WO2018180194A1 - Semi-conducteur organique, et procédé de fabrication de celui-ci - Google Patents

Semi-conducteur organique, et procédé de fabrication de celui-ci Download PDF

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WO2018180194A1
WO2018180194A1 PCT/JP2018/008004 JP2018008004W WO2018180194A1 WO 2018180194 A1 WO2018180194 A1 WO 2018180194A1 JP 2018008004 W JP2018008004 W JP 2018008004W WO 2018180194 A1 WO2018180194 A1 WO 2018180194A1
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group
formula
atom
same
alkyl
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大次 池田
岡本　敏宏
純一 竹谷
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株式会社ダイセル
国立大学法人東京大学
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an organic semiconductor including a condensed polycyclic compound having a bent skeleton (for example, a skeleton such as a benzodithiophene ring), a manufacturing method thereof, and an electronic device (for example, an organic thin film transistor) including the organic semiconductor. .
  • a condensed polycyclic compound having a bent skeleton for example, a skeleton such as a benzodithiophene ring
  • an electronic device for example, an organic thin film transistor
  • a condensed polycyclic compound is a polycyclic compound having a structure in which two or more atoms are shared in two or more adjacent rings, and a plurality of 5- or 6-membered rings (for example, a benzene ring, a thiophene ring, etc.) )
  • Condensed polycyclic aromatic compounds for example, acene compounds such as pentacene
  • condensed polycyclic aromatic compounds especially acene compounds such as pentacene
  • an organic semiconductor material eg, organic It is used as a material for thin film transistors.
  • printed electronics in which an organic semiconductor layer is formed by a wet process such as a coating method or a printing method (for example, spin coating) has recently attracted attention.
  • a wet process such as a coating method or a printing method (for example, spin coating)
  • the manufacturing cost can be effectively reduced.
  • a material having low heat resistance such as a plastic substrate can be used, it is expected to be used in various applications utilizing characteristics such as lightness and flexibility (or flexibility).
  • acene-based compounds such as pentacene not only have a high planarity in the molecular structure but also have extremely low solubility in organic solvents because molecules tend to aggregate due to the influence of ⁇ - ⁇ interaction. Therefore, application to printed electronics in which an organic semiconductor layer is formed by a wet process is difficult.
  • the operating voltage of the element tends to increase. That is, the long-chain alkyl group is used to increase the contact resistance by trapping carriers at the device interface (electrode / organic semiconductor interface, etc.), or the mobility at the initial driving stage (rising of the current) is reduced.
  • the current injection resistance increases to several tens to several thousand k ⁇ ⁇ cm. Therefore, the operating voltage of the element is as high as several tens to 100 V, and the practical operating voltage cannot be reduced.
  • the mobility tends to vary easily.
  • an organic semiconductor layer is coated and formed using a condensed polycyclic compound having an alkyl group
  • an alkyl portion in which flexible alkyl groups are aggregated and a condensed ring skeleton portion in which rigid condensed ring skeletons are stacked are in phase. Separated and formed in the organic semiconductor layer.
  • the alkyl part and the condensed ring skeleton part are usually formed in an alternately stacked form, and the conductivity (or mobility) is excellent in the stacking direction ( ⁇ stacking direction or crystal growth direction) of the condensed ring skeleton.
  • the mobility is extremely large due to the influence of the alkyl part. It is known to decline. Due to the anisotropy of the mobility, it is difficult to make the mobility uniform in three dimensions, and the variation varies depending on the element.
  • Patent Document 1 discloses a non-light-emitting organic semiconductor device containing a compound having a thienobisbenzothiophene (TBBT) skeleton represented by the following formula and a solvent having a boiling point of 100 ° C. or higher. A coating solution is disclosed.
  • TBT thienobisbenzothiophene
  • R 11 and R 12 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, which may have a substituent, and the aromatic moiety is substituted with a halogen atom. May be).
  • the solubility tends to be improved because the condensed ring skeleton is bent by the central thiophene ring to increase the dipole moment of the compound.
  • the solubility is not sufficient, in the examples of this document, compounds in which an alkyl group or the like is introduced into the groups R 11 and R 12 are used.
  • Patent Document 1 the condensed ring skeleton is bent by a thiophene ring skeleton, but a vinylene group (—CH 2 ⁇ CH 2 —) is introduced instead of the sulfur atom (—S—) of the thiophene ring.
  • a compound (flexible compound) in which the condensed ring skeleton is further bent has not been studied because it is difficult to synthesize.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2013-177399 (Patent Document 2) exemplifies a compound having a benzodithiophene skeleton (for example, Compound 71). In addition to being synthesized, no mention is made of solubility or semiconductor properties (electrical properties).
  • an object of the present invention is to provide an organic semiconductor having high mobility (or carrier mobility) and a method for producing the same.
  • Another object of the present invention is to provide an organic semiconductor that can achieve both high solubility and high mobility even if it does not contain an alkyl group, and a method for producing the same.
  • Still another object of the present invention is to provide a method for easily or efficiently producing a condensed polycyclic compound having a bent skeleton in which a condensed ring is formed at each of the 1,2-position and 3,4-position of the benzene ring. Is to provide.
  • an organic semiconductor containing a condensed polycyclic compound having a specific bent skeleton has high mobility, and further has solubility in a solvent. It was found that it was excellent and completed the present invention.
  • the organic semiconductor of the present invention contains a compound represented by the following formula (A).
  • rings A 1 and A 2 are the same or different and have at least one carbon-carbon unsaturated bond;
  • R 1a and R 1b are the same or different and are hydrogen atoms or substituents;
  • R A and R B are The same or different hydrogen atoms, substituents, or atoms selected from Group 16 elements of the periodic table;
  • p1 and p2 are the same or different and represent an integer of 0 or more;
  • the bond represented by represents a single bond or a double bond.
  • the rings A 1 and A 2 may be an aromatic ring which may have a hetero atom.
  • the compound represented by the formula (A) may be at least one selected from the compounds represented by the following formula (A-1) and the following formula (A-2).
  • Z 1 and Z 2 are the same or different and are atoms selected from Group 13 to Group 16 elements of the periodic table; R 2a , R 2b , R 4a , R 4b , R 5a and R 5b are the same or different. Hydrogen atoms or substituents; R 3a and R 3b are the same or different and are selected from Group 16 elements of the periodic table; m1 and m2 are the same or different and are integers from 0 to 4; n1 and n2 are the same or different And an integer of 0 to 2; R 1a and R 1b are the same as those in the formula (A)).
  • the rings Ar 1 and Ar 2 are C 6-18 arene rings (eg, C 6-14 arene rings, preferably C 6-10 arene rings);
  • R 1a and R 1b are hydrogen An atom or a hydrocarbon group (for example, a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, preferably a hydrogen atom or a C 1-30 alkyl group);
  • R a and R b are a hydrocarbon group (for example, an alkyl group, Cycloalkyl group or aryl group);
  • q1 and q2 may be an integer of about 0 to 8 (for example, an integer of about 0 to 4, preferably 0).
  • Z 1 and Z 2 are atoms selected from Group 14 to 16 elements of the periodic table (for example, Z 1 and Z 2 are carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, An atom selected from antimony, oxygen, sulfur, selenium and tellurium, preferably an atom selected from oxygen, sulfur and selenium);
  • R 1a , R 1b , R 2a , R 2b , R 5a and R 5b are hydrogen atoms Or a hydrocarbon group [for example, R 1a , R 1b , R 2a , R 2b , R 5a and R 5b are hydrogen atoms, alkyl groups, cycloalkyl groups or aryl groups, preferably R 1a and R 1b are hydrogen atoms or C 1-30 alkyl group, R 5a and R 5b are hydrogen atom or the like];
  • R 3a and R 3b represents an oxygen atom or a sulfur atom (e.g., oxygen atom);
  • the present invention also includes a method for producing the organic semiconductor including a heating step of heating a compound represented by the following formula (1).
  • Z is an atom selected from Group 13 to 16 elements of the periodic table; R 2 is the same or different and is a hydrogen atom or a substituent; R 3 is the same or different and is selected from Group 16 elements of the periodic table) Atom; m represents an integer of 0 to 4; n represents an integer of 0 to 2, and A 1 , A 2 , R 1a , R 1b , R A , R B , p1, p2 and
  • the heating temperature in the heating step may be about 100 to 400 ° C. (for example, 200 to 300 ° C.), for example.
  • the present invention also includes an electronic device including the organic semiconductor.
  • the organic semiconductor of the present invention not only has high mobility (or carrier mobility) but also exhibits high solubility without containing an alkyl group, so that both solubility and mobility can be achieved. Further, according to the method of the present invention, a condensed polycyclic compound having a bent skeleton in which condensed rings are formed at the 1,2-position and 3,4-position of the benzene ring can be easily or efficiently produced.
  • the organic semiconductor of the present invention contains a compound represented by the following formula (A).
  • rings A 1 and A 2 are the same or different and have at least one carbon-carbon unsaturated bond;
  • R 1a and R 1b are the same or different and are hydrogen atoms or substituents;
  • R A and R B are The same or different hydrogen atoms, substituents, or atoms selected from Group 16 elements of the periodic table;
  • p1 and p2 are the same or different and represent an integer of 0 or more;
  • the bond represented by represents a single bond or a double bond.
  • the ring represented by A 1 and A 2 includes a benzene ring substituted by the groups R 1a and R 1b, and two carbon atoms (1,2-position and 3, A 4-ring carbon atom) is shared to form a condensed ring. Therefore, the rings A 1 and A 2 are not particularly limited as long as they have at least one carbon-carbon unsaturated bond (C ⁇ C bond), and heteroatoms (for example, nitrogen (N), oxygen (O), sulfur ( S) etc.) may be sufficient and the hydrocarbon ring which does not have a hetero atom may be sufficient.
  • heteroatoms for example, nitrogen (N), oxygen (O), sulfur ( S) etc.
  • a ring examples include an aliphatic ring ⁇ eg, an aliphatic hydrocarbon ring [eg, a monocyclic aliphatic ring such as a cycloalkene ring (cyclopentene ring, cyclohexene ring, etc.); a bridged ring (bornene (bornylene)]; ) Ring, norbornene ring, polycycloaliphatic ring such as dicyclopentadiene ring, etc.]; aliphatic heterocyclic ring [for example, heteroatoms such as 3-pyrroline, dihydropyran, etc.
  • an aliphatic ring eg, an aliphatic hydrocarbon ring [eg, a monocyclic aliphatic ring such as a cycloalkene ring (cyclopentene ring, cyclohexene ring, etc.); a bridged ring (bornene (bornylene)]; ) Ring, norbornene
  • aromatic rings A 1 and A 2 from the viewpoint of excellent electrical characteristics (semiconductor characteristics), usually an aromatic ring that may have a hetero atom [for example, an aromatic hydrocarbon ring (arene ring), An aromatic heterocycle (heteroarene ring) and the like] in many cases.
  • aromatic hydrocarbon ring examples include monocyclic arene rings such as benzene ring; condensed polycyclic arene rings [for example, indene ring, indane ring, naphthalene ring, tetralin ring, azulene ring, indacene ring , Acenaphthylene ring, biphenylene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, fluoranthene ring, acanthrylene ring, acephenanthrylene ring, naphthacene ring, chrysene ring, pyrene ring, triphenylene ring, pentacene ring, pentaphen ring C 9-30 condensed polycyclic arene rings such as a picene ring and a perylene ring, preferably a condensed polycyclic C 9-30 condensed polycyclic are
  • Preferred aromatic hydrocarbon rings include C 6-22 arene rings (eg, C 6-18 arene rings), more preferably C 6-14 arene rings (eg, C 6-10 arene rings), particularly benzene rings or It may be a naphthalene ring (particularly a naphthalene ring).
  • aromatic heterocycle examples include, for example, a monocyclic heteroarene ring [for example, a nitrogen (N) -containing monocyclic heteroarene ring (for example, a pyrrole ring, an imidazole ring, a pyrazole ring, Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, etc.); oxygen (O) -containing monocyclic heteroarene ring (eg, furan ring, pyran ring, etc.); sulfur (S) -containing monocyclic heteroarene ring (eg, Thiophene rings, etc.); monocyclic heteroarene rings containing two or more heteroatoms (eg, oxazole ring, isoxazole ring, thiazol ring, isothiazole ring, thiazine ring, furazane ring, thiadiazine) C 2
  • N nitrogen
  • N -containing mono
  • Preferred heteroarene rings include C 2-13 heteroarene rings (eg, nitrogen (N) containing monocyclic or polycyclic C 2-13 heteroarene rings, sulfur (S) containing monocyclic or polycyclic C 2-13 heteroarene rings, etc., more preferably C 3-9 heteroarene rings (especially sulfur (S) -containing monocyclic or polycyclic C 3-9 heteroarene rings such as thiophene ring and benzothiophene ring) It may be.
  • C 2-13 heteroarene rings eg, nitrogen (N) containing monocyclic or polycyclic C 2-13 heteroarene rings, sulfur (S) containing monocyclic or polycyclic C 2-13 heteroarene rings, etc.
  • C 3-9 heteroarene rings especially sulfur (S) -containing monocyclic or polycyclic C 3-9 heteroarene rings such as thiophene ring and benzothiophene ring
  • a C 6-30 arene ring or a C 2-20 heteroarene ring is preferable, and among them, a C 6-14 arene ring or a C 2-13 heteroarene ring, particularly C 6- A 10 arene ring or a C 4-8 heteroarene ring (for example, a benzene ring, a naphthalene ring, a thiophene ring, a benzothiophene ring, particularly a naphthalene ring or a thiophene ring) is preferable.
  • the types of the rings A 1 and A 2 may be different but are usually the same.
  • Rings A 1 and A 2 share the condensed position (positions sharing the carbon atoms (or C ⁇ C bond) at the 1,2-position and the 3,4-position in the benzene ring condensed with rings A 1 and A 2. ) Is not particularly limited.
  • Examples of the substituent represented by R 1a and R 1b include a hydrocarbon group ⁇ eg, alkyl group (eg, methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group).
  • alkyl group eg, methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group.
  • arylthio groups etc.
  • a hydroxyl group a formyl group
  • acyl group e.g., acetyl group, etc. C 1-10 acyl group such as benzoyl group
  • an alkoxycarbonyl group e.g., methoxycarbonyl, ethoxycarbonyl, etc.
  • a substituted amino group e.g., a dialkylamino group (e.g., di-C 1-6 alkylamino group such as dimethylamino group) ; diacylamino group (e.g., di-and di acetylamino group C 1- 0 acylamino group, etc.), etc.]; thiol group; a sulfonic acid group (sulfo group), a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, and the like iodine atom), etc.].
  • a dialkylamino group e.g., di-C 1-6 alkylamino group such as dimethylamino group
  • diacylamino group e.g., di-and di acetylamino group C 1- 0 acylamino group, etc.
  • thiol group e.g., a sulfonic acid group (sulf
  • R 1a and R 1b are a hydrogen atom or a hydrocarbon group (eg, an alkyl group (eg, a C 1-30 alkyl group), a cycloalkyl group, an aryl group, etc.), more preferably a hydrogen atom, A C 1-25 alkyl group, a C 5-10 cycloalkyl group or a C 6-12 aryl group (for example, a hydrogen atom, a C 1-20 alkyl group, a C 5-8 cycloalkyl group or a C 6-10 aryl group) In particular, it may be a hydrogen atom, a C 4-18 alkyl group or a C 6-10 aryl group (for example, a hydrogen atom, a C 6-16 alkyl group, particularly a hydrogen atom).
  • a hydrocarbon group eg, an alkyl group (eg, a C 1-30 alkyl group), a cycloalkyl group, an aryl group, etc.
  • Examples of the substituent represented by R A and R B include the same substituents as the groups R 1a and R 1b, and metal (or semimetal) -containing groups.
  • the metal (or metalloid) -containing group is not particularly limited as long as it contains a metal atom or metalloid atom (for example, silicon, boron, etc.).
  • a lithium atom (lithio group), a group —B (OH) 2 , group —ZnX 4 (wherein X 4 represents a halogen atom), group —MgX 5 (wherein X 5 represents a halogen atom), group —Sn (R 8 ) 3 (
  • R 8 represents an alkyl group
  • the group —Si (R 9 ) 3 wherein R 9 represents fluorine, chlorine or an alkyl group).
  • Examples of the halogen atom represented by X 4 and X 5 include chlorine, bromine, iodine and the like.
  • Examples of the alkyl group represented by R 8 and R 9 include a C 1-6 alkyl group such as a methyl group and an n-butyl group (preferably a C 1-4 alkyl group such as a methyl group). .
  • the three groups R 8 may be the same or different from each other, and the three groups R 9 may be the same or different from each other.
  • Examples of atoms selected from Group 16 elements of the periodic table represented by R A and R B include oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and polonium (Po). Is mentioned.
  • the number of substitutions p1 and p2 of the groups R A and R B can be selected according to the type of the rings A 1 and A 2 , and is, for example, an integer of about 0 to 12 (eg 0 to 8), preferably 0 to 6 ( For example, it may be an integer of about 0 to 4), more preferably an integer of about 0 to 3 (eg, 0 to 2), particularly 0 or 1.
  • the types of 2 or more R A and R B may be the same or different from each other, and are usually the same.
  • the bond represented by the examples and the broken line is a single bond when R A and R B are a hydrogen atom or a substituent (for example, a hydrocarbon group), and R A and R B are Group 16 In the case of an atom selected from an element (for example, an oxygen atom), a double bond is often exhibited.
  • Representative examples of the compound represented by the formula (A) include compounds represented by the formula (A-1) and the formula (A-2).
  • rings Ar 1 and Ar 2 are the same or different and arene rings; R a and R b are the same or different substituents; q1 and q2 are the same or different and represent an integer of 0 or more; R 1a and R 1b is the same as formula (A) including preferred embodiments.
  • examples of the arene ring represented by Ar 1 and Ar 2 include the aromatic hydrocarbon rings exemplified in the items of the rings A 1 and A 2 in the formula (A).
  • Preferred arene rings include C 6-22 arene rings (eg, C 6-18 arene rings), more preferably C 6-14 arene rings (eg, C 6-10 arene rings such as benzene ring or naphthalene ring), In particular, it may be a naphthalene ring.
  • the types of the rings Ar 1 and Ar 2 may be the same or different from each other, and are usually the same. Rings Ar 1 and Ar 2 share the condensation position (positions sharing carbon atoms (or C ⁇ C bonds) at the 1,2-position and the 3,4-position in the benzene ring condensed with rings Ar 1 and Ar 2. ) Is not particularly limited.
  • R a and R b examples include the substituents exemplified in the paragraphs R A and R B of the formula (A) (substituents similar to the groups R 1a and R 1b , metal (or semimetal) ) Containing group) and the like.
  • the types of groups R a and R b may be different from each other but are usually the same.
  • Preferred groups R a and R b include hydrocarbon groups (eg, alkyl groups (eg, C 1-30 alkyl groups, preferably C 1-20 alkyl groups), cycloalkyl groups, aryl groups, etc.), metals ( Or a semimetal) -containing group, more preferably a C 1-16 alkyl group, a C 5-10 cycloalkyl group or a C 6-12 aryl group (eg, a C 1-12 alkyl group, a C 5-8 cycloalkyl group).
  • hydrocarbon groups eg, alkyl groups (eg, C 1-30 alkyl groups, preferably C 1-20 alkyl groups), cycloalkyl groups, aryl groups, etc.
  • metals Or a semimetal) -containing group, more preferably a C 1-16 alkyl group, a C 5-10 cycloalkyl group or a C 6-12 aryl group (eg, a C 1-12 alkyl group, a
  • a metal (or metalloid) -containing group for example, a lithium atom (lithio group), a group —B (OH) 2 , a halogincio group (such as a bromogincio group), a halomagnesio group (such as a bromomagnesio group).
  • trialkylstannyl group such as tri-C 1-6 alkylstannyl group such as trimethylstannyl group
  • trihalosilyl group trifluoro
  • a trialkylsilyl group such as a tri-C 1-6 alkylsilyl group such as a trimethylsilyl group
  • a C 4-10 alkyl group or a C 6-10 aryl group in particular a C 4-10 alkyl group or a C 6-10 aryl group.
  • substitution numbers q1 and q2 of the groups R a and R b represent an integer of 0 or more, and may be selected from the range of, for example, about 0 to 14 depending on the type of the rings Ar 1 and Ar 2 , for example, 0 An integer of about 12 to 12 (for example, 0 to 8), preferably an integer of about 0 to 6 (for example, 0 to 4), more preferably an integer of about 0 to 3 (for example, 0 to 2), particularly 0 or 1 It may be (especially 0).
  • the number of substitutions q1 and q2 is 2 or more, the types of 2 or more R a and R b may be the same or different from each other, and are usually the same.
  • rings Ar 1 and Ar 2 are A C 6-14 arene ring (for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc.), a group in which R 1a and R 1b are a hydrogen atom or a C 1-30 alkyl group, and q1 and q2 are 0 [for example, C 14-22 arenes such as phenanthrene; corresponding to the C 14-22 arenes, the groups R 1a and R 1b in formula (A-1) are alkyl groups (eg, C 1-25 alkyl groups, preferably C 1-20 alkyl group, etc.) (for example, 9,10-dihexadecylphenanthrene, etc.)] and the like.
  • R 1a and R 1b in formula (A-1) are alkyl groups (eg, C 1-25 alkyl groups, preferably C 1-20 alkyl group, etc.) (for example, 9,10
  • Z 1 and Z 2 are the same or different and are atoms selected from Group 13 to Group 16 elements of the periodic table; R 2a , R 2b , R 4a , R 4b , R 5a and R 5b are the same or different. Hydrogen atoms or substituents; R 3a and R 3b are the same or different and are selected from Group 16 elements of the periodic table; m1 and m2 are the same or different and are integers from 0 to 4; n1 and n2 are the same or different R 1a and R 1b are the same as those in formula (A) including preferred embodiments.
  • Periodic Table Group 13 (Group 3B) elements include boron (B), aluminum (Al), gallium (Ga), and indium (In ), Thallium (Tl) [preferably boron, aluminum, gallium, indium, more preferably boron, aluminum, gallium, etc.].
  • Group 14 elements of the periodic table, for example, carbon (C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb) [preferably carbon, silicon, germanium, tin, More preferably, carbon, silicon, germanium, etc.] are mentioned.
  • Group 15 elements of the periodic table, for example, nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi) [preferably nitrogen, phosphorus, arsenic, antimony, More preferably, nitrogen, phosphorus, arsenic, etc.] can be mentioned.
  • Group 16 elements of the periodic table for example, oxygen (O), sulfur (S), selenium (Se), tellurium (Te), polonium (Po) [preferably oxygen, sulfur, selenium, tellurium, More preferably, oxygen, sulfur, selenium, especially sulfur, selenium (especially sulfur), and the like] are included.
  • Z 1 and Z 2 may be different from each other, but usually Z 1 and Z 2 are often the same.
  • Preferred atoms represented by Z 1 and Z 2 are atoms selected from the group consisting of Group 14 elements, Group 15 elements, and Group 16 elements of the periodic table (for example, carbon, nitrogen, phosphorus, oxygen, sulfur). And an atom selected from selenium and tellurium, and more preferably a group 16 element of the periodic table (for example, an atom selected from oxygen, sulfur and selenium, particularly sulfur).
  • each valence v1 and v2 can be selected according to the type of the corresponding atom. For example, group 13 elements (for example, boron) in the periodic table are often trivalent, and group 14 elements in the periodic table.
  • carbon, silicon, etc. are often divalent or tetravalent (particularly tetravalent), and in the periodic table group 15 elements (for example, nitrogen, phosphorus, etc.) are often trivalent to pentavalent,
  • the Group 16 elements of the periodic table eg, oxygen, sulfur, selenium, etc. are often divalent to hexavalent.
  • Examples of the substituent represented by R 2a and R 2b include the same substituents as the substituents exemplified in the section of the groups R 1a and R 1b of the formula (A).
  • the types of the groups R 2a and R 2b may be different from each other, but usually the groups R 2a and R 2b are often the same.
  • R 2a and R 2b include a hydrogen atom or a hydrocarbon group [eg, alkyl group (eg, C 1-30 alkyl group, preferably C 1-20 alkyl group), cycloalkyl group, aryl group, aralkyl] Group, alkylaryl group, preferably alkyl group, cycloalkyl group, aryl group, etc.], more preferably hydrogen atom, C 1-16 alkyl group, C 5-10 cycloalkyl group or C 6-12 aryl group ( For example, a hydrogen atom, a C 1-10 alkyl group, a C 5-8 cycloalkyl group or a C 6-10 aryl group), particularly a hydrogen atom, a C 1-6 alkyl group or a C 6-10 aryl group [particularly a hydrogen atom , C 1-4 alkyl group (such as methyl group) or C 6-8 aryl group (such as phenyl group)].
  • substitution numbers m1 when the substitution numbers
  • substitution numbers m1 and m2 of the groups R 2a and R 2b may be the same or different from each other, and may be, for example, an integer of 0 to 3, preferably an integer of 0 to 2 (eg 0 or 1, particularly 0). Good.
  • the number of substitutions m1 and m2 may be selected according to the valences v1 and v2 of Z 1 and Z 2 to which the corresponding groups R 2a and R 2b are bonded.
  • substitution numbers m1 and m2 are 0, and when the valence is trivalent, the substitution numbers m1 and m2 are 1, and when the valence is tetravalent, the substitution numbers m1 and m2 are 0 or 2,
  • substitution numbers m1 and m2 are 1 or 3
  • substitution numbers m1 and m2 are 0, 2 or 4 (for example, 0 or 2, especially 0).
  • the substitution numbers m1 and m2 may be different from each other, but usually m1 and m2 are often the same. For example, m1 and m2 may be 0.
  • Periodic Table Group 16 represented by R 3a and R 3b (6B Group) as the element can include, for example, the formula Z 1 and exemplified periodic table group 16 in the section Z 2 (6B Group) element .
  • the types of R 3a and R 3b may be different from each other, but usually R 3a and R 3b are often the same. When the substitution numbers n1 and n2 are 2, the types of the two groups R 3a and R 3b may be the same or different from each other.
  • the number of substitutions n1 and n2 of the groups R 3a and R 3b may be selected according to the respective valences v1 and v2 of Z 1 and Z 2 to which the corresponding R 3a and R 3b are bonded, for example, the valence Is divalent or trivalent, the substitution numbers n1 and n2 are 0, the valence is tetravalent or pentavalent, the substitution numbers n1 and n2 are 0 or 1, and the valence is hexavalent.
  • the number of substitutions n1 and n2 is often an integer from 0 to 2 (eg, 1 or 2, especially 2).
  • the numbers of substitutions n1 and n2 may be different from each other, but usually, n1 and n2 are often the same. For example, n1 and n2 may be 0.
  • Examples of the substituent represented by R 4a and R 4b include the substituents exemplified in the groups R A and R B of the formula (A) (substituents similar to the groups R 1a and R 1b , metal (Or a semi-metal) -containing group), a heteroaryl group optionally having a hydrocarbon group, and the like.
  • substituents usually, a halogen atom, a hydrocarbon group, a heteroaryl group which may have a hydrocarbon group, a metal (or metalloid) -containing group and the like are often used.
  • halogen atom examples include fluorine, chlorine, bromine, and iodine (preferably chlorine, bromine, iodine, and more preferably bromine).
  • hydrocarbon group examples include alkyl groups (eg, methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-hexyl group).
  • alkyl groups eg, methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-hexyl group).
  • a linear or branched C 1-20 alkyl group such as a group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group (lauryl group); cycloalkyl group (for example, cyclopentyl)
  • a C 5-10 cycloalkyl group such as a cyclohexyl group; an aryl group; a group in which two or more of these groups are combined [for example, an aralkyl group (for example, a C 6-12 aryl- such as a benzyl group or a phenethyl group) C 1-10 alkyl group, etc.); alkylaryl group, etc.].
  • an aryl group and an alkylaryl group are preferable.
  • aryl group examples include a C 6-20 aryl group such as a phenyl group, a biphenylyl group, a naphthyl group, a binaphthyl group, an anthryl group, and a phenanthryl group, preferably a C 6-14 aryl group, and more preferably a C 6-10 aryl group. Group and the like.
  • alkylaryl group examples include a tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), n-hexylphenyl group, n-octylphenyl group, 2-ethylhexyl-phenyl group, n-decylphenyl group, n A mono to penta (C 1-20 alkyl) C 6-20 aryl group, such as a dodecylphenyl group, preferably a mono to tri (C 1-16 alkyl) C 6-14 aryl group (eg mono or di (C 4 -12 alkyl) C 6-12 aryl group and the like, more preferably C 6-10 alkyl C 6-10 aryl group and the like.
  • the heteroaryl group can be broadly classified into, for example, a monocyclic heteroaryl group and a polycyclic heteroaryl group.
  • a nitrogen (N) -containing monocyclic heteroaryl group for example, pyrrolyl group, 2H-pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, etc .; oxygen (O) -containing monocyclic heteroaryl group (eg, furyl group, pyranyl group, etc.) ); A sulfur (S) -containing monocyclic heteroaryl group (eg, thienyl group (2-thienyl group, 3-thienyl group), etc.); a monocyclic heteroaryl group containing two or more heteroatoms (eg, Oxazolyl group, isoxazolyl group, thiazolyl group, iso
  • polycyclic heteroaryl group examples include a nitrogen (N) -containing polycyclic heteroaryl group (for example, indolizinyl group, indolyl group, 3H-indolyl group, isoindolyl group, 1H-indazolyl group, purinyl group, quinolyl group, Isoquinolyl group, 4H-quinolidinyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, carbazolyl group, 4aH-carbazolyl group, ⁇ -carbolinyl group, acridinyl group, phenanthridinyl group, phenazinyl group , Phenanthrolinyl group, perimidinyl group, etc.); oxygen (O) -containing polycyclic heteroaryl group (eg, benzofuranyl,
  • a monocyclic heteroaryl group is preferable from the viewpoint that both solubility and electrical characteristics can be achieved at a high level.
  • a nitrogen (N) -containing monocyclic heteroaryl group, sulfur ( S) -containing monocyclic heteroaryl groups are preferred, and sulfur (S) -containing monocyclic heteroaryl groups such as thienyl groups are particularly preferred.
  • Examples of the hydrocarbon group substituted for the heteroaryl group include the hydrocarbon groups exemplified above (for example, an alkyl group, a cycloalkyl group, an aryl group, etc.). Further, the number of substitutions is not particularly limited and can be selected according to the heteroaryl group. For example, it is an integer of about 0 to 5, preferably an integer of about 0 to 3 (eg, 0 to 2), more preferably 0 or 1. It may be a degree. Therefore, examples of the heteroaryl group substituted with a hydrocarbon group include an alkyl-heteroaryl group, a cycloalkyl-heteroaryl group, an aryl-heteroaryl group, and the like.
  • C 1-20 alkyl-C 1 -13 heteroaryl group C 6-12 aryl-C 1-13 heteroaryl group (eg, C 1-16 alkyl-C 3-9 heteroaryl group, especially C 1-12 alkyl-C 3-5 heteroaryl group ) In many cases.
  • Examples of the metal (or metalloid) -containing group include groups similar to the groups exemplified in the above-mentioned groups R A and R B.
  • Examples of the metal (or metalloid) -containing group include a lithium atom (lithio group), a group —B (OH) 2 , a halogincio group (such as a bromogincio group), a halomagnesio group (such as a bromomagnesio group), and a trialkylstannyl.
  • Groups such as tri-C 1-6 alkylstannyl groups such as trimethylstannyl group, trihalosilyl groups (such as trifluorosilyl group and trichlorosilyl group), trialkylsilyl groups (such as tri-C 1-6 alkylsilyl groups such as trimethylsilyl group) In many cases).
  • R 4a and R 4b a hydrogen atom, a halogen atom, an aryl group (for example, a C 6-14 aryl group), an alkylaryl group (for example, a C 1-20 alkyl C 6-14 aryl group)
  • a heteroaryl group for example, a C 4-13 heteroaryl group
  • an alkyl heteroaryl group for example, a C 1-20 alkyl C 4-13 heteroaryl group
  • a hydrogen atom, a halogen atom for example, chlorine, bromine, iodine, especially bromine, C 6-12 aryl group (especially C 6-10 aryl group), C 1-16 alkyl C 6-12 aryl group (eg C 1-12 alkyl C 6- 10 aryl group), C 4-9 heteroaryl group (e.g., C 4-5 heteroaryl group), C 1-16 alkyl C 4-9 heteroaryl group
  • C 1-12 alkyl C 4-5 heteroaryl group for example, C 1-12 alkyl C 4-5
  • Examples of the substituent represented by R 5a and R 5b include the same substituents as those exemplified in the section of the groups R 1a and R 1b in the formula (A).
  • the types of the groups R 5a and R 5b may be different from each other, but usually the groups R 5a and R 5b are often the same.
  • R 5a and R 5b are hydrogen atoms or hydrocarbon groups (for example, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkylaryl groups, preferably alkyl groups, cycloalkyl groups, aryl groups, etc.) More preferably a hydrogen atom, a C 1-16 alkyl group, a C 5-10 cycloalkyl group or a C 6-12 aryl group (for example, a hydrogen atom, a C 1-10 alkyl group, a C 5-8 cycloalkyl group or C 6-10 aryl group, etc.), in particular a hydrogen atom, a C 1-6 alkyl group or a C 6-10 aryl group (particularly a hydrogen atom).
  • hydrocarbon groups for example, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkylaryl groups, preferably alkyl groups, cycloalkyl groups, aryl groups, etc
  • the compound represented by the formula (A-2) is typically a compound corresponding to the compound exemplified in the section of the compound represented by the formula (1B) described later, for example, Z 1 and Z 2 are sulfur atoms.
  • M1 and m2 and n1 and n2 are 0,
  • the groups R 1a and R 1b are hydrogen atoms or alkyl groups (for example, C 1-30 alkyl group, etc.)
  • the groups R 5a and R 5b are hydrogen atoms
  • the groups R 4a and R 4b is a hydrogen atom, a halogen atom, a C 6-14 aryl group, a C 1-20 alkyl C 6-14 aryl group, a C 4-13 heteroaryl group, a C 1-20 alkyl C 4-13 heteroaryl group, a lithium atom , group -B (OH) 2, (such as Buromojinshio group) Harojinshio group, (such as bromomagnesio group) Haromaguneshio
  • More specific compounds include, for example, (A-2a) benzo [1,2-b: 4,3-b ′] dithiophene; (A-2b) 2,7-diphenyl-benzo [1,2-b : 2,3-b ′] dithiophene, etc.
  • the organic semiconductor of the present invention only needs to contain at least the compound represented by the formula (A), and can be used alone or in combination of two or more.
  • the compounds represented by the formula (A) it is preferable to include at least one compound selected from the compounds represented by the formula (A-1) and the formula (A-2). From the viewpoint of solubility, it is preferable to contain at least the compound represented by the formula (A-2).
  • the compound represented by the formula (A) exhibits high solubility because of the bent skeleton even if it does not have a substituent such as a long-chain alkyl group. It can be compatible with mobility. Therefore, the solubility of the compound represented by the formula (A) in toluene is, for example, 0.01% by weight or more (for example, about 0.05 to 30% by weight), preferably 0.1% by weight or more (for example, It may be about 0.5 to 10% by weight), more preferably 1% by weight or more (for example, about 1.5 to 5% by weight). In addition, you may measure solubility by the method as described in the Example mentioned later.
  • the compound represented by the formula (A) (flexible compound) has high mobility (electric mobility or carrier mobility) despite having high solubility. is doing. Therefore, the mobility of the field-effect transistor manufactured using the compound represented by the formula (A) is, for example, 0.001 to 0.5 cm 2 / Vs, preferably 0.01 to 0.3 cm 2 / It may be about Vs, more preferably about 0.02 to 0.2 cm 2 / Vs (for example, 0.05 to 0.15 cm 2 / Vs). The mobility may be measured by the method described in the examples described later.
  • the operating voltage can be reduced.
  • the absolute value of the threshold voltage may be, for example, 100 V or less (for example, about 0.1 to 80 V), preferably 70 V or less. (For example, about 1 to 60 V), more preferably 50 V or less (for example, about 10 to 50 V) may be used.
  • the method for producing the organic semiconductor (compound represented by the formula (A)) of the present invention is not particularly limited, and may be prepared by a conventional method (for example, a method utilizing a photocyclization reaction), but is easy. Or a method including a heating step of heating a compound represented by the following formula (1) corresponding to the compound represented by the formula (A) from the point that it can be produced efficiently (or with high purity). preferable.
  • Z is an atom selected from Group 13 to 16 elements of the periodic table; R 2 is the same or different and is a hydrogen atom or a substituent; R 3 is the same or different and is selected from Group 16 elements of the periodic table) Atom; m represents an integer of 0 to 4; n represents an integer of 0 to 2, and A 1 , A 2 , R 1a , R 1b , R A , R B , p1, p2 and
  • examples of the atom represented by Z include the same atoms as those represented by Z 1 and Z 2 in the formula (A-2).
  • group 13 (group 3B) elements of the periodic table boron, aluminum, gallium, and indium are preferable, and boron, aluminum, gallium, and particularly boron are preferable.
  • group 14 (Group 4B) of the periodic table carbon, silicon, germanium, and tin are preferable, and carbon, silicon, germanium, and particularly silicon are preferable.
  • the elements in Group 15 (Group 5B) of the periodic table nitrogen, phosphorus, arsenic, antimony are preferable, and nitrogen, phosphorus, arsenic, particularly phosphorus are preferable.
  • group 16 (group 6B) elements of the periodic table oxygen, sulfur, selenium, tellurium, and more preferably oxygen, sulfur, selenium, particularly sulfur, selenium (especially sulfur), and the like.
  • Preferred atoms represented by Z include atoms selected from the group consisting of Group 14 elements, Group 15 elements, and Group 16 elements of the periodic table (for example, carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic).
  • An atom selected from antimony, oxygen, sulfur, selenium and tellurium, and more preferably an atom selected from silicon, germanium, nitrogen, phosphorus, arsenic, oxygen, sulfur and selenium (for example, silicon, germanium, An atom selected from phosphorus, arsenic, sulfur and selenium, etc.) is selected from Group 15 to 16 elements of the periodic table from the viewpoint of easy production of the compound.
  • an atom selected from sulfur, selenium and phosphorus especially sulfur.
  • the valence v can be selected according to the type of the corresponding Z.
  • the periodic table group 13 element for example, boron
  • the valence v is often trivalent
  • the periodic table group 14 element for example, carbon
  • Silicon, etc. are often divalent or tetravalent (especially tetravalent)
  • group 15 elements for example, nitrogen, phosphorus, etc.
  • Group elements eg, oxygen, sulfur, selenium, etc.
  • Examples of the substituent represented by R 2 may be the same as those of the groups R 2a and R 2b of the formula (A-2) including preferred embodiments.
  • substitution number m is 2 or more
  • the types of the two or more groups R 2 may be the same or different from each other.
  • the substitution number m of the group R 2 may be, for example, an integer from 0 to 3, preferably an integer from 0 to 2. Further, the substitution number m may be selected according to the valence v of the atom Z to which the corresponding group R 2 is bonded. For example, when the valence is divalent, the substitution number m is 0, Is trivalent, the substitution number m is 1, when the valence is tetravalent, the substitution number m is 0 or 2, and when the valence is pentavalent, the substitution number m is 1 or 3, When the valence is hexavalent, the substitution number m is often 0, 2 or 4 (eg, 0 or 2, particularly 0).
  • the group 16 (group 6B) element of the periodic table represented by R 3 may be the same as the groups R 3a and R 3b of the formula (A-2) including preferred embodiments.
  • the number of substitutions n is 2, the types of the two atoms R 3 may be the same or different from each other.
  • the substitution number n of atoms R 3 may be selected depending on the valence v of atoms Z which corresponding atoms R 3 are attached, for example, if the valence of divalent or trivalent, substitution number n is 0 When the valence is tetravalent or pentavalent, the substitution number n is 0 or 1, and when the valence is hexavalent, the substitution number n is an integer of 0 to 2 (eg, 1 or 2, particularly 2 ) In many cases.
  • Ar 1 , Ar 2 , R 1a , R 1b , R a , R b , q1 and q2 are the same as those in the formula (A-1) including preferred embodiments; Z, R 2 , R 3 , M and n are the same as those in the formula (1) including preferred embodiments.
  • the rings Ar 1 and Ar 2 are C 6-14 arene rings (for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.), groups Examples thereof include compounds in which R 1a and R 1b are hydrogen atoms or alkyl groups (for example, C 1-30 alkyl groups), and q1 and q2 are 0 (for example, compounds described in Table 1 below).
  • the rings Ar 1 and Ar 2 are C 6-14 arene rings (eg, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.), and the groups R 1a and R 1b are hydrogen atoms or C 1- More specifically, the compound in which 25 alkyl group, q1 and q2 are 0, for example, (1A-a) a compound in which Z is a sulfur atom, (1A-b) a compound in which Z is a selenium atom, (1A -c) a compound in which Z is a phosphorus atom, (1A-d) a compound in which Z is a silicon atom, (1A-e) a compound in which Z is an oxygen atom, (1A-f) a compound in which Z is a carbon atom, etc. Is mentioned.
  • Examples of the compound in which (1A-a) Z is a sulfur atom include (1A-a1) dialenothiepines [eg, dibenzo [b, f] thiepine, dinaphthothiepine (eg, dinaphtho [2,3-b: 2,3 -F] thiepine, dinaphtho [2,1-b: 2,3-f] thiepine, dinaphtho [1,2-b: 2,3-f] thiepin, dinaphtho [1,2-b: 1,2-f ] Thiepine, dinaphtho [1,2-b: 2,1-f] thiepin, dinaphtho [2,1-b: 1,2-f] thiepin, etc.), phenanthronaphthothiepin (for example, phenanthro [2, 1-b] naphtho [such as 1, 2-f] thiepin), di phenanthrolato Chie pins (e.
  • thiepin di C 6-14 such Arenochiepin , a preferably di C 6-10 Arenochiepin (1A-a2) S-oxide (sulfinyl) or S, S-dioxide (sulfonyl) corresponding to the compound exemplified in (1A-a1) (for example, 5,5-dioxo-dibenzo [ b, f] thiepine, 6,6-dioxo-dinaphtho [2,3-b: 2,3-f] thiepine and the like.
  • (1A-b) As the compound in which Z is a selenium atom, for example, (1A-a) a compound in which the sulfur atom of Z is replaced with a selenium atom corresponding to the compound in which Z is a sulfur atom (1A-b1 ) [Eg, dinaphtho [2,1-b: 1,2-f] selenepine etc.] to (1A-b2) [eg, Se, Se-dioxo-dinaphtho [2,1-b: 1,2-f] Selenepin etc.].
  • (1A-c) Compounds in which Z is a phosphorus atom include (1A-c1) dialenophospines [eg, dibenzophosphepines (eg, dibenzo [b, f] phospine); P-methyl-dibenzo PC 1-4 alkyl-dibenzo [b, f] phospine, such as [b, f] phospine; PC 6-10 aryl-dibenzo [b, such as P-phenyl-dibenzo [b, f] phospine , F] phosphapine); dinaphtho phosfepines (eg dinaphtho [2,1-b: 1,2-f] phospine, dinaphth [2,3-b: 2,3-f] naphthaldehyde phosphepinium pin; P- methyl - dinaphtho [2,1-b: 1,2-f ] Hosuf
  • Examples of the compound in which (1A-d) Z is a silicon atom include (1A-d1) dialenosilepins [eg, dibenzosilepins (eg, dibenzo [b, f] silepin; Si-methyl-dibenzo [b, f] Si-C 1-4 alkyl-dibenzo [b, f] silepin such as silepin; Si-C 6-10 aryl-dibenzo [b, f] such as Si-phenyl-dibenzo [b, f] silepin Silepine; Si, Si-diC 1-4 alkyl-dibenzo [b, f] silepin such as Si, Si-dimethyl-dibenzo [b, f] silepin; Si-methyl-Si-phenyl-dibenzo [b, f] Si-C 1-4 alkyl -Si-C 6-10 aryl, such Shirepin - dibenzo [b, f] Shirepin
  • Si-C 6-10 aryl-dinaphtho silepine Si, Si-dimethyl-dinaphtho [2,1-b: 1,2-f] silepin, Si, Si-dimethyl-dinaphtho [2,3-b: 2 , 3-f] Silepin and other Si Si-di-C 1-4 alkyl-dinaphtho silepine; Si-methyl-Si-phenyl-dinaphtho [2,1-b: 1,2-f] silepin, Si-methyl-Si-phenyl-dinaphtho [2,3- b: Si-C 1-4 alkyl-Si-C 6-10 aryl-dinaphtho silepin such as 2,3-f] silepin; Si, Si-diphenyl-dinaphtho [2,1-b: 1,2-f] silepin Si, Si-diphenyl-dinaphtho [2,3-b: 2,3-f] silepin,
  • (1A-e) As the compound in which Z is an oxygen atom, for example, a compound (1A-e1) in which the sulfur atom of Z is replaced with an oxygen atom corresponding to the compound exemplified in the above (1A-a1) dialenothiepines [For example, dinaphtho [2,1-b: 1,2-f] oxepin and the like] and the like.
  • the compound in which (1A-f) Z is a carbon atom is, for example, a compound in which the silicon atom in Z is replaced with a carbon atom, corresponding to the compound in which (1A-d) Z is a silicon atom.
  • (1A-f1) [for example, 7,7-dimethyl-dinaphtho [1,2-a: 2,1-d] cycloheptene and the like] and the like.
  • the in (1A-a) ⁇ (1A -f) is based on R 1a and R 1b is exemplified for the compound is a hydrogen atom, corresponding to the exemplified compounds, radicals R 1a and R 1b In which is an alkyl group (eg, a C 1-25 alkyl group, preferably a C 1-20 alkyl group).
  • R 1a and R 1b In which is an alkyl group (eg, a C 1-25 alkyl group, preferably a C 1-20 alkyl group).
  • compounds (1A-a) to (1A-f) compounds (1A-a), (1A-b), (1A-c), (1A-d) [for example, compound (1A-a) , (1A-b), (1A-c)] are preferred, and compound (1A-a) is particularly preferred.
  • Z 1 , Z 2 , R 1a , R 1b , R 2a , R 2b , R 3a , R 3b , R 4a , R 4b , R 5a , R 5b , m1, m2, n1, and n2 are preferred embodiments.
  • Z, R 2 , R 3 , m, and n are the same as those in formula (1) including preferred embodiments, and the present specification and claims. In the range, the position number in the condensed ring of the formula (1B) is shown in the formula on the right side).
  • Z 1 and Z 2 are sulfur atoms.
  • M1 and m2 and n1 and n2 are 0,
  • the groups R 1a and R 1b are hydrogen atoms or alkyl groups (for example, C 1-30 alkyl group, etc.)
  • the groups R 5a and R 5b are hydrogen atoms
  • the groups R 4a and R 4b is a hydrogen atom, a halogen atom, a C 6-14 aryl group, a C 1-20 alkyl C 6-14 aryl group, a C 4-13 heteroaryl group, a C 1-20 alkyl C 4-13 heteroaryl group, a lithium atom , group -B (OH) 2, (such as Buromojinshio group) Harojinshio group, (such as bromomagnesio group) Haromaguneshio group, tri C 1-4, such as trial
  • trihalosilyl group trifluoro silyl group, such as trichloro silyl group
  • compound is a trialkylsilyl group (such as tri-C 1-4 alkylsilyl group such as trimethylsilyl group) and the like.
  • Z 1 and Z 2 are sulfur atoms, m1 and m2, n1 and n2 are 0, groups R 1a and R 1b are hydrogen atoms or C 1-25 alkyl groups, and groups R 5a and R 5b are More specifically, as the strain type compound that is a hydrogen atom, for example, (1B-a) a compound in which Z is a sulfur atom, (1B-b) a compound in which Z is a selenium atom, (1B-c) Z is Examples include compounds that are phosphorus atoms, compounds in which (1B-d) Z is a silicon atom, compounds in which (1B-e) Z is an oxygen atom, and compounds in which (1B-f) Z is a carbon atom.
  • Examples of the compound in which (1B-a) Z is a sulfur atom include (1B-a1) dithieno [3,2-b: 2,3-f] thiepine; (1B-a2) 2,6-dichloro-dithieno [3,2-b: 2,3-f] thiepine, 2,6-dibromo-dithieno [3,2-b: 2,3-f] thiepine, 2,6-diiodo-dithieno [3,2-b 2,6-dihalo-dithieno [3,2-b: 2,3-f] thiepine such as 2,3-f] thiepine; (1B-a3) 2,6-diphenyl-dithieno [3,2-b : 2,3-diC 6-10 aryl-dithieno [3,2-b: 2,3-f] thiepine such as 2,3-f] thiepine; (1B-a4) 2,6-bis (4- Hexylpheny
  • Examples of (1B-b) compounds in which Z is a selenium atom correspond to the compounds (1B-a1) to (1B-a14) exemplified in the compounds in which (1B-a) Z is a sulfur atom, Compounds (1B-b1) to (1B-b14) in which Z is replaced from a sulfur atom to a selenium atom (for example, (1B-b1) selenepino [3,2-b: 6,7-b ′] dithiophene, etc.) Can be mentioned.
  • Examples of the compound in which (1B-c) Z is a phosphorus atom include (1B-c1) phosfepino [3,2-b: 6,7-b ′] dithiophenes (for example, phosfepino [3,2-b: 6,7-b ′] dithiophene; 4-C 1-4 alkyl-phosfepino [3,2-b: 6,7 such as 4-methyl-phosfepino [3,2-b: 6,7-b ′] dithiophene -B '] dithiophene; 4-C 6-10 aryl-phosfepino [3,2-b: 6,7-b' such as 4-phenyl-phosfepino [3,2-b: 6,7-b '] dithiophene
  • the compounds (1B-a2) to (1B-a13) exemplified in the section of the compound in which (1B-a) Z is a sulfur atom, dithieno [3,2-b: 2, 3-f] thie
  • Examples of the compound in which (1B-d) Z is a silicon atom include (1B-d1) cilepino [3,2-b: 6,7-b ′] dithiophenes (for example, cilepino [3,2-b: 6,7-b ′] dithiophene; 4-C 1-4 alkyl-cilepino [3,2-b: 6,7 such as 4-methyl-cilepino [3,2-b: 6,7-b ′] dithiophene -B '] dithiophene; 4-C 6-10 aryl-cilepino [3,2-b: 6,7-b' such as 4-phenyl-cilepino [3,2-b: 6,7-b '] dithiophene Dithiophene; 4,4-DiC 1-4 alkyl-cilepino [3,2-b: 6,7-, such as 4,4-dimethyl-cilepino [3,2-b: 6,7-b ′] dithiophene b ′] dithiophene; 4-
  • Examples of the compound in which (1B-f) Z is a carbon atom correspond to the compounds (1B-d1) to (1B-d13) exemplified as the compounds in which (1B-d) Z is a silicon atom, Compounds in which the silicon atom of Z is replaced by a carbon atom (1B-f1) to (1B-f13) [for example, 4,4-dimethyl-cyclohepta [1,2-b: 5,4-b ′] dithiophene, etc.], etc. Is mentioned.
  • compounds (1B-a) to (1B-f) compounds (1B-a), (1B-b), (1B-c), (1B-d) [for example, compound (1B-a) , (1B-b), (1B-c)] are preferred, and compound (1B-a) is particularly preferred.
  • the compound represented by the formula (1) is a compound other than the compounds represented by the formula (1A) and the formula (1B) (for example, thieno [3,2-e: 6,7-e ′] di [ 1] Thiepinodibenzoheteroarene such as benzothiophene, thiepino [3,2-e: 6,7-e ′] di [1] benzofuran, thiepino [3,2-e: 6,7-e ′] diindole Etc.).
  • thieno [3,2-e: 6,7-e ′] di [ 1] Thiepinodibenzoheteroarene such as benzothiophene, thiepino [3,2-e: 6,7-e ′] di [1] benzofuran, thiepino [3,2-e: 6,7-e ′] diindole Etc.
  • These compounds represented by the formula (1) can be used alone or in combination of two or more.
  • the heating temperature in the heating step may be selected according to the type of atom Z and the like, and can be selected, for example, from the range of about 100 to 400 ° C., for example, 150 to 400 ° C. (for example, 180 to 350 ° C.), Preferably, it may be about 200 to 300 ° C. (for example, 210 to 250 ° C.).
  • the heating time may be, for example, about 10 seconds to 1 hour (eg, 1 to 40 minutes), preferably about 3 to 30 minutes.
  • the heating step may be performed in air, but is usually performed in an inert gas atmosphere (for example, a rare gas such as helium gas or argon gas; nitrogen gas or the like).
  • the heating step may be performed under normal pressure, reduced pressure, or increased pressure.
  • X 1a , X 1b and X 2 are halogen atoms
  • Ph is a phenyl group
  • L 1 is a halogen atom or a group —SO 2 R 6 (R 6 is a hydrocarbon group or a fluorinated hydrocarbon group).
  • Z, A 1 , A 2 , R 1a , R 1b , R 2 , R 3 , R A , R B , m, n, p1 and p2 are each described in the formula (1) including preferred embodiments. The same).
  • examples of the halogen atom represented by X 1a include chlorine, bromine and iodine, and bromine is preferable.
  • the carbonyl compound represented by the formula (2a) may be a carbonyl compound corresponding to the compound represented by the formula (1), and usually R 1a is a hydrogen atom in many cases.
  • Typical examples of the carbonyl compound represented by the formula (2a) include aldehydes [eg, halo- such as o-bromo-benzaldehyde, 2-bromo-1-naphthaldehyde, 3-bromo-2-naphthaldehyde, etc.
  • Formylarenes 3-halo-heteroarenes such as 3-bromopyrrole-2-carboxaldehyde, 3-bromofuran-2-carboxaldehyde, 3-bromothiophene-2-carboxaldehyde, 3-bromoselenophene-2-carboxaldehyde -2-carboxaldehyde etc.]; ketones [eg halo-C 2-31 alkanoyl such as o-bromo-heptanoyl-benzene, 2-bromo-1-undecanoyl-naphthalene, 3-bromo-2-heptadecanoylnaphthalene, etc.
  • the reducing agent is not particularly limited, and examples thereof include conventional reducing agents such as lithium borohydride (LiBH 4 ), sodium borohydride (NaBH 4 ), lithium aluminum hydride (LiAlH 4 ), and the like.
  • the ratio of the reducing agent used is, for example, about 0.1 to 5 mol, preferably 1 to 3 mol, more preferably about 1.5 to 2 mol, relative to 1 mol of the carbonyl compound represented by the formula (2a). There may be.
  • a reducing agent can also be used individually or in combination of 2 or more types.
  • the reaction may be performed in the presence of a solvent inert to the reaction.
  • the solvent is not particularly limited, and is a conventional organic solvent such as aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, etc.), Alcohols (methanol, ethanol, etc.), ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran, dioxane, etc.) may be used. These solvents can be used alone or in combination of two or more. Of these solvents, alcohols such as ethanol are usually used in many cases.
  • the reaction may be performed in an inert gas atmosphere (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about ⁇ 20 to 40 ° C., preferably about ⁇ 10 to 30 ° C. (usually 0 ° C. to room temperature).
  • the reaction time may be, for example, about 1 to 48 hours, preferably about 12 to 36 hours.
  • it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • the phosphonium salt represented by the formula (5) can be prepared by reacting the hydroxy compound represented by the formula (3) with the triphenylphosphine hydrohalide salt represented by the formula (4). .
  • examples of the halogen atom represented by X 2 include chlorine, bromine and iodine, and bromine is preferable.
  • examples of the triphenylphosphine hydrogen halide salt represented by the formula (4) include triphenylphosphine hydrogen chloride salt, triphenylphosphine hydrobromide salt, triphenylphosphine hydrogen iodide salt, and the like.
  • the triphenylphosphine hydrogen halide salt represented by the formula (4) can be used alone or in combination of two or more. A commercially available product may be used as the triphenylphosphine hydrogen halide salt represented by the formula (4).
  • the proportion of the triphenylphosphine hydrogen halide salt represented by the formula (4) is, for example, 1 to 3 mol, preferably 1 to 2 mol, relative to 1 mol of the hydroxy compound represented by the formula (3). It may be about 1 mol, and usually about 1 mol.
  • the reaction may be performed in the presence of a solvent inert to the reaction.
  • a solvent inert examples include aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, etc.), ethers (chain ethers such as diethyl ether). , Cyclic ethers such as tetrahydrofuran and dioxane, and the like.
  • a solvent can also be used individually or in combination of 2 or more types. Of these solvents, usually halogenated hydrocarbons such as chloroform are often used.
  • the reaction may be performed in an inert gas atmosphere (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about 40 to 100 ° C., preferably about 50 to 70 ° C., and the reaction may be performed under reflux conditions.
  • the reaction time may be, for example, about 1 to 40 hours, preferably about 10 to 30 hours.
  • After completion of the reaction it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • examples of the halogen atom represented by X 1b include the same atoms as those of X 1a and preferred embodiments.
  • examples of the compound represented by Formula (2b) include the same compounds as those exemplified in the formula (2a).
  • the compounds represented by the formulas (2a) and (2b) are often the same compound.
  • the proportion of the phosphonium salt represented by the formula (5) is, for example, 1 to 1.5 mol, preferably 1.05 to 1.2 mol, relative to 1 mol of the carbonyl compound represented by the formula (2b). It may be a degree.
  • the base examples include metal hydroxides (alkali metal hydroxides such as sodium hydroxide and calcium hydroxide or alkaline earth metal hydroxides), metal carbonates (alkali carbonates such as sodium carbonate and sodium hydrogen carbonate).
  • Inorganic bases such as metal or alkaline earth metal carbonates), metal alkoxides (such as alkali metal C 1-6 alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide); amines (trialkyls such as triethylamine)
  • organic bases such as aromatic tertiary amines such as amine and benzyldimethylamine, and heterocyclic tertiary amines such as pyridine.
  • the bases may be used alone or in combination of two or more. Of these bases, metal alkoxides such as potassium t-butoxide are usually used in many cases.
  • the ratio of the base used may be, for example, about 1 to 5 equivalents, preferably about 2 to 4 equivalents, relative to 1 equivalent of the phosphonium salt represented by the formula (5).
  • the reaction may be performed in the presence of a solvent inert to the reaction.
  • a solvent inert examples include aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, etc.), alcohols (methanol, ethanol, etc.), ethers (Chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane) and ethers such as tetrahydrofuran are usually used in many cases.
  • the reaction may be performed in an inert gas atmosphere (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about ⁇ 20 to 50 ° C., preferably about ⁇ 10 to 30 ° C. (usually 0 ° C. to room temperature).
  • the reaction time may be, for example, about 1 to 100 hours, preferably about 24 to 72 hours.
  • it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • the compound represented by the formula (1) is represented by the lithiated product produced by reacting the dihalo compound represented by the formula (6) and a lithiating agent (lithiation reaction), and the formula (7). It can be prepared by reacting with a compound (ring-closing agent) (cyclization reaction).
  • the lithiating agent is not particularly limited, and a conventional lithiating agent, for example, alkyl lithium (eg, C 1-4 alkyl lithium such as methyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, etc.) ), Aryl lithium (such as phenyl lithium), lithium amides (lithium diisopropylamide (LDA), lithium-2,2,6,6-tetramethylpiperidine (LiTMP), lithium-bis (trimethylsilyl) amide (LHMDS), etc.) Etc.
  • alkyl lithium eg, C 1-4 alkyl lithium such as methyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, etc.
  • Aryl lithium such as phenyl lithium
  • lithium amides lithium diisopropylamide (LDA), lithium-2,2,6,6-tetramethylpiperidine (LiTMP), lithium-bis (trimethylsily
  • alkyllithiums such as n-butyllithium are usually used.
  • the ratio of the lithiating agent used may be, for example, 2 to 5 mol, preferably about 2 to 3 mol, usually about 2 mol, per 1 mol of the dihalo compound represented by the formula (6). It may be.
  • the reaction may be performed in the presence of a solvent inert to the reaction.
  • the solvent may be, for example, ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane) and the like, and usually diethyl ether is often used.
  • the reaction may be performed in an inert gas atmosphere (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about ⁇ 100 to ⁇ 50 ° C., preferably about ⁇ 80 to ⁇ 70 ° C.
  • the reaction time may be, for example, about 1 to 120 minutes, preferably about 30 to 90 minutes.
  • the reaction solution containing the lithiated product may be subjected to the next cyclization reaction, if necessary, without purification by conventional separation and purification means.
  • examples of the halogen atom represented by L 1 include chlorine, bromine, iodine and the like (especially chlorine).
  • examples of the hydrocarbon group represented by R 6 include the hydrocarbon groups exemplified in the above-mentioned groups R 1a and R 1b .
  • examples of the fluorinated hydrocarbon group represented by R 6 include a group in which part or all of the hydrogen atoms in the hydrocarbon group are fluorinated, such as a fluorinated alkyl group such as a trifluoromethyl group, a pentafluorophenyl group, and the like. And the like.
  • Representative examples of the group —SO 2 R 6 represented by L 1 include, for example, an alkylsulfonyl group (eg, a C 1-6 alkylsulfonyl group such as a methylsulfonyl group (mesyl group)); an arylsulfonyl group (a phenylsulfonyl group)
  • a C 6-10 arylsulfonyl group such as an alkylarylsulfonyl group (a C 1-6 alkyl C 6-10 arylsulfonyl group such as a p-toluenesulfonyl group (tosyl group)); a nitroarylsulfonyl group (o- Nitro C 6-10 arylsulfonyl group such as nitrobenzenesulfonyl group); fluorinated alkylsulfonyl group (fluorinated C 1-6 alkylsulfonyl group such as triflu
  • the two groups L 1 may be different from each other but are usually the same.
  • a halogen atom for example, chlorine
  • an arylsulfonyl group for example, benzenesulfonyl group
  • the compound represented by the formula (7) (ring-closing agent) can be selected corresponding to the compound represented by the formula (1), and typically, for example, benzenethiosulfonic anhydride ((PhSO 2 )) Sulfonic acid anhydrides such as 2 S); dihalides such as selenium dichloride (SeCl 2 ), dimethyldichlorosilane, and phenyldichlorophosphine.
  • benzenethiosulfonic anhydride ((PhSO 2 )) Sulfonic acid anhydrides such as 2 S
  • dihalides such as selenium dichloride (SeCl 2 ), dimethyldichlorosilane, and phenyldichlorophosphine.
  • SeCl 2 selenium dichloride
  • phenyldichlorophosphine phenyldichlorophosphine
  • the use ratio of the compound represented by the formula (7) (ring-closing agent) is, for example, 1 to 1.5 mol with respect to 1 mol of the dihalo compound represented by the formula (6) subjected to the lithiation reaction. Preferably, it may be about 1.05 to 1.2 mol.
  • the reaction may be performed in the presence of a solvent inert to the reaction, and a solvent may be further added to the reaction solution of the lithiation reaction.
  • a solvent may include ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane) and the like, and tetrahydrofuran is usually used in many cases.
  • the reaction may be performed in an inert gas atmosphere (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about ⁇ 100 to 50 ° C., preferably about ⁇ 90 to 30 ° C. (usually ⁇ 78 ° C. to room temperature).
  • the reaction time may be, for example, about 1 to 12 hours, preferably about 6 to 10 hours.
  • it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • Method B The compound represented by the formula (1) can also be prepared according to the following reaction formula (Method B).
  • Method B is advantageous in that it has fewer reaction steps than Method A. Moreover, it is useful when introducing a hydrocarbon group (such as an alkyl group) into the groups R 1a and R 1b .
  • Each of the bonds represented by formula (1) is the same as in the description of formula (1), including preferred embodiments; and X 1a and X 1b are the same as in the description of formula (2a), including preferred embodiments, respectively;
  • the group —Sn (R 8 ) 3 is the same as described in the section of the metal (or metalloid) -containing group including preferred embodiments.
  • a 1 and A 2 , R 1a and R 1b , R A and R B , X 1a and X 1b , and p1 and p2 may be the same or different. Are usually the same.
  • halo-C 2-31 alkanoyl-arene eg, 2-bromo-1-heptadecanoyl-naphthalene
  • 3-halo-2-alkanoyl-heteroarene eg, 3-bromo-2-heptanoyl-thiophene
  • the compounds represented by the formula (2a) and the formula (2b) may be purchased from the market.
  • a 3-halo-heteroarene and an alkanoic acid chloride or an alkanoic acid anhydride may be chlorinated.
  • You may prepare by the method of making it react in the presence of Lewis' acid catalysts, such as aluminum (Friedel Crafts acylation reaction).
  • Lewis' acid catalysts such as aluminum (Friedel Crafts acylation reaction).
  • the compound represented by the formula (2a) and the formula (2b) is substituted with an alkanoyl group at a position other than the substitution position adjacent to the by-product (for example, X 1a and X 1b ).
  • the compound or the like may be subjected to the reaction with the compound represented by the formula (9) without being completely removed and purified after completion of the reaction.
  • the types of the six groups R 8 may be different from each other but are usually the same.
  • a compound represented by the formula (9) typically, for example, bis (trialkyltin) sulfide (or bis (trialkylstannyl) sulfide) [for example, bis (trimethyltin) sulfide, bis (tributyltin) sulfide bis (such as tri-C 1-4 alkyltin) sulfide, etc.]; (or bis (trialkyltin) oxide (or bis (trialkyltin) ether) [e.g., bis bis (tributyltin) oxide (tri C 1- 4 alkyl tin) oxide]; bis (trialkyl tin) selenide [for example, bis (tri C 1-4 alkyl tin) selenide such as bis (tributyl tin) selenide, etc., and bis (trialkyl tin) such as bis (tribu
  • the ratio of the total amount of the compounds represented by the formula (2a) and the formula (2b) is, for example, 2 to 3 mol, preferably 2.05 to 2. mol per 1 mol of the compound represented by the formula (9). It may be about 5 mol (usually 2.1 to 2.2 mol).
  • the reaction may be performed in the presence of a catalyst.
  • a catalyst examples include palladium complexes [palladium complexes such as palladium (0) catalyst (for example, palladium acetate, tris (dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0), etc.), etc.] ] Etc. are mentioned.
  • the catalyst is used in an amount of, for example, 0.01 to 0.2 mol, preferably 0.05 to 0.15 mol (usually 0.1 to 0 mol) per mol of the compound represented by formula (9). About 12 mol).
  • the reaction may be performed in the presence of a solvent inert to the reaction.
  • a solvent inert examples include ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), aromatic hydrocarbons (benzene, toluene, xylene and the like), and the like. These solvents can be used alone or in combination of two or more. Of these solvents, toluene and the like are usually used in many cases.
  • the reaction may be performed in an atmosphere of inert gas (nitrogen; a rare gas such as helium or argon) (or under an air stream).
  • the reaction temperature may be, for example, about 80 to 200 ° C., preferably about 100 to 150 ° C. (usually 110 to 130 ° C.).
  • the reaction time may be, for example, about 1 to 48 hours, preferably about 12 to 24 hours.
  • it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • Low-valent titanium is produced by reducing a titanium compound with a reducing agent in an inert gas atmosphere such as argon, and is usually produced in a reaction system containing a compound represented by formula (10). Many.
  • the titanium compound include titanium halides such as titanium chloride (III) (TiCl 3 ) and titanium chloride (IV) (TiCl 4 ).
  • the titanium compound may form a complex with a ligand (such as dimethoxyethane).
  • the reducing agent examples include alkali metals such as lithium (Li) and potassium (K); aluminum hydride compounds such as lithium aluminum hydride (LiAlH 4 ); zinc (Zn) or zinc-containing compounds (or alloys) [for example, Zinc (Zn) -copper (Cu) couple, etc.], etc., and zinc (Zn) or a zinc-containing compound (for example, zinc (Zn)) is often used.
  • alkali metals such as lithium (Li) and potassium (K)
  • aluminum hydride compounds such as lithium aluminum hydride (LiAlH 4 )
  • zinc (Zn) or zinc-containing compounds (or alloys) for example, Zinc (Zn) -copper (Cu) couple, etc.
  • zinc (Zn) or a zinc-containing compound for example, zinc (Zn)
  • the proportion of the titanium compound is, for example, 1 to 20 mol (eg 5 to 10 mol), preferably 7 to 9 mol (usually 7.5 to 8 mol) per mol of the compound represented by the formula (10). About 5 mol).
  • the ratio of the reducing agent is, for example, 1 to 5 mol (for example, 1.8 to 3 mol), preferably 1.5 to 2.5 mol (usually 1.8 to 2. mol) with respect to 1 mol of the titanium compound. It may be about 2 mol).
  • the reaction may be performed in the presence of a solvent inert to the reaction.
  • the solvent is not particularly limited, and is a conventional organic solvent such as aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, etc.), Ethers (chain ethers such as diethyl ether and dimethoxyethane, cyclic ethers such as tetrahydrofuran and dioxane, etc.) may be used. These solvents can be used alone or in combination of two or more. Of these solvents, aromatic hydrocarbons such as toluene, ethers such as tetrahydrofuran, and mixed solvents thereof are often used.
  • the reaction may be performed in an inert gas atmosphere (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about 30 to 100 ° C., preferably about 40 to 80 ° C. (usually 50 to 70 ° C.).
  • the mixing of the compound represented by the formula (1), the titanium compound and the reducing agent (or the initial reaction) may be performed in a low temperature environment, for example, ⁇ 30 to 10 ° C., preferably ⁇ 20 to 0 ° C. It may be about (normally ⁇ 15 to ⁇ 5 ° C.).
  • the reaction time may be, for example, about 1 to 30 hours, preferably about 12 to 18 hours. After completion of the reaction, it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • R 1a , R 1b , R 2 , R 3 , R A and R B are compounds obtained by cyclization reaction May be introduced by subjecting to a conventional chemical reaction (modification reaction).
  • a modification reaction is not particularly limited, but typically includes, for example, a halogenation reaction, a cross-coupling reaction, an oxidation reaction, and a metal (or semimetal) -containing group introduction reaction.
  • Halogenation Reaction for example, a compound in which R 4a and R 4b in the formula (1B) are halogen atoms (compound represented by the following formula (1b)) may be prepared.
  • a compound produced by reacting a compound (a compound represented by the following formula (1a)) in which R 4a and R 4b prepared by the cyclization reaction are hydrogen atoms with a lithiating agent is produced. It can be prepared by reacting a compound with a halogenating agent.
  • X 3a and X 3b represent a halogen atom
  • Z, Z 1 , Z 2 , R 1a , R 1b , R 2 , R 2a , R 2b , R 3 , R 3a , R 3b , R 5a , R 5b , m, m 1, m 2, n, n 1, and n 2 are the same as described in the formula (1B) including preferred embodiments.
  • the conventional lithiating agents described in the above lithiation reaction can be used, and lithium amides such as lithium-2,2,6,6-tetramethylpiperidine (LiTMP) are usually used.
  • LiTMP lithium-2,2,6,6-tetramethylpiperidine
  • the ratio of the lithiating agent used may be, for example, about 2 to 5 mol, preferably about 2 to 3 mol, per 1 mol of the compound represented by the formula (1a).
  • the reaction with the lithiating agent may be performed in the presence of a solvent inert to the reaction.
  • a solvent inert examples include ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane) and the like, and tetrahydrofuran is usually used in many cases.
  • the reaction with the lithiating agent may be performed in an inert gas (nitrogen; rare gas such as helium or argon) atmosphere.
  • the reaction temperature may be, for example, about ⁇ 100 to ⁇ 50 ° C., preferably about ⁇ 80 to ⁇ 70 ° C.
  • the reaction time may be, for example, about 1 to 300 minutes, preferably about 60 to 180 minutes.
  • the reaction solution may be subjected to a reaction with a halogenating agent, if necessary, without purification by conventional separation and purification means.
  • examples of the halogen atom represented by X 3a and X 3b include chlorine, bromine, iodine and the like (particularly bromine).
  • the halogen atoms represented by X 3a and X 3b may be different from each other but are usually the same.
  • the halogenating agent is not particularly limited, and is a conventional halogenating agent such as halogen alone (chlorine (Cl 2 ), bromine (Br 2 ), iodine (I 2 ), etc.), halogenated hydrocarbon (eg, 1 , 2-dibromoethane, halogenated C 2-6 alkane such as 1,2-dibromo-1,1,2,2-tetrachloroethane, etc.).
  • the proportion of the halogenating agent used is, for example, about 2 to 5 mol, preferably about 2 to 3 mol, relative to 1 mol of the compound represented by the formula (1a) subjected to the reaction with the lithiating agent. Also good.
  • the reaction may be performed in the presence of a solvent inert to the reaction, and a solvent may be further added to the reaction solution of the lithiation reaction.
  • a solvent may include ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane) and the like, and tetrahydrofuran is usually used in many cases.
  • the reaction may be performed in an inert gas atmosphere (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about ⁇ 100 to 50 ° C., preferably about ⁇ 90 to 30 ° C. (usually ⁇ 78 ° C. to room temperature).
  • the reaction time may be, for example, about 1 to 48 hours, preferably about 12 to 24 hours.
  • it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • R 4a and R 4b in the formula (1B) are a hydrocarbon group or a compound having a heteroaryl group optionally having a hydrocarbon group (the following formula (1c ))) May be prepared.
  • Such a reaction is not particularly limited, but representative examples include Suzuki-Miyaura coupling, Negishi coupling, Kashiyama coupling, Kumada-Tamao coupling, Kosugi-Uita-Still coupling, and the like. It is done.
  • the compound represented by the formula (1c) is, for example, a compound (a compound represented by the following formula (1b)) in which R 4a and R 4b prepared by the halogenation reaction are halogen atoms. It can be prepared by reacting with a compound represented by the following formula (8).
  • R 7 is a hydrocarbon group or a heteroaryl group optionally having a hydrocarbon group
  • L 2 is a group —B (OH) 2 , group —ZnX 4 (wherein X 4 is a halogen atom)
  • a group —MgX 5 (wherein X 5 represents a halogen atom), a group —Sn (R 8 ) 3 (wherein R 8 represents an alkyl group), a group —Si (R 9 ) 3 (Wherein R 9 represents fluorine, chlorine or an alkyl group)
  • Z, Z 1 , Z 2 , R 1a , R 1b , R 2 , R 2a , R 2b , R 3 , R 3a , R 3b , R 5a , R 5b , m, m1, m2, n, n1 and n2 are the same as those described in the formula (1B) including preferred embodiments, and X 3a and X 3b include the preferred embodiments
  • the heteroaryl group optionally having a hydrocarbon group and a hydrocarbon group represented by R 7
  • the hydrocarbon group and hydrocarbon exemplified in the above R 4a and R 4b section It is the same including the heteroaryl group which may have a group, and a preferable aspect.
  • the compound represented by the formula (8) is not particularly limited.
  • a boronic acid compound, a zinc halide compound (such as zinc chloride) corresponding to the group R 7 introduced into the compound represented by the formula (1c) include reagents, trialkylstannyl compounds, and trialkylsilyl compounds. Of these, boronic acid compounds and zinc halide compounds are usually used.
  • the compound represented by the formula (8) is more specifically arylboronic acid (for example, C 6-14 arylboronic acid such as phenylboronic acid, C 1-20 alkylC such as 4-hexylphenylboronic acid, etc.
  • arylboronic acid for example, C 6-14 arylboronic acid such as phenylboronic acid, C 1-20 alkylC such as 4-hexylphenylboronic acid, etc.
  • 6-14 aryl boronic acids such as heteroaryl boronic acids (eg C 4-13 heteroaryl boronic acids such as 2-thienyl boronic acid); aryl zinc halides (eg phenyl zinc chloride etc.) C 1-20 alkyl C 6-14 aryl zinc halide such as C 6-14 aryl zinc halide, 4-decylphenyl zinc chloride), heteroaryl zinc halide (eg, C 4-13 hetero, such as 2-thienyl zinc chloride) Zinc halide compounds such as aryl zinc halides) Etc., and the like.
  • heteroaryl halides eg C 4-13 heteroaryl boronic acids
  • Etc. e.g C 4-13 heteroaryl boronic acids
  • boronic acid compounds such as heteroaryl boronic acids (eg C 4-13 heteroaryl boronic acids such as 2-thienyl boronic acid); aryl zinc halides (eg phenyl zinc chloride etc
  • the ratio of the compound represented by the formula (8) to be used is, for example, about 2 to 5 mol, preferably about 2.5 to 3.5 mol, with respect to 1 mol of the halide represented by the formula (1b). It may be.
  • the reaction may usually be performed in the presence of a catalyst.
  • the type of the catalyst can be selected according to the group L 2 , for example, palladium catalyst [palladium complex such as palladium (0) catalyst (for example, palladium acetate, tris (dibenzylideneacetone) dipalladium (0) chloroform complex)], Examples include transition metal complexes such as nickel catalysts (nickel complexes such as nickel (0) catalysts) and iron catalysts (iron complexes such as iron (III) catalysts). Of these catalysts, palladium catalysts and nickel catalysts (particularly palladium catalysts) are often used.
  • the amount of the catalyst used is, for example, 0.001 to 1 mol, preferably 0.01 to 0.5 mol (usually 0.02 to 0 mol) per mol of the halide represented by the formula (1b). About 2 mol).
  • a ligand capable of forming a complex by coordination with the catalyst may be added.
  • the ligand include phosphine-based ligands such as tri (t-butyl) phosphine, 1,3-bis (diphenylphosphino) propane (dppp), and 1,1′-bis (diphenylphosphino) ferrocene. Etc.
  • These ligands may be added as salts (for example, phosphonium salts with anions such as tetrafluoroborate).
  • the amount of the ligand used can be selected according to the type of the catalyst, and may be, for example, about 1 to 10 mol, preferably about 1.1 to 5 mol, with respect to 1 mol of the catalyst.
  • the reaction may be carried out in the presence or absence of a base.
  • the base include the bases exemplified in the section of the Wittig reaction.
  • the bases may be used alone or in combination of two or more. Of these bases, metal hydroxides such as sodium hydroxide are usually used in many cases.
  • the use ratio of the base may be, for example, about 1 to 10 mol, preferably about 3 to 5 mol, per 1 mol of the halide represented by the formula (1b).
  • the reaction may be performed in the presence of a solvent.
  • a solvent may include ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), water, and the like. Usually, tetrahydrofuran, water, and the like are often used.
  • the reaction may be performed in an atmosphere of an inert gas (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature can be selected according to the group L 2 and may be, for example, about 10 to 100 ° C., preferably about 20 to 70 ° C. (usually room temperature to 50 ° C.).
  • the reaction time may be, for example, about 1 to 24 hours, preferably about 3 to 20 hours.
  • it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • Oxidation reaction for example, a compound (compound represented by the following formula (1e)) in which R 3 , R 3a and R 3b in formula (1B) are oxygen atoms may be prepared.
  • the compound represented by the formula (1e) is obtained by, for example, reacting a compound in which n, n1 and n2 are 0 prepared by the cyclization reaction (a compound represented by the following formula (1d)) with an oxygenating agent.
  • r is 1 or 2
  • r1 and r2 represent integers of 0 to 2
  • Z, Z 1 , Z 2 , R 1a , R 1b , R 2 , R 2a , R 2b , R 4a , R 4b , R 5a , R 5b , m, m1 and m2 are the same as those described in the formula (1B) including preferred embodiments.
  • r, r1 and r2, Z can be selected according to the kind of Z 1 and Z 2 type and oxygenates, may be the same or different.
  • Z 1 and Z 2 are sulfur atoms
  • r 1 and r 2 are often 0 because Z on the seven-membered ring has higher electron density and is more easily oxidized.
  • oxygenating agent examples include organic peroxides [eg, alkyl peroxides such as hydroperoxides (eg, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide).
  • alkyl peroxides such as hydroperoxides (eg, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide).
  • Peroxides aralkyl hydroperoxides such as cumene hydroperoxide, arylhydroxy peroxides such as diisopropylbenzene hydroperoxide); dialkyl peroxides (eg, di-t-butyl peroxide, dicumyl peroxide, etc.); peroxycarboxylic acids (eg, performic acid, Peracetic acid, perpropionic acid, perbenzoic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, etc.); peroxy esters (eg, t-butylperoxybenzoate, t-butylperoxyacetate, etc.) Diacyl peroxides (eg, benzoyl peroxide (BPO), lauroyl peroxide, etc.); peroxycarbonates (eg, peroxymonocarbonates such as O, Ot-butyl-O-isopropylperoxycarbonate, diisopropylperoxydicarbonate, di
  • oxygenating agents can be used alone or in combination of two or more.
  • peroxycarboxylic acids such as m-chloroperbenzoic acid are often used.
  • the use ratio of the oxygenating agent may be, for example, about 1 to 5 mol, preferably about 1.3 to 3 mol, per 1 mol of the compound represented by the formula (1d).
  • the reaction may be performed in the presence of a solvent.
  • the solvent may be, for example, halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, etc.), and methylene chloride is usually used in many cases.
  • the reaction may be performed in an inert gas atmosphere (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about ⁇ 50 to 50 ° C., preferably about ⁇ 30 to 30 ° C. (usually ⁇ 20 ° C. to room temperature).
  • the reaction time may be, for example, about 30 to 300 minutes, preferably about 120 to 180 minutes.
  • it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • the metal (or metalloid) -containing group can be introduced by a conventional method, for example, the compound represented by the formula (1a) (or the formula (1a)).
  • a compound obtained by chemically modifying a compound) and a metal (or metalloid) -containing reagent corresponding to the type of the group may be introduced by a method of reacting.
  • the metal-containing group is a lithium atom
  • it can be prepared by a reaction between the compound represented by the formula (1a) described in the above-mentioned halogenation reaction and a lithiating agent as a metal-containing reagent. .
  • the metal-containing group is a trialkylstannyl group
  • the lithiated product of the compound represented by the formula (1a) described in the section of the halogenation reaction and a trialkyltin halide as a metal-containing reagent can be prepared by reaction.
  • the lithiated product may be subjected to a reaction with a trialkyltin halide without separating and purifying the reaction solution after the lithiation reaction.
  • trialkyl tin halide examples include tri C 1-6 alkyl tin halides such as trimethyl tin chloride, trimethyl tin bromide and n-butyl tin chloride, preferably tri C 1-4 alkyl tin halide. These trialkyltin halides can be used alone or in combination of two or more. Of these trialkyl tin halides, tri C 1-4 alkyl tin chlorides such as trimethyl tin chloride are often used.
  • the proportion of the trialkyltin halide used may be, for example, about 1 to 5 mol, preferably about 2 to 3 mol, per 1 mol of the compound represented by the formula (1a) before lithiation.
  • the reaction may be performed in the presence of a solvent.
  • a solvent may include ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane) and the like, and tetrahydrofuran is usually used in many cases.
  • the amount of the solvent is not particularly limited and may be, for example, a level that can homogenize the reaction system.
  • the reaction may be performed in an inert gas atmosphere (nitrogen; a rare gas such as helium or argon).
  • the reaction temperature may be, for example, about ⁇ 100 to ⁇ 50 ° C., preferably about ⁇ 80 to ⁇ 70 ° C.
  • the reaction time may be, for example, about 1 to 300 minutes, preferably about 60 to 180 minutes.
  • it may be purified by conventional separation and purification means such as washing, extraction, drying, filtration, concentration, recrystallization, column purification and the like, if necessary.
  • the organic semiconductor of this invention should just contain the compound represented by said Formula (A) at least, and may contain the conventional semiconductor material as needed.
  • semiconductor materials include acenes (eg, naphthacene, pentacene, hexacene, heptacene, etc.); phthalocyanines (eg, phthalocyanine (eg, copper phthalocyanine), naphthalocyanine, subphthalocyanine, etc.); carbazoles [eg, 1,3,5-tris [2,7- (N, N- (p-methoxyphenyl) amino) -9H-carbazol-9-yl] benzene (SGT405) and the like]; thiophenes [eg, 2,5- Bis [4- (N, N-bis (p-methoxyphenyl) amino) phenyl] -3,4-ethylenedioxythiophene (H101), 2,3,4,5-tetrakis [4
  • the ratio of the compound represented by the formula (A) is, for example, 10% by weight or more (for example, 30 to 100% by weight), preferably 50% by weight or more with respect to the entire semiconductor material. (For example, 70 to 99.9% by weight), more preferably about 80% by weight or more (for example, 90 to 99% by weight), and substantially 100% by weight (represented by the formula (A)). Only compound).
  • the organic semiconductor (organic semiconductor thin film or organic semiconductor layer) of the present invention may be formed by a dry process such as a vacuum deposition method, a sputtering method, a PVT (physical vapor transport) method (physical vapor transport method), or a wet process. You may form by (coating etc.).
  • the wet process includes a film forming step of applying a composition (or solution) containing the organic semiconductor and a solvent to at least one surface of a base material (or substrate) and removing the solvent.
  • the substrate is not particularly limited, and may be, for example, a glass plate, a silicon wafer, a plastic film (for example, a transparent resin film such as a polyethylene terephthalate film), or the like. If necessary, these base materials have one or more functional layers (for example, a conductive layer such as ITO, an insulating layer such as SiO 2 , a self-organization such as ⁇ -phenethyltrimethoxysilane ( ⁇ -PTS) on the surface.
  • a monomolecular film (SAM) or the like may be formed.
  • the solvent examples include aromatic hydrocarbons (eg, benzene, toluene, xylene, anisole, chlorobenzene, etc.); halogenated hydrocarbons (eg, halo C 1-6 such as dichloromethane, chloroform, 1,2-dichloroethane, etc.) Alcohols (eg, C 1-6 alkane monools such as methanol, ethanol, 2-propanol, n-butanol, t-butanol; C 2-4 alkane diols such as ethylene glycol); ethers (diethyl) Ethers, chain ethers such as diisopropyl ether, cyclic ethers such as tetrahydrofuran and dioxane, etc.); glycol ethers [for example, cellosolves (such as methyl cellosolve), carbitols (such as methylcarbitol), triethylene group Glycol monomethyl ether, and propylene
  • Carbonates chain carbonates such as dimethyl carbonate, cyclic carbonates such as ethylene carbonate and propylene carbonate); nitriles (acetonitrile, propionitrile, benzonitrile, etc.); amides (N, N- Dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.); sulfoxides (dimethylsulfoxide, etc.); and mixed solvents thereof. Of these solvents, they are usually aromatic hydrocarbons such as toluene and anisole.
  • the concentration (solid content concentration) of the composition (or solution) may be selected according to the coating method and the like, for example, 0.001 to 10% by weight (for example, about 0.005 to 5% by weight), preferably May be about 0.01 to 1% by weight (for example, 0.02 to 0.5% by weight), more preferably about 0.03 to 0.1% by weight.
  • the coating method is not particularly limited, and a conventional coating method such as an air knife coating method, a roll coating method, a gravure coating method, a blade coating method, a bar coating method, a die coating method, a dip coating method, a spray coating method, or a spin coating method.
  • a casting method, an edge casting method, a screen printing method, an ink jet printing method and the like can be employed. Of these coating methods, spin coating, edge casting, and ink jet printing are often used.
  • An organic semiconductor (layer) can be formed by removing the solvent by a conventional method such as natural drying or drying by heat treatment.
  • the temperature in the heat treatment may be, for example, about 30 to 100 ° C., preferably about 40 to 80 ° C. Moreover, you may dry under reduced pressure as needed.
  • the thickness of the organic semiconductor (layer) thus obtained may be, for example, about 1 to 5000 nm, preferably 30 to 1000 nm, more preferably about 50 to 500 nm, depending on the application.
  • the organic semiconductor of the present invention may be an n-type semiconductor, a p-type semiconductor, or an intrinsic semiconductor. Since the organic semiconductor of the present invention has high electron and / or hole mobility (carrier mobility or electrical mobility), it is a material for semiconductor devices such as electronic devices such as switching elements, rectifier elements, and transistors. Suitable as Such an organic thin film transistor includes a gate electrode layer, a gate insulating layer, a source / drain electrode layer, and an organic semiconductor layer. The organic thin film transistor can be classified into a top gate type and a bottom gate type (top contact type and bottom contact type) depending on the laminated structure of these layers.
  • an organic semiconductor film is formed on a gate electrode (such as a p-type silicon wafer on which an oxide film is formed), and a source / drain electrode (gold electrode) is formed on the organic semiconductor film, whereby a top contact type electric field is formed.
  • a carrier injection layer (dopant layer) may be formed between the source / drain electrode layer and the organic semiconductor layer.
  • TCNQs such as tetracyanoquinone dimethane (TCNQ), 2,3,5,6-tetrafluorotetracyanoquinone dimethane (F4TCNQ), and metals such as iron (III) chloride. It may be formed of a halide or fullerene.
  • the organic semiconductor of the present invention has high carrier mobility (photoelectric conversion rate) due to light absorption and has photoelectric conversion ability. Therefore, the organic semiconductor of this invention is suitable also as a material of a photoelectric conversion device or a photoelectric conversion element (a solar cell element, an organic electroluminescence (EL) element, etc.) and a rectifier element (diode).
  • a solar cell as a typical photoelectric conversion device has a structure in which a surface electrode is laminated on a pn junction type semiconductor, for example, an organic semiconductor layer is laminated on a p-type silicon semiconductor, and a transparent electrode (ITO electrode or the like) is formed on the organic semiconductor layer. ) May be laminated.
  • the organic EL element may have a structure in which a light emitting layer containing an organic semiconductor is formed on a transparent electrode (ITO electrode or the like), and an electrode (metal electrode or the like) is laminated on the light emitting layer. If necessary, an electron transport agent and a hole transport agent may be dispersed.
  • a field effect transistor was fabricated and mobility was evaluated. More specifically, a silicon (Si) substrate with a silicon dioxide (SiO 2 ) insulating film (film thickness 500 nm) was subjected to ultrasonic cleaning with acetone and 2-propanol for 3 minutes each and dried at 120 ° C. for 30 minutes. Subsequently, UV ozone treatment was performed for 30 minutes. A self-assembled monomolecular film (SAM) of perfluorodecyltrichlorosilane (F-DTS) was formed on the cleaned substrate surface by a vapor phase method.
  • SAM self-assembled monomolecular film
  • F-DTS perfluorodecyltrichlorosilane
  • a single crystal film was formed on the surface of the substrate by the PVT (physical vapor transport) method [PVT conditions: high temperature part 200 ° C., no low temperature part, argon flow amount 40 ccm, time 22 h] using the compound obtained in Example 1. Formed.
  • a metal mask is placed on the surface of the single crystal film, and tetrafluorotetracyanoquinodimethane (F4TCNQ) (film thickness of about 2 nm) is used as a carrier injection layer, and gold (film thickness of 70 nm) is used as a source electrode and a drain electrode by vacuum evaporation.
  • F4TCNQ tetrafluorotetracyanoquinodimethane
  • F4TCNQ tetrafluorotetracyanoquinodimethane
  • gold film thickness of 70 nm
  • the mobility was 0.08 cm 2 / Vs, and the threshold voltage Vth was ⁇ 47V.
  • the organic semiconductor of the present invention includes various electronic devices such as a rectifying element (diode), a switching element or a transistor (organic thin film transistor) [for example, a junction transistor (bipolar transistor), a field effect transistor (unipolar transistor), etc.] It can be effectively used as an organic semiconductor device such as a photoelectric conversion element (solar cell element, organic EL element, etc.).
  • a rectifying element diode
  • a switching element or a transistor organic thin film transistor
  • organic thin film transistor for example, a junction transistor (bipolar transistor), a field effect transistor (unipolar transistor), etc.
  • a photoelectric conversion element solar cell element, organic EL element, etc.

Landscapes

  • Thin Film Transistor (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Le semi-conducteur organique de l'invention contient un composé représenté par la formule (A). (Dans la formule, les cycles Ａ１ et Ａ２ sont identiques ou différents, et représentent des cycles possédant au moins une liaison insaturée carbone-carbone, Ｒ１ａ et Ｒ１ｂ sont identiques ou différents, et représentent un atome d'hydrogène ou un substituant, ＲＡ et ＲＢ sont identiques ou différents, et représentent un atome d'hydrogène, un substituant ou un atome choisi parmi les éléments du seizième groupe du tableau de classification périodique, p1 et p2 sont identiques ou différents, et représentent un nombre entier supérieur ou égal à 0, et la liaison représentée par la formule (2) représente une liaison simple ou une liaison double.) Ledit semi-conducteur organique présente une mobilité (ou mobilité de porteur de charge) élevée.
PCT/JP2018/008004 2017-03-31 2018-03-02 Semi-conducteur organique, et procédé de fabrication de celui-ci WO2018180194A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007063986A1 (fr) * 2005-12-02 2007-06-07 Toyo Ink Manufacturing Co., Ltd. Compose de diaminoarylene a groupe carbazolyle et ses utilisations
JP5322091B2 (ja) * 2008-01-30 2013-10-23 国立大学法人 和歌山大学 有機電界発光素子用重合体、有機電界発光素子および有機ｅｌディスプレイ
JP2017063155A (ja) * 2015-09-25 2017-03-30 富士フイルム株式会社 有機薄膜トランジスタ、有機薄膜トランジスタ用材料、有機薄膜トランジスタ用材料セット、有機薄膜トランジスタの製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003255857A (ja) * 2002-02-28 2003-09-10 Nippon Hoso Kyokai <Nhk> 有機ｅｌディスプレイ
JP5145544B2 (ja) * 2005-11-02 2013-02-20 和歌山県 ベンゾジチオフェン誘導体およびこのベンゾジチオフェン誘導体を発光層として用いた有機エレクトロルミネセンス素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007063986A1 (fr) * 2005-12-02 2007-06-07 Toyo Ink Manufacturing Co., Ltd. Compose de diaminoarylene a groupe carbazolyle et ses utilisations
JP5322091B2 (ja) * 2008-01-30 2013-10-23 国立大学法人 和歌山大学 有機電界発光素子用重合体、有機電界発光素子および有機ｅｌディスプレイ
JP2017063155A (ja) * 2015-09-25 2017-03-30 富士フイルム株式会社 有機薄膜トランジスタ、有機薄膜トランジスタ用材料、有機薄膜トランジスタ用材料セット、有機薄膜トランジスタの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BEDI, ANJAN ET AL.: "Synthesis of benzodithiophene and bithiazole based copolymer and its transistor property", EUROPEAN POLYMER JOURNAL, vol. 59, 24 July 2014 (2014-07-24), pages 19 - 24, XP055556425 *

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