキサン基、又は、トリアルキルシリル基を表し、ただし、Zがトリアルキルシリル基を表すのは、Zに隣接するLが下記式L-3で表される連結基である場合に限り、水素原子を表すのは、Zに隣接するLが下記式L-1、L-2、L-3、L-10、L-11、又は、L-12で表される連結基である場合に限る。
    Figure JPOXMLDOC01-appb-C000023
     式L-1~式L-12中、*及び波線部分は他の構造との結合位置を表し、式L-1、式L-2及び式L-10~式L-12におけるRL1はそれぞれ独立に、水素原子又は置換基を表す。
    The organic semiconductor film according to claim 22, wherein R 'is represented by the following formula 3.
    Figure JPOXMLDOC01-appb-C000022
    In Formula 3, L is each independently a divalent linking group represented by any one of the following Formulas L-1 to L-12, or any of two or more of the following Formulas L-1 to L-12. And each of Z's independently represents a hydrogen atom, an alkyl group, or an oligooxyethylene group having a repeating number of oxyethylene units of 2 or more. And an oligosiloxane group having a silicon atom number of 2 or more, or a trialkylsilyl group, provided that Z represents a trialkylsilyl group, and a linkage in which L adjacent to Z is represented by the following formula L-3 Only when it is a group, it means that L adjacent to Z is represented by the following formula L-1, L-2, L-3, L-10, L-11 or L-12. Limited if it is a
    Figure JPOXMLDOC01-appb-C000023
    In Formula L-1 to Formula L-12, * and a wavy line portion indicate bonding positions with other structures, and R L1 in Formula L-1, Formula L-2 and Formula L-10 to Formula L-12 is respectively Independently, it represents a hydrogen atom or a substituent.
  24.  Xがそれぞれ独立に、O又はSを表す、請求項20~23のいずれか1項に記載の有機半導体膜。 The organic semiconductor film according to any one of claims 20 to 23, wherein each X independently represents O or S.
  25.  溶液塗布法により製膜された、請求項20~24のいずれか1項に記載の有機半導体膜。 The organic semiconductor film according to any one of claims 20 to 24, which is formed by a solution coating method.
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