WO2012111487A1 - Composé ayant des groupes accepteurs, et couche mince organique et élément de couche mince organique utilisant celui-ci - Google Patents

Composé ayant des groupes accepteurs, et couche mince organique et élément de couche mince organique utilisant celui-ci Download PDF

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WO2012111487A1
WO2012111487A1 PCT/JP2012/052768 JP2012052768W WO2012111487A1 WO 2012111487 A1 WO2012111487 A1 WO 2012111487A1 JP 2012052768 W JP2012052768 W JP 2012052768W WO 2012111487 A1 WO2012111487 A1 WO 2012111487A1
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thin film
compound
organic thin
organic
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家　裕隆
隆裕 櫻井
安蘇　芳雄
上田　将人
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住友化学株式会社
国立大学法人大阪大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30—Devices controlled by radiation
    • H10K39/32—Organic image sensors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • 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

Definitions

  • the present invention relates to a compound having an acceptor group, an organic thin film using the compound, and an organic thin film element.
  • Thin films containing organic materials that have electric charge are expected to be applied to photoelectric conversion elements (eg, organic thin film solar cells, photosensors), organic electroluminescence elements, and organic thin film transistors.
  • photoelectric conversion elements eg, organic thin film solar cells, photosensors
  • organic electroluminescence elements e.g., organic electroluminescence elements
  • organic thin film transistors e.g, organic thin film transistors
  • a structure composed of a combination of an organic p-type semiconductor and an organic n-type semiconductor has been proposed.
  • an organic p-type semiconductor poly [(2-methoxy-5- (2′-ethylhexyloxy) 1-4-phenylenevinylene], which is a polyphenylene vinylene derivative, and polyhexylthiophene, an electron-donating ⁇ -conjugated compound
  • an electron acceptor fullerene derivative see, for example, C 60 , Patent Document 1, and Non-Patent Document 1 as an organic n-type semiconductor.
  • organic n-type semiconductors do not necessarily have sufficient electron transport properties, and organic n-type semiconductors having higher electron transport properties are required.
  • the present invention comprises a core part which is a tetravalent or higher group derived from a cage compound or an aliphatic hydrocarbon compound, and four or more side chain groups bonded to the core part, and among the side chain groups It relates to a compound in which two or more have an acceptor group.
  • the compound according to the present invention Since the compound according to the present invention has an acceptor group contained in a side chain group, it can function as an organic semiconductor having the properties of an organic n-type semiconductor (electron acceptor property). And since the side chain group couple
  • the cage compound is adamantane or silsesquioxane, and the aliphatic hydrocarbon compound is methane.
  • the acceptor group is preferably a group containing a fullerene derivative residue, a group containing a naphthaleneimide derivative residue, or a group containing a peryleneimide derivative residue.
  • a compound having such a structure has good interaction between molecules, and the stability of the compound is particularly excellent. Therefore, more excellent electron transport properties are exhibited.
  • the present invention provides an organic thin film containing the compound according to the present invention, and an organic thin film element, an organic thin film transistor, an organic thin film solar cell, and an optical sensor including the organic thin film element.
  • the organic thin film element, the organic thin film transistor, the organic thin film solar cell, and the optical sensor according to the present invention are provided with the organic thin film containing the compound of the present invention exhibiting excellent electron transport properties as described above, and thus exhibit excellent performance. can do.
  • a novel compound that can be used as an organic semiconductor having excellent charge transportability is provided.
  • the organic thin film element provided with this organic thin film containing this compound and this organic thin film is provided. This organic thin film element can be excellent in stability.
  • the compound according to the present invention is excellent in stability and solubility in an organic solvent. Therefore, an organic thin film element having excellent performance can be easily produced by forming an organic thin film using a solution. can do.
  • the compound according to the present embodiment includes a core part which is a tetravalent or higher group derived from a cage compound or an aliphatic hydrocarbon compound, and four or more side chains bonded to the core part. It is composed of a group. Two or more of the four or more side chain groups have an acceptor group.
  • the compound having such a configuration is sometimes referred to as an “acceptor compound”.
  • the core part has 4 or more atoms to which a side chain group is bonded as a bonding site.
  • three atoms that bind to the binding site of the core are selected from the atoms that constitute the side chain group, they are placed outside (out of the plane) of the plane formed by these three atoms.
  • the core part forming such a configuration is preferably a vertex of a polygonal pyramid such as a triangular pyramid, a quadrangular pyramid and a pentagonal pyramid, a vertex of a polygonal column such as a triangular prism, a quadrangular prism and a pentagonal prism, or a regular tetrahedron , Having a binding site arranged at the apex of a regular polyhedron such as a regular octahedron, regular dodecahedron, and regular icosahedron.
  • the connecting part of the core is arranged at the apex of the structure in which the structure of the polygonal pyramid, polygonal column, or regular polyhedron is distorted, or at the apex of the structure in which part of the apex is missing from the structure of the polygonal pyramid, polygonal column, or regular polyhedron May be.
  • the tetravalent group as the core part may be a residue obtained by removing 4 or more hydrogen atoms from an aliphatic hydrocarbon compound.
  • This aliphatic hydrocarbon compound is preferably methane.
  • the tetravalent group as the core part may be a residue obtained by removing four or more hydrogen atoms or substituents from a cage compound.
  • the cage compound is preferably selected from cubane, adamantane, silsesquioxane and analogs thereof. Of these, silsesquioxane is particularly preferable.
  • the core part may be composed of a plurality of residues derived from the same or different cage compounds, and the plurality of residues may be bonded to each other.
  • adamantane and its analogs include adamantane (100), biadamantane (101), diamantane (102), triamantane (103), tetramantane (104) and isotetramantane (105) represented by the following structural formula. Illustrated. Of these, adamantane is preferred.
  • the cage silsesquioxane is generally obtained by partial hydrolysis / condensation of a trifunctional silane, and has the formula: (RSiO 3/2 ) n (R represents a hydrogen atom or a substituent, Is a polyhedral cluster having a structure represented by:
  • R represents a hydrogen atom or a substituent
  • Silsesquioxane which is not completely condensed can also be used.
  • the core part derived from silsesquioxane is a residue excluding 4 or more Rs.
  • the side chain group bonded to the core part is a group represented by the following formula (10).
  • L represents a single bond or a divalent organic group
  • T represents a hydrogen atom, a halogen atom or a monovalent organic group.
  • T is an acceptor group.
  • a plurality of L and T present in the same molecule may be the same or different from each other, but since the compound is easy to produce and the interaction between molecules is easy, the plurality of L and T are the same. It is preferable that
  • the acceptor group is selected from groups that function as an electron acceptor in combination with a donor group.
  • Acceptor groups include, for example, oxadiazole derivative residues, anthraquinodimethane derivative residues, benzoquinone derivative residues, naphthoquinone derivative residues, anthraquinone derivative residues, tetracyanoanthraquinodimethane derivative residues, fluorenone derivatives.
  • a group containing a fullerene derivative residue, a group containing a naphthaleneimide derivative residue, and a group containing a peryleneimide derivative residue are preferable.
  • the acceptor group is more preferably a group containing a fullerene derivative residue, a group containing a naphthaleneimide derivative residue, or a group containing a peryleneimide derivative residue.
  • a group containing a naphthaleneimide derivative residue is particularly preferred because it is easy to synthesize.
  • an acceptor group contains a fluorine atom.
  • the group containing a fullerene derivative residue is represented by the following structural formula, for example.
  • the group containing a peryleneimide derivative residue is represented by the following structural formula, for example.
  • a group containing a naphthaleneimide derivative residue is represented by the following structural formula, for example.
  • the group containing a terylene imide derivative residue is represented by the following structural formula, for example.
  • R 01 represents a monovalent organic group
  • R 02 represents a divalent organic group
  • R 03 represents a trivalent organic group
  • R 01 , R 02 and R 03 are in the same formula. They are the same or different.
  • A represents an alkyl group, an alkoxy group, a sulfonyl group, an amino group, an ammonio group, a hydroxy group, a nitro group or a halogen atom
  • e is an integer of 0 to 4
  • f is an integer of 0 to 12
  • g is 0 to 8 Indicates an integer.
  • Examples of the monovalent organic group represented by R 01 include linear, branched or cyclic alkyl groups, alkoxy groups, aryl groups, monovalent heterocyclic groups, amino groups, nitro groups, and cyano groups. Is done.
  • the alkyl group may have 1 to 20 carbon atoms
  • the alkoxy group may have 1 to 20 carbon atoms
  • the aryl group may have 6 to 60 carbon atoms.
  • the monovalent heterocyclic group is, for example, a heterocyclic compound selected from furan, thiophene, thienothiophene, benzothiophene, thiazole, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine.
  • the aryl group and monovalent heterocyclic group may have a substituent such as a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amino group, a cyano group, or a nitro group. Good.
  • Examples of the divalent organic group represented by R 02 include an alkylene group, vinylene group, oxy group (—O—), thio group (—S—), carbonyl group, thiocarbonyl group, sulfenyl group, sulfonyl group, And a mono-substituted amino group, and a residue having a ring structure in which two hydrogen atoms are removed from a cyclic compound such as benzene, a condensed ring compound, and a heterocyclic compound.
  • the alkylene group may have 1 to 20 carbon atoms.
  • the mono-substituted amino group is an amino group substituted with one substituent such as an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • substituent such as an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • an alkylene group and a residue obtained by removing two hydrogen atoms from benzene are particularly preferable.
  • the residue having a ring structure may have a substituent.
  • the substituent include a halogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group.
  • the saturated or unsaturated aliphatic hydrocarbon group may have 1 to 20 carbon atoms
  • the aryl group may have 6 to 60 carbon atoms
  • the alkoxy group has 1 to 2 carbon atoms. It may be 20, and the aryloxy group may have 7 to 80 carbon atoms.
  • the monovalent heterocyclic group is, for example, a heterocyclic compound selected from furan, thiophene, thienothiophene, benzothiophene, thiazole, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. Is a residue obtained by removing one hydrogen atom from
  • Examples of the trivalent organic group represented by R 03 include a residue having a ring structure in which three hydrogen atoms are removed from a cyclic compound such as benzene, a condensed ring compound, and a heterocyclic compound. Among these, a residue obtained by removing three hydrogen atoms from benzene is particularly preferable.
  • the residue having a ring structure may have a substituent. Examples of the substituent include a halogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group.
  • the saturated or unsaturated aliphatic hydrocarbon group may have 1 to 20 carbon atoms
  • the aryl group may have 6 to 60 carbon atoms
  • the alkoxy group has 1 to 2 carbon atoms. It may be 20, and the aryloxy group may have 7 to 80 carbon atoms.
  • the monovalent heterocyclic group is, for example, a heterocyclic compound selected from furan, thiophene, thienothiophene, benzothiophene, thiazole, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. Is a residue obtained by removing one hydrogen atom from
  • the acceptor compound according to the present embodiment has two or more side chain groups having an acceptor group. Since the electron transport property of the acceptor compound according to the present embodiment is further enhanced, the number of acceptor groups is preferably 4 or more, more preferably 6 or more. Moreover, since the electron transport property of the acceptor compound according to the present embodiment is further enhanced, it is particularly preferable that all of the side chain groups bonded to the core portion have an acceptor group.
  • the acceptor group is preferably arranged at the end of the side chain group.
  • the acceptor groups are preferably arranged as far apart as possible from each other in space. Therefore, it is preferable that two or more side chain groups having an acceptor group are bonded to a binding site having a symmetrical arrangement.
  • T in the side chain group having no acceptor group is preferably a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a substituted phenyl group.
  • substituent of the substituted phenyl group include a halogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group. It is done.
  • the saturated or unsaturated aliphatic hydrocarbon group may have 1 to 20 carbon atoms
  • the aryl group may have 6 to 60 carbon atoms
  • the alkoxy group has 1 to 2 carbon atoms. It may be 20, and the aryloxy group may have 7 to 80 carbon atoms.
  • the monovalent heterocyclic group is, for example, a heterocyclic compound selected from furan, thiophene, thienothiophene, benzothiophene, thiazole, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine.
  • L in the formula (10) is preferably a group represented by the following general formula (11).
  • Q is preferably an alkylene group
  • the alkylene group as Q is a divalent saturated hydrocarbon group represented by the formula: —C n H 2n — (where n is an integer of 1 or more).
  • the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
  • the alkylene group is selected from, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
  • a part or all of the hydrogen atoms of the alkylene group may be substituted with a halogen atom, and this halogen atom is preferably a fluorine atom.
  • the divalent aromatic hydrocarbon group as Q is a residue obtained by removing two hydrogen atoms from benzene or a condensed ring compound.
  • the aromatic hydrocarbon group usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms.
  • Examples of the condensed ring include a naphthalene ring, an anthracene ring, and a fluorene ring.
  • the divalent aromatic hydrocarbon group is preferably a residue obtained by removing two hydrogen atoms from benzene.
  • the divalent aromatic hydrocarbon group may have a substituent. The carbon number of the divalent aromatic hydrocarbon group does not include the carbon number of the substituent.
  • the substituent examples include a halogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group.
  • the saturated or unsaturated aliphatic hydrocarbon group may have 1 to 20 carbon atoms
  • the aryl group may have 6 to 60 carbon atoms
  • the alkoxy group has 1 to 2 carbon atoms. It may be 20, and the aryloxy group may have 7 to 80 carbon atoms.
  • the monovalent heterocyclic group is, for example, a heterocyclic compound selected from furan, thiophene, thienothiophene, benzothiophene, thiazole, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. Is a residue obtained by removing one hydrogen atom from furan, thiophene, thienothiophene, benzothiophene, thiazole, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. Is a residue obtained by removing one hydrogen atom from furan, thiophene, thienothiophene, benzothiophene, thiazole,
  • the divalent heterocyclic group as Q is a residue obtained by removing two hydrogen atoms from a heterocyclic compound, and the carbon number thereof is usually 3 to 60, preferably 3 to 20.
  • the heterocyclic compound is selected from, for example, thiophene, thienothiophene, dithienothiophene, pyrrole, pyridine, pyrimidine, pyrazine and triazine.
  • the divalent heterocyclic group is preferably a residue obtained by removing two hydrogen atoms from thiophene or thienothiophene.
  • the divalent heterocyclic group may have a substituent, and the carbon number of the divalent heterocyclic group does not include the carbon number of the substituent.
  • the substituent examples include a halogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group.
  • the saturated or unsaturated aliphatic hydrocarbon group may have 1 to 20 carbon atoms
  • the aryl group may have 6 to 60 carbon atoms
  • the alkoxy group has 1 to 2 carbon atoms. It may be 20, and the aryloxy group may have 7 to 80 carbon atoms.
  • the monovalent heterocyclic group is, for example, a heterocyclic compound selected from furan, thiophene, thienothiophene, benzothiophene, thiazole, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. Is a residue obtained by removing one hydrogen atom from furan, thiophene, thienothiophene, benzothiophene, thiazole, benzothiazole, benzothiadiazole, oxazole, pyrrole, imidazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. Is a residue obtained by removing one hydrogen atom from furan, thiophene, thienothiophene, benzothiophene, thiazole,
  • Suitable examples of the acceptor compound according to this embodiment are compounds represented by the following general formula (a), (b), (c), (d), (e), (f), or (g). is there.
  • L and T in the formulas (a), (b), (c), (d), (e), (f) and (g) are synonymous with L and T in the formula (10).
  • a plurality of L and T in the same molecule may be the same or different. Two or more of the plurality of T are acceptor groups.
  • the acceptor compound is particularly preferably a compound represented by the following formula (h), (i) or (j), since the charge transporting property is high and the stability is excellent.
  • X represents a single bond or — (Q) q —
  • Q and q have the same meanings as Q and q in the formula (11), and in the same molecule
  • a plurality of Q and q may be the same or different.
  • Ac represents an acceptor group, a hydrogen atom, or a phenyl group, and a plurality of Ac in the same molecule may be the same or different, and two or more of the plurality of Ac in the same molecule are acceptor groups.
  • the acceptor compound according to the present embodiment can be produced by the method of Scheme A or Scheme B described below.
  • the acceptor compound (54) is produced using the compound (50), the compound (51) and the compound (53) as monomers.
  • Q, Ac, and q are synonymous with Q, Ac, and q in formulas (h), (i), and (j).
  • Td represents a core part
  • h is the number of binding sites of the core part, and represents an integer of 4 or more.
  • V and W each independently represent an active functional group that reacts and binds to each other. When there are a plurality of V, they may be the same or different.
  • the acceptor compound (58) is produced using the compound (56) and the compound (55) as monomers.
  • the core part of the acceptor compound (58) is a tetravalent or higher group derived from silsesquioxane.
  • R ' represents a hydrogen atom or an alkyl group, and a plurality of R's may be the same or different.
  • the reaction for generating a chemical bond from the active functional group V and the active functional group W is, for example, a Suzuki coupling reaction, a Grignard reaction, a Stille reaction, or a dehalogenation reaction.
  • a Suzuki coupling reaction a Grignard reaction
  • a Stille reaction a reaction for generating a chemical bond from the active functional group V and the active functional group W
  • a dehalogenation reaction a reaction for a chemical bond from the active functional group V and the active functional group W.
  • the Suzuki coupling reaction and the Stille reaction are preferable because the raw materials are easily available and the reaction operation is simple.
  • the Suzuki coupling reaction uses, for example, palladium [tetrakis (triphenylphosphine)] or palladium acetate as a catalyst, an inorganic base such as potassium carbonate, sodium carbonate and barium hydroxide, an organic base such as triethylamine, or cesium fluoride.
  • the inorganic salt is used in an amount of not less than the equivalent, preferably 1 to 10 equivalents, based on the monomer.
  • the reaction may be performed in a two-phase system using an aqueous solution of an inorganic salt.
  • the solvent is selected from, for example, N, N-dimethylformamide (hereinafter referred to as “DMF”), toluene, dimethoxyethane, and tetrahydrofuran.
  • the reaction temperature is preferably 50 to 160 ° C. depending on the solvent used. The temperature may be raised to near the boiling point of the solvent and refluxed.
  • the reaction time is usually 1 to 200 hours.
  • the Suzuki coupling reaction is described, for example, in Chemical Review (Chem. Rev.), 95, 2457 (1995).
  • the Stille reaction is performed, for example, using palladium [tetrakis (triphenylphosphine)] or palladium acetate as a catalyst and using an organic tin compound as a monomer.
  • the solvent is selected from, for example, DMF, toluene, dimethoxyethane, and tetrahydrofuran.
  • the reaction temperature depends on the solvent used, but is preferably 50 to 160 ° C. The temperature may be raised to near the boiling point of the solvent and refluxed.
  • the reaction time is usually 1 to 200 hours.
  • V and W are, for example, halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, boric acid ester residues, sulfonium methyl groups, phosphonium methyl groups, phosphonate methyl groups, monohalogenated methyl groups, boric acid residues.
  • the combination of V and W is selected according to the reaction used.
  • boric acid ester residue examples include groups represented by the following formula (300), (301), (302) or (303).
  • the combination of V and W is preferably a combination of a halogen atom and a boric acid ester residue or a boric acid residue.
  • the combination of V and W is preferably a combination of a halogen atom and an alkylstannyl group.
  • the functional group in the monomer is protected by a protecting group as necessary.
  • This protecting group is selected according to the site to be protected and the reaction used.
  • Protective groups described in Protective Groupes in Organic Syntehesis, 3rd ed. T.W. GreeneandP.G. M .. Wuts, 1999 John Willey & Sons, Inc. are preferred.
  • a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, an aryldialkylsilyl group such as a biphenyldimethylsilyl group, a 2-hydroxypropyl group, etc.
  • a trimethylsilyl group is particularly preferred.
  • the monomer to be reacted is dissolved in an organic solvent as necessary. If necessary, the reaction can be carried out using an alkali or a suitable catalyst at a melting point or higher and a boiling point or lower of the organic solvent. It is preferable that the alkali or the catalyst is sufficiently soluble in the solvent used for the reaction.
  • the organic solvent varies depending on the compound used and the reaction, it is generally preferable that a sufficient deoxygenation treatment is performed in order to suppress side reactions.
  • the reaction is preferably allowed to proceed under an inert atmosphere.
  • this is not the case in the case of a reaction in a two-phase system of an aqueous layer and an organic layer such as a Suzuki coupling reaction.
  • Solvents used in the reaction are, for example, saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, Halogenated saturated hydrocarbons such as chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol And alcohols such as tert-butyl alcohol, carboxylic acids such as formic acid, ace
  • the acceptor compound according to this embodiment When the acceptor compound according to this embodiment is used as a material for an organic thin film element, the purity may affect the element characteristics. Therefore, it is preferable to purify the monomer before the reaction by a method such as distillation, sublimation purification, and recrystallization. After the synthesis of the acceptor compound, purification by a method such as sublimation purification, recrystallization, reprecipitation purification, or fractionation by chromatography is also preferred.
  • the product can be obtained by usual operations such as, for example, stopping the reaction with water and then extracting with an organic solvent and distilling off the solvent.
  • the isolation and purification of the product can be performed by a method such as fractionation by chromatography or recrystallization.
  • Organic Thin Film contains one or more acceptor compounds according to the preferred embodiments described above.
  • the thickness of the organic thin film is preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.
  • the organic thin film is different from the acceptor compound of the present invention in addition to the acceptor compound according to the present embodiment. It may contain a molecular compound (hereinafter referred to as “electron transporting material”), a low molecular compound having a hole transporting property or a high molecular compound (hereinafter referred to as “hole transporting material”).
  • electron transporting material a molecular compound having a hole transporting property
  • hole transporting material a high molecular compound
  • the hole transporting material can be selected from known materials.
  • pyrazoline derivatives arylamine derivatives, stilbene derivatives, triaryldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain
  • examples include polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyarylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.
  • the electron transporting material can also be selected from known materials. For example, oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, fullerenes and derivatives thereof such as C 60.
  • oxadiazole derivatives anthraquinodimethane and its derivatives
  • benzoquinone and its derivatives naphthoquinone and its derivatives
  • anthraquinone and its derivatives tetracyanoanthraquinodimethane and
  • the organic thin film may contain a charge generation material in order to generate a charge by light absorbed in the organic thin film.
  • the charge generation material can be selected from known materials. For example, azo compounds and derivatives thereof, diazo compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, polycyclic quinone compounds and derivatives thereof, squarylium compounds and derivatives thereof, azulenium compounds and their derivatives, thiapyrylium compounds and their derivatives, fullerenes and derivatives thereof such as C 60.
  • the organic thin film may contain other materials necessary for developing various functions.
  • Other materials include, for example, a sensitizer for sensitizing the function of generating charge by absorbed light, a stabilizer for increasing stability, and a UV absorber for absorbing ultraviolet (UV) light. Etc.
  • the organic thin film may contain a polymer material other than the acceptor compound according to the present embodiment as a polymer binder in order to enhance its mechanical properties.
  • a polymer binder those not extremely disturbing the charge transporting property are preferable, and those not strongly absorbing visible light are preferably used.
  • polymer binder examples include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, Examples include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.
  • the organic thin film according to the present embodiment includes, for example, a solution containing the acceptor compound according to the present embodiment, other materials such as an electron transport material, a hole transport material, and a polymer binder as necessary, and a solvent. Can be produced by a method of removing the solvent from the film-formed solution.
  • an organic thin film can be formed by a vacuum deposition method.
  • the solvent of the above solution only needs to dissolve the acceptor compound and other materials.
  • unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene and tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, Halogenated saturated hydrocarbon solvents such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, and tetrahydrofuran
  • ether solvents such as tetrahydropyran can be used.
  • film forming methods using a solution examples include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing.
  • Application methods such as flexographic printing, offset printing, ink jet printing, dispenser printing, nozzle coating, and capillary coating can be used. Of these, spin coating, flexographic printing, ink jet printing, dispenser printing, nozzle coating, and capillary coating are preferred.
  • the method for producing the organic thin film may include a step of orienting the acceptor compound. By this step, the main chain and / or the side chain are arranged along a certain direction, and the charge mobility of the organic thin film is further improved.
  • a method for aligning the acceptor compound a method known as a liquid crystal alignment method can be used.
  • the rubbing method, the photo-alignment method, the sharing method (shear stress application method) and the pulling coating method are simple, useful and easy to use as the alignment method.
  • the rubbing method and the sharing method are preferable.
  • the method for producing the organic thin film may include a step of annealing the thin film after removing the solvent. Annealing promotes the interaction between the acceptor compounds, improves the film quality of the organic thin film, and further improves the charge mobility.
  • the annealing temperature is preferably a temperature between 50 ° C. and the vicinity of the glass transition temperature (Tg) of the acceptor compound, and more preferably a temperature between (Tg ⁇ 30 ° C.) and Tg.
  • the annealing time is preferably 1 minute to 10 hours, and more preferably 10 minutes to 1 hour.
  • the atmosphere for annealing is preferably in a vacuum or an inert gas atmosphere.
  • the organic thin film of this embodiment has a charge transporting property, it can control various charges such as an organic thin film transistor, an organic thin film solar cell, and a photosensor by controlling the transport of a charge injected from an electrode or a charge generated by light absorption. It can be used for the organic thin film element.
  • an organic thin film is used for these organic thin film elements, it is more preferable to align the acceptor compound by an alignment treatment because high charge transport properties can be obtained.
  • Organic Thin Film Element The organic thin film according to the preferred embodiment described above has an excellent charge transport property because it includes the acceptor compound according to the present embodiment. Therefore, this organic thin film can efficiently transport charges injected from electrodes or the like, or charges generated by light absorption. Since the acceptor compound according to the present embodiment is excellent in environmental stability, it is possible to obtain an organic thin film element whose performance is stable even in normal air by forming a thin film using these compounds. Is possible.
  • preferred embodiments of various organic thin film elements will be described.
  • the organic thin film transistor includes a source electrode and a drain electrode, an active layer that functions as a current path between them, and a gate electrode that controls the amount of current passing through the current path.
  • Examples of the organic thin film transistor include a field effect type and an electrostatic induction type.
  • As the active layer an organic thin film containing the acceptor compound according to the above-described embodiment is used.
  • a field-effect organic thin film transistor includes a source electrode and a drain electrode, an active layer that is a current path provided between them, a gate electrode that controls the amount of current passing through the current path, and between the organic thin film and the gate electrode. It is preferable to provide an insulating layer. It is preferable that a source electrode and a drain electrode are provided in contact with the organic thin film, and a gate electrode is provided with an insulating layer in contact with the organic thin film interposed therebetween.
  • An electrostatic induction type organic thin film transistor includes a source electrode and a drain electrode, an active layer that is a current path provided therebetween, and a gate electrode that controls the amount of current passing through the current path, and the gate electrode is organic It is preferable to be provided in the thin film. It is preferable that the source electrode, the drain electrode, and the gate electrode are provided in contact with the active layer.
  • the gate electrode only needs to have a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode.
  • the gate electrode is, for example, a comb electrode.
  • FIG. 1 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a first embodiment.
  • An organic thin film transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1 with a predetermined interval, and a source electrode 5 and a drain electrode 6 so as to cover the substrate 1. Formed on the insulating layer 3 so as to cover the region of the insulating layer 3 between the source electrode 5 and the drain electrode 6, the insulating layer 3 formed on the active layer 2, and the insulating layer 3 formed between the source electrode 5 and the drain electrode 6.
  • FIG. 2 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a second embodiment.
  • An organic thin film transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the substrate 1 so as to cover the source electrode 5, a source electrode 5 and a predetermined electrode.
  • the drain electrode 6 formed on the active layer 2 with an interval of the insulating layer 3 formed on the active layer 2 and the drain electrode 6, and the insulating layer 3 between the source electrode 5 and the drain electrode 6.
  • a gate electrode 4 formed on the insulating layer 3 so as to cover the region.
  • FIG. 3 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a third embodiment.
  • the organic thin film transistor 120 shown in FIG. 3 includes a substrate 1, an active layer 2 formed on the substrate 1, a source electrode 5 and a drain electrode 6 formed on the active layer 2 at a predetermined interval, and a source electrode. 5 and the drain electrode 6 so as to partially cover the insulating layer 3 formed on the active layer 2, the region of the insulating layer 3 where the source electrode 5 is formed below, and the drain electrode 6 are formed below.
  • a gate electrode 4 formed on the insulating layer 3 so as to partially cover the region of the insulating layer 3.
  • FIG. 4 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fourth embodiment.
  • 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom.
  • an active layer 2 formed on the insulating layer 3 so as to cover it.
  • FIG. 5 is a schematic cross-sectional view of an organic thin film transistor (field effect type organic thin film transistor) according to a fifth embodiment.
  • An organic thin film transistor 140 shown in FIG. 5 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom.
  • a source electrode 5 formed on the insulating layer 3 so as to partially cover the region of the insulating layer 3 formed on the active layer 2 and an active layer 2 formed on the insulating layer 3 so as to partially cover the source electrode 5.
  • a source electrode 5 and a drain electrode 6 formed on the insulating layer 3 at a predetermined interval so as to partially cover a region of the active layer 2 formed below the gate electrode 4.
  • FIG. 6 is a schematic cross-sectional view of an organic thin film transistor (field effect type organic thin film transistor) according to a sixth embodiment.
  • An organic thin film transistor 150 shown in FIG. 6 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom.
  • the active layer 2 is formed on the insulating layer 3 so as to partially cover the region of the active layer 2 formed under the active layer 2 and the gate electrode 4 formed below.
  • a source electrode 5 and a drain electrode 6 formed on the insulating layer 3 at a predetermined interval so as to partially cover the region of the active layer 2 where the gate electrode 4 is formed below. .
  • FIG. 7 is a schematic cross-sectional view of an organic thin film transistor (electrostatic induction type organic thin film transistor) according to a seventh embodiment.
  • the organic thin film transistor 160 shown in FIG. 7 includes a substrate 1, a source electrode 5 formed on the substrate 1, an active layer 2 formed on the source electrode 5, and a plurality on the active layer 2 at a predetermined interval.
  • a drain electrode 6 formed on the active layer 2a.
  • the active layer 2 and / or the active layer 2a contains the acceptor compound according to the present embodiment, and a current path (channel) between the source electrode 5 and the drain electrode 6 is obtained. ).
  • the gate electrode 4 controls the amount of current passing through the current path (channel) in the active layer 2 and / or the active layer 2a by applying a voltage.
  • Such a field effect organic thin film transistor can be produced by a known method, for example, a method described in JP-A-5-110069.
  • the electrostatic induction organic thin film transistor can be produced by a known method, for example, a method described in JP-A-2004-006476.
  • the substrate 1 is selected so as not to disturb the characteristics as an organic thin film transistor.
  • a glass substrate, a flexible film substrate, or a plastic substrate can be used as the substrate 1.
  • the insulating layer 3 can be formed from a material selected from known insulating materials. For example, SiOx, SiNx, Ta 2 O 5, polyimide, polyvinyl alcohol, polyvinyl phenol, organic glass and photoresists. Since the voltage can be lowered, it is preferable to form the insulating layer 3 using a material having a high dielectric constant.
  • the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the active layer 2. It is also possible to form the active layer 2 after the modification.
  • a surface treatment agent such as a silane coupling agent
  • the surface treatment agent include silylamine compounds such as long-chain alkylchlorosilanes, long-chain alkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxysilanes, and hexamethyldisilazane.
  • the surface of the insulating layer can be treated with ozone UV or O 2 plasma.
  • an organic thin-film transistor is interrupted
  • Examples of the method for forming the protective film include a method of covering with a UV curable resin, a thermosetting resin, or an inorganic SiONx film.
  • a method of covering with a UV curable resin, a thermosetting resin, or an inorganic SiONx film In order to effectively cut off from the atmosphere, it is preferable to perform the steps from the preparation of the organic thin film transistor to the formation of the protective film without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).
  • An organic thin film transistor array can be formed by integrating a plurality of organic thin film transistors, and can also be used as a backplane of a flat panel display.
  • FIG. 8 is a schematic cross-sectional view of an organic thin-film solar cell according to a preferred embodiment.
  • An organic thin film solar cell 200 shown in FIG. 8 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the active layer 2 formed on the first electrode 7a, and the active layer 2.
  • the active layer 2 is an organic thin film containing the acceptor compound according to the present embodiment.
  • At least one of the first electrode 7a and the second electrode 7b is a transparent or translucent electrode.
  • a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used.
  • each electrode is preferably selected so that the difference in work function is large.
  • the active layer 2 may contain a charge generating agent, a sensitizer and the like in order to increase photosensitivity.
  • the substrate 1 a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.
  • the operation mechanism of the organic thin film solar cell will be described.
  • Light energy incident from a transparent or translucent electrode is absorbed by the acceptor compound and / or donor compound, and excitons in which electrons and holes are combined are generated.
  • excitons When the generated excitons move and reach the heterojunction interface where the acceptor compound and the donor compound are adjacent to each other, electrons and holes are separated due to the difference in HOMO and LUMO energy of each compound at the interface.
  • the generated electrons can be taken out as electrical energy (current) by moving to the cathode and the generated holes to the anode.
  • organic thin-film solar cells in order to obtain an organic thin film solar cell with high photoelectric conversion efficiency, an acceptor compound and / or a donor having an absorption region capable of efficiently absorbing a spectrum of desired incident light. It is important that organic thin-film solar cells contain many heterojunction interfaces in order to efficiently separate excitons, and that materials that have charge transportability to quickly transport generated charges to the electrode are important in order to efficiently separate excitons. is there.
  • an additional layer may be provided between at least one of the first electrode 7a and the second electrode 7b and the active layer 2 in the element.
  • the additional layer include a charge transport layer that transports charges, and a buffer layer that separates the electrode from the organic layer.
  • the organic layer having a buffer layer between the active layer 2 containing the acceptor compound and the donor compound and one or both of the pair of electrodes.
  • Thin film solar cells are preferred.
  • An organic thin film solar cell can be operated as a solar cell by generating a photovoltaic force between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode.
  • An organic thin film solar cell module can be constituted by integrating a plurality of organic thin film solar cells.
  • FIG. 9 is a schematic cross-sectional view of the photosensor according to the first embodiment.
  • An optical sensor 300 shown in FIG. 9 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the active layer 2 formed on the first electrode 7a, and the active layer 2.
  • the charge generation layer 8 and a second electrode 7b formed on the charge generation layer 8 are provided.
  • the active layer 2 is an organic thin film containing the acceptor compound according to the present embodiment.
  • FIG. 10 is a schematic cross-sectional view of an optical sensor according to the second embodiment.
  • An optical sensor 310 illustrated in FIG. 10 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the charge generation layer 8 formed on the first electrode 7a, and the charge generation layer 8.
  • the active layer 2 is an organic thin film containing the acceptor compound according to the present embodiment.
  • An optical sensor including an organic thin film according to the present embodiment can operate as an optical sensor by irradiating light from a transparent or translucent electrode with a voltage applied between the electrodes, thereby causing a photocurrent to flow.
  • An image sensor can be configured by integrating a plurality of optical sensors.
  • FIG. 11 is a schematic cross-sectional view of an optical sensor according to the third embodiment.
  • An optical sensor 320 shown in FIG. 11 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the active layer 2 formed on the first electrode 7a, and the active layer 2. And a second electrode 7b.
  • the active layer 2 is an organic thin film containing the acceptor compound according to the present embodiment.
  • one of the first electrode 7a and the second electrode 7b is a transparent or translucent electrode.
  • the charge generation layer 8 is a layer that absorbs light and generates charges.
  • an electrode material a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or a transparent conductive film thereof can be used.
  • the active layer 2 may contain a carrier generating agent, a sensitizer and the like in order to increase photosensitivity.
  • the substrate 1 a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.
  • the nuclear magnetic resonance (NMR) spectrum was measured using the product name JMN-270 (270 MHz at 1 H measurement) manufactured by JEOL (JEOL Ltd.) or the product name JMNLA-600 (150 MHz at 13 C measurement) manufactured by the same company. It was measured. Chemical shifts are expressed in parts per million (ppm). Tetramethylsilane (TMS) was used as an internal standard of 0 ppm. Coupling constants (J) are shown in hertz, and the abbreviations s, d, t, q, m and br are respectively singlet, doublet, triplet, four.
  • MS Mass spectrometry
  • the silica gel used in the column chromatography (GPC) separation was the product name Silicagel 60N (40-50 ⁇ m) manufactured by Kanto Chemical Co., Ltd.
  • the product name aluminum oxide 90standardized manufactured by Merck was used for alumina. Is a reagent grade and was purchased from Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., Kanto Chemical Co., Ltd., Nacalai Tesque Co., Ltd., or Sigma Aldrich Japan Co., Ltd.
  • Cyclic voltammetry (hereinafter referred to as “CV”) was measured using an apparatus manufactured by BAS, using a Pt electrode manufactured by BAS as a working electrode, a Pt line as a counter electrode, and an Ag line as a reference electrode. During this measurement, the sweep speed was 100 mV / second, and the scanning potential region was ⁇ 2.8 V to 1.6 V. The reduction potential and oxidation potential were measured by completely dissolving 1 ⁇ 10 ⁇ 3 mol / L of the compound to be measured and 0.1 mol / L of tetrabutylammonium hexafluorophosphate as a supporting electrolyte in methylene chloride. This was done using the solution.
  • the absorption spectrum of the solution was measured using a self-recording spectrophotometer (UV-3100PC: manufactured by Shimadzu Corporation) under the conditions of a quartz cell having a cell width of 1 cm and a slit width of 1 mm.
  • the fluorescence spectrum of the solution was measured using a fluorescence spectrophotometer (FluoroMax-2: manufactured by Horiba, Ltd.) and using a photomultiplier tube (R928: manufactured by Hamamatsu Photonics) as a detector.
  • the fluorescence spectrum was measured under the conditions that the solution was put in a quartz cell and the slit width was 1 mm and the integration time (1 nm / second).
  • Example 1 Synthesis of Compound B> Compound A used as a raw material was synthesized according to the method described in Toshifumi Dohi et al. J. Org. Chem. 2007, 72, 109.
  • Example 2 ⁇ Synthesis of Compound D> A test tube with a lid is charged with perylene-3,4,9,10-tetracarboxylic dianhydride (550 mg, 1.40 mmol), ethylhexylamine (435 mg, 3.37 mmol), and DMF (10 mL). Stir overnight at ° C. The obtained product was washed with hexane and then purified with a silica gel column (chloroform) to obtain a red solid compound D (542 mg, yield 63%). The analysis results and structural formula of Compound D are as follows. 1 H NMR (400 MHz, CDCl 3 ): ⁇ 0.91 (m), 1.41 (m), 4.13 (m), 8.45 (d, 4H), 8.57 (d, 4H)
  • Example 3 Synthesis of Compound H> Compound G used as a raw material was synthesized according to the method described in Yutaka Ie et al. Chem. Comm. 2009, 10, 1213.
  • Example 4 Synthesis of Compound L> Compound K used as a raw material was synthesized by the method described in Lyle D. Wescott and Daniell Lewis Mattern, J. Org. Chem. 2003, 68, 10058.
  • Example 5 Synthesis of Compound O> Compound N used as a raw material was synthesized according to the method described in Michael R. Wasielewski et al. J. Am. Chem. Soc. 2000, 122, 5563.
  • Example 6 Preparation of Organic Thin Film Element 1 and Evaluation of Transistor Characteristics> A substrate in which a 300 nm silicon oxide film was formed as an insulating film by thermal oxidation on the surface of a heavily doped p-type silicon substrate as a gate electrode was prepared. On this substrate, comb-shaped source and drain electrodes having a channel width of 38 mm and a channel length of 25 ⁇ m were formed by a lift-off method. The obtained substrate with electrodes was ultrasonically cleaned with acetone for 10 minutes and then with isopropyl alcohol for 10 minutes, and then irradiated with ozone UV for 30 minutes to clean the surface of the substrate.
  • Example 1 Compound C synthesized in Example 1 was dissolved in chloroform at a concentration of 1% by mass. Compound C was completely dissolved in chloroform, and thus it was confirmed that it could be dissolved in an organic solvent. This solution was applied onto the washed substrate by spin coating at a rotational speed of 1500 rpm for 1 minute and dried to form an organic thin film of Compound C. Thereafter, an annealing process was performed in nitrogen at 200 ° C. for 30 minutes to obtain an organic thin film element 1.
  • the gate voltage Vg and the source-drain voltage Vsd are varied in the range of 0 to 80 V in vacuum, and the organic thin film element 1 is organic
  • the gate voltage Vg and the source-drain voltage Vsd are varied in the range of 0 to 80 V in vacuum, and the organic thin film element 1 is organic
  • Mobility at this time was 1.2 ⁇ 10 -4 cm 2 / Vs
  • the threshold voltage is 59V
  • the on / off ratio was 10 5
  • the organic thin film element 1 functions effectively as an n-type organic transistor.
  • the compound C can be used as an organic n-type semiconductor having excellent electron transport properties.
  • Example 7 Preparation of organic thin film element 2 and evaluation of solar cell characteristics>
  • a regioregular poly-3-hexylthiophene as a donor compound and compound C as an acceptor compound are mixed in a 1: 1 ratio (mass ratio) and dissolved in a chloroform solvent to prepare a coating solution.
  • a glass substrate provided with an ITO film by sputtering is surface-treated with ozone UV, and then the coating solution is applied on the surface-treated substrate by spin coating to obtain an active layer of an organic thin-film solar cell. Thereafter, lithium fluoride is deposited on the active layer and then aluminum is deposited on the lithium fluoride layer by vacuum deposition to produce the organic thin film element 2.
  • the organic thin film element 2 operates as a solar cell when the characteristics of the organic thin film solar cell are measured under light irradiation by a solar simulator (AM1.5G filter, irradiance 100 mW / cm 2 ).
  • Example 8 Preparation of Organic Thin Film Element 3 and Evaluation of Transistor Characteristics>
  • compound P synthesized in Example 5 was added to chloroform at a concentration of 1% by mass, compound P was completely dissolved in chloroform, so that it could be confirmed that it could be dissolved in an organic solvent.
  • An organic thin film element 3 was produced in the same manner as in Example 6 except that the solution thus obtained was used instead of the chloroform solution of Compound C. Next, the organic transistor characteristics of the organic thin film element 3 were measured in the same manner as in Example 6. As a result, good Id-Vg characteristics of the n-type semiconductor were obtained.
  • the mobility was 1.1 ⁇ 10 ⁇ 4 cm 2 / Vs
  • the threshold voltage was 14 V
  • the on / off ratio was 10 7 , both of which were favorable. From this, it was confirmed that the organic thin film element 3 functions effectively as an n-type organic transistor. In addition, it was confirmed that the compound P can be used as an organic n-type semiconductor having excellent electron transport properties.

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Abstract

La présente invention concerne un composé comprenant : une partie formant cœur, laquelle est un groupe tétravalent ou supérieur dérivé d'un composé cage ou d'un composé hydrocarbure aliphatique ; et au moins quatre groupes à chaînes latérales liés à la partie formant cœur, au moins deux des groupes à chaînes latérales ayant un groupe accepteur.
PCT/JP2012/052768 2011-02-17 2012-02-07 Composé ayant des groupes accepteurs, et couche mince organique et élément de couche mince organique utilisant celui-ci WO2012111487A1 (fr)

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