WO2014157497A1 - Élément de conversion photoélectrique organique, cellule solaire à pellicule mince organique, composition utilisée dans ledit élément, pellicule de revêtement, composé utile pour ladite pellicule, et procédé de production du composé - Google Patents

Élément de conversion photoélectrique organique, cellule solaire à pellicule mince organique, composition utilisée dans ledit élément, pellicule de revêtement, composé utile pour ladite pellicule, et procédé de production du composé Download PDF

Info

Publication number
WO2014157497A1
WO2014157497A1 PCT/JP2014/058811 JP2014058811W WO2014157497A1 WO 2014157497 A1 WO2014157497 A1 WO 2014157497A1 JP 2014058811 W JP2014058811 W JP 2014058811W WO 2014157497 A1 WO2014157497 A1 WO 2014157497A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
atom
photoelectric conversion
formula
compound
Prior art date
Application number
PCT/JP2014/058811
Other languages
English (en)
Japanese (ja)
Inventor
寛記 杉浦
淳志 若宮
整 吉川
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2014157497A1 publication Critical patent/WO2014157497A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/15—Six-membered rings
    • C07D285/16—Thiadiazines; Hydrogenated thiadiazines
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/146—Side-chains containing halogens
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/414—Stille reactions
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • 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
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • 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
    • 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 photoelectric conversion device, an organic thin film solar cell, a composition used for the organic photoelectric conversion device, a coating film, a compound useful for the same, and a method for producing the compound.
  • the present invention relates to a compound useful as an organic semiconductor of an organic photoelectric conversion element, a compound useful for synthesizing the compound, and a method for producing the compound.
  • Organic semiconductor polymers have been actively researched in recent years in the electronics field. For example, it is used for an organic electroluminescence element that emits light when electricity is passed, an organic photoelectric conversion element that generates power by light irradiation, an organic thin film transistor element that controls the amount of current and voltage, and the like.
  • an organic semiconductor material in which a p-type conductivity / semiconductor material as an electron donating material and an n-type conductivity / semiconductor material as an electron-accepting material are combined is used as in the case of the inorganic semiconductor material.
  • fossil energy such as petroleum has a problem of releasing carbon dioxide into the atmosphere
  • demand for solar cells is increasing in order to protect the global environment by suppressing global warming.
  • Known organic solar cells include wet dye-sensitized solar cells (Gretzel cells) and all-solid organic thin-film solar cells. Since the latter does not use an electrolytic solution, there is no need to consider evaporation or leakage of the electrolytic solution. Moreover, it is possible to give flexibility, and the structure and manufacture of the solar cell become simpler than the former.
  • the photoelectric conversion efficiency of organic thin film solar cells is still insufficient. Since the photoelectric conversion efficiency is calculated by the short circuit current density (Jsc) ⁇ the open circuit voltage (Voc) ⁇ the fill factor (FF), it is necessary to improve each of them in order to increase the photoelectric conversion efficiency.
  • Jsc short circuit current density
  • Voc open circuit voltage
  • FF fill factor
  • the p having a deep HOMO level It is important to use type conductive / semiconductor materials. That is, in order to achieve both a high open-circuit voltage and a high short-circuit current density, development of a p-type conductive / semiconductor material having a deep HOMO level and a small band gap, that is, a deep LUMO level is required. In order to improve the fill factor, it is important to use a p-type conductive / semiconductor material having high carrier mobility, that is, strong association.
  • organic thin-film solar cells Compared to dye-sensitized solar cells that use the same organic materials, organic thin-film solar cells have the advantages described above and, despite their wide application range, the photoelectric conversion efficiency is higher than that of dye-sensitized solar cells. The reality is that it does not reach the battery.
  • the present inventors photoelectrically convert light in the near-infrared region by deepening the LUMO of the p-type semiconductor compound (decreasing the band gap) and lengthening the absorption edge. I thought it was important to be able to do it. Therefore, the present inventors have examined many conventionally proposed heteroaromatic rings including the Patent Documents 1 and 2 and their substituents. As a result, it has been found that the above can be achieved by carefully selecting the heteroaromatic ring and adjusting the substituent and the substitution mode strictly. Furthermore, it has also been found that a photoelectric conversion element using the compound of the present invention as a p-type semiconductor has little variation in current when formed into an element and is excellent in production suitability.
  • the present invention is excellent by developing a p-type organic semiconductor compound in which the absorption edge in the absorption spectrum has a longer wavelength (for example, near infrared region of 865 nm or more) in addition to deep LUMO level and band gap reduction. It is an object of the present invention to provide an organic photoelectric conversion device having high performance, an organic thin film solar cell, a composition used therefor, a coating film, a compound useful for this, and a method for producing the compound.
  • the object of the present invention has been achieved by the following means.
  • An organic photoelectric conversion element comprising a first electrode, a second electrode, and a photoelectric conversion layer disposed therebetween, wherein at least one layer of the photoelectric conversion layer is represented by the following formula (I)
  • Ar represents an arylene group, a heteroarylene group, or a group in which these are combined.
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may be bonded to each other to form a ring structure.
  • Y represents an electron withdrawing group having a Hammett's substituent constant ⁇ m of greater than 0.50.
  • n represents an integer of 2 to 2000.
  • D represents a group represented by the formula (D1), (D2) or (D3).
  • W 1 represents a sulfur atom, a selenium atom, an oxygen atom or —NR a —.
  • W 2 represents ⁇ C (L 2 —R 1D ) — or ⁇ N— , and R 1D represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or a halogen atom.
  • me represents an integer of 0-2.
  • md represents 0 or 1. However, when md is 0, me represents 1 or 2.
  • R a represents a hydrogen atom or a hydrocarbon group.
  • the rings A and C each independently represent a thiophene ring, and the ring B represents any of the rings represented by the above formulas (B-1) to (B-3).
  • L 1A to L 1C are each independently synonymous with L 2 above.
  • R 1A to R 1C are each independently synonymous with R 1D above.
  • mb represents an integer of 0 to 4, and ma and mc each independently represents 0 or 1.
  • Z b is —C (R 1Z ) (R 2Z ) —, —C [ ⁇ C (R 3Z ) (R 4Z )] —, —Si (R 1Z ) (R 2Z ) —, —Ge (R 1Z ) (R 2Z ) — or —N (R a ) — is represented.
  • R 1Z and R 2Z each independently represent an alkyl group, an alkenyl group, or an alkynyl group.
  • R 3Z and R 4Z each independently represents an alkyl group, an alkenyl group, an alkynyl group, an acyl group or an alkoxycarbonyl group.
  • R a represents a hydrogen atom or a hydrocarbon group.
  • W 1 and W 2 are each independently synonymous with W 1 and W 2 in formula (1).
  • the plurality of W 1 , W 2 and me in the above formulas (1), (D2) and (D3) may be the same or different.
  • Z a has the same meaning as Z b in the formula (B-1).
  • L 2 and R 1D are the formula (1) have the same meanings as L 2 and R 1D in (D2) and (D3).
  • L 1B and R 1B has the same meaning as L 1B and R 1B in Formula (D1).
  • X, Y and n have the same meanings as X, Y and n in the formula (I).
  • Z a has the same meaning as Z b in formula (B-1).
  • L 2 and R 1D are the formula (1) have the same meanings as L 2 and R 1D in (D2) and (D3).
  • (8) The organic photoelectric conversion device according to any one of (1) to (7), wherein Y is a cyano group or a nitro group.
  • Y is a cyano group.
  • X is a sulfur atom.
  • Ar represents an arylene group, a heteroarylene group, or a group in which these are combined.
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may be bonded to each other to form a ring structure.
  • Y represents an electron withdrawing group having a Hammett's substituent constant ⁇ m of greater than 0.50.
  • n represents an integer of 2 to 2000.
  • a composition comprising the compound according to (16) and an organic solvent.
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may be bonded to each other to form a ring structure.
  • Y 1 represents an electron-attracting group having a Hammett's substituent constant ⁇ m of greater than 0.50.
  • Z 1 and Z 2 each independently represents a halogen atom, a perfluoroalkanesulfonyloxy group, a trialkyltin group, a trialkylsilyl group or —B (OR ⁇ ) 2 .
  • R ⁇ represents a hydrogen atom, an alkylsulfonyl group, an alkyl group, or an aryl group. Two R ⁇ s may be bonded to each other to form a ring.
  • (21) The compound according to (20), wherein Z 1 and Z 2 are each independently a halogen atom or a perfluoroalkanesulfonyloxy group.
  • (22) The compound according to (20) or (21), wherein Y 1 is a cyano group.
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may combine with each other to form a ring.
  • Z 3 , Z 4 and Z 5 each independently represent a halogen atom or a perfluoroalkanesulfonyloxy group.
  • Z 5 is a chlorine atom, bromine atom, iodine atom or perfluoroalkanesulfonyloxy group
  • Z 3 and Z 4 are both chlorine atoms or
  • Z 5 is a bromine atom or an iodine atom
  • Z 3 and Z 4 are both bromine atoms
  • Z 5 is an iodine atom.
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may combine with each other to form a ring.
  • Z 6 , Z 7 and Z 8 each independently represent a halogen atom.
  • Z 8 is a fluorine atom
  • Z 6 and Z 7 are both a chlorine atom, a bromine atom or an iodine atom
  • Z 8 is a chlorine atom
  • Z 6 and Z 7 are both bromine atoms or iodine Is an atom.
  • Z 8 is a bromine atom
  • both Z 6 and Z 7 are iodine atoms.
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may combine with each other to form a ring.
  • Z 3 , Z 4 and Z 5 each independently represent a halogen atom or a perfluoroalkanesulfonyloxy group.
  • Z 5 is a chlorine atom, bromine atom, iodine atom or perfluoroalkanesulfonyloxy group
  • Z 3 and Z 4 are both chlorine atoms or
  • Z 5 is a bromine atom or an iodine atom
  • Z 3 and Z 4 are both bromine atoms
  • Z 5 is an iodine atom.
  • an aromatic ring is used to mean including an aromatic hydrocarbon ring and an aromatic heterocycle
  • an alicyclic ring is an aliphatic hydrocarbon ring, which is a non-aromatic aliphatic hydrocarbon ring
  • a heterocycle means a heterocycle including an aromatic group
  • a heterocycle that is not an aromatic heterocycle is referred to as a non-aromatic heterocycle.
  • Each of these rings may be monocyclic, polycyclic, or condensed.
  • a polycycle or a condensed ring it may be composed of the same ring or different rings as described above.
  • Each of these rings may have a substituent unless otherwise specified.
  • the same symbol is present in the group including the substituent and the partial structure in the same formula, that is, when there are a plurality of groups, these may be the same or different from each other. It is. Further, adjacent groups may be bonded to each other to form a ring. Further, when a double bond is present, it may be either E-form or Z-form, and includes a mixture thereof. Similarly, when an optical isomer is present, any of these may be used as a mixture thereof. Is also included.
  • the compound of the present invention having a deep LUMO level and a small band gap, that is, an absorption edge having a long wavelength (for example, a near-infrared region of 865 nm or more), an organic photoelectric that can photoelectrically convert light in the long wavelength region.
  • a conversion element, an organic thin-film solar cell, a composition used therefor, a coating film, a compound, and a method for producing the compound can be provided.
  • the organic photoelectric conversion element using the compound of the present invention has little variation in current value and is excellent in production suitability.
  • FIG. 1 is a side view schematically showing the configuration of a preferred embodiment of the organic thin film solar cell of the present invention.
  • the organic photoelectric conversion element of the present invention comprises a first electrode, a second electrode, and a photoelectric conversion layer disposed therebetween, and at least one layer of the photoelectric conversion layer is an excellent book as an organic semiconductor. Having the compounds of the invention. First, the compound of the present invention will be described.
  • the compound of the present invention is a compound represented by the following formula (I).
  • the following compounds of the present invention are dimer or higher compounds containing at least two repeating units described below, and include oligomers and polymers.
  • Ar represents an arylene group, a heteroarylene group, or a group in which these are combined.
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may be bonded to each other to form a ring structure.
  • Y represents an electron withdrawing group having a Hammett's substituent constant ⁇ m of greater than 0.50.
  • n represents an integer of 2 to 2000.
  • X (R 1) - R 1 , -C (R 2) (R 3) of the medium - the alkyl group in R 2 and R 3 in the middle is a linear or branched alkyl group
  • a C1- 24 alkyl groups are preferred, for example, methyl, ethyl, isopropyl, n-butyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-methylheptyl, 2- Ethylhexyl, n-nonyl, n-decyl, 3,7-dimethyloctyl, isodecyl, n-undecyl, n-dodecyl, 2-butyloctyl, n-tridecyl, 3-butylnonyl, n-tetradecyl, n-pentade
  • the alkenyl group preferably has 2 to 24 carbon atoms.
  • the alkynyl group preferably has 2 to 24 carbon atoms, and examples thereof include ethynyl, 2-propynyl, 2-penten-4-ynyl, 5-hexynyl, 7-octynyl and 2-nonyl-3-butynyl.
  • the aryl group preferably has 6 to 18 carbon atoms, and examples thereof include phenyl and naphthyl.
  • Each of these groups may be further substituted with a substituent.
  • substituents include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, and arylthio groups.
  • R 2 and R 3 may be bonded to each other to form a ring structure.
  • a ring is preferably a 5- or 6-membered ring, and may be a carbocyclic ring or a heterocyclic ring.
  • X is preferably a sulfur atom, an oxygen atom or a selenium atom, more preferably a sulfur atom or an oxygen atom, and particularly preferably a sulfur atom.
  • Y represents an electron withdrawing group having a Hammett's substituent constant ⁇ m of greater than 0.50.
  • an electron-withdrawing group having Hammett's substituent constant ⁇ m greater than 0.50 the energy level of the compound of the present invention is controlled in a more preferable region as an organic photoelectric conversion element, and the absorption edge is lengthened. Can be preferable.
  • the substituent constant ⁇ m value is described in Chemical Reviews, 1991, 91, p. Reference can be made to 165-195.
  • Examples of the electron withdrawing group having Hammett's substituent constant ⁇ m larger than 0.50 include nitro group (0.71), perfluoroalkylcarbonyl group (—COCF 3 : 0.63), alkyl or aryl sulfonyl group.
  • an alkyl or aryl sulfinyl group —SOCH 3 : 0.52
  • a sulfamoyl group [—SO 2 N (CH 3 ) 2 : 0.51].
  • a cyano group and a nitro group are preferable, and a cyano group is particularly preferable.
  • N represents an integer of 2 to 2000, preferably 10 to 2000.
  • Ar represents an arylene group, a heteroarylene group or a group in which these are combined, and the arylene group is preferably an arylene group having 6 to 18 carbon atoms, and examples thereof include phenylene and naphthylene.
  • examples of the hetero atom of the ring atom include a sulfur atom, an oxygen atom, a nitrogen atom, and a selenium atom.
  • the hetero atom constituting the aryl ring is preferably 1 to 4, and preferably 2 or 3 Is more preferable, and 1 is particularly preferable.
  • the aromatic ring of the heteroaryl ring is preferably a 5-membered ring or a 6-membered ring, and may be monocyclic or condensed.
  • heteroaryl ring thiophene ring, thiazole ring, selenophene ring, pyrrole ring, furan ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, oxazole ring, oxadiazole ring, thiadiazole ring, pyridine ring, pyrazine ring
  • Examples include a pyrimidine ring and a pyridazine ring.
  • the group in which an arylene group and heteroarylene group in Ar are combined includes an arylene group, a heteroarylene group, or a group in which an arylene group and a heteroarylene group are combined.
  • a combination of two or more of these groups, preferably a combination of 2 to 6 groups, can be represented as —Ar 1 (—Ar 2 ) 1 —.
  • Ar 1 and Ar 2 each independently represent an arylene group or a heteroarylene group, preferably an arylene group or a heteroarylene group in Ar, more preferably a heteroarylene group, and particularly preferably a five-membered heteroarylene group.
  • l represents an integer of 0 or more, preferably an integer of 0 to 4, more preferably 0, 2 or 4.
  • the plurality of Ar 2 may be the same or different.
  • Ar 2 is a divalent thiophene ring group (preferably 2,5-thiophenediyl) and Ar 1 does not contain a thiophene ring, A tri- or tetracyclic fused ring containing a thiophene ring is preferred.
  • Ar 2 is linked to a benzene ring condensed to a 5-membered ring having Y in formula (I) and including ⁇ N—X—N ⁇ .
  • the arylene group and heteroarylene group in Ar may have a substituent, and examples of the substituent include substituents that the groups R 1 to R 3 may have.
  • substituents include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, alkylamino groups, arylamino groups, acyl groups, alkoxy groups.
  • a carbonyl group, an acyloxy group and a halogen atom are preferred, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group and an alkylamino group are more preferred, and an alkyl group and an alkoxy group are particularly preferred.
  • Ar preferably has a calculated value of the energy level of Ar's highest occupied orbit (HOMO) of ⁇ 5.3 eV or more, more preferably ⁇ 5.3 to ⁇ 4.6 eV. preferable.
  • HOMO highest occupied orbital
  • the energy level of the highest occupied orbital (HOMO) of Ar is a ring including a substituent that substitutes for the ring, and molecular orbital calculation software Gaussian09 is used for a ring in which a bond is replaced with a hydrogen atom.
  • Ar is preferably a heteroarylene group, and the heterocyclic ring preferably contains at least a thiophene ring.
  • the heterocycle of the heteroaryl group is preferably a condensed ring (preferably a condensed ring of 3 to 4 rings) rather than a single ring, and among these, a condensed ring containing a thiophene ring is preferable, and a ring condensed with a thiophene ring
  • an aromatic ring (benzene ring, naphthalene ring), cyclopentadiene ring, or a ring in which a non-conjugated carbon atom of the cyclopentadiene ring is replaced with a nitrogen atom, Si atom, or Ge atom (pyrrole ring, silacyclopentadiene ring, Germacyclopentadiene ring) is preferred.
  • the condensed ring of 3 to 4 rings is preferably a ring in which both sides of the central ring, that is, a ring having a bond of a repeating unit is a thiophene ring.
  • Ar has Y in the formula (I) and a thiophene ring is connected to a portion connected to a benzene ring fused to a 5-membered ring containing ⁇ N—X—N ⁇ .
  • Ar is represented by the following formula (1).
  • D represents a group represented by the formula (D1), (D2) or (D3).
  • W 1 represents a sulfur atom, a selenium atom, an oxygen atom or —NR a —.
  • W 2 represents ⁇ C (L 2 —R 1D ) — or ⁇ N— , and R 1D represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or a halogen atom.
  • me represents an integer of 0-2.
  • md represents 0 or 1. However, when md is 0, me represents 1 or 2.
  • R a represents a hydrogen atom or a hydrocarbon group.
  • R a
  • the rings A and C each independently represent a thiophene ring
  • the ring B represents any of the rings represented by the above formulas (B-1) to (B-3).
  • L 1A to L 1C are each independently synonymous with L 2 above.
  • R 1A to R 1C are each independently synonymous with R 1D above.
  • mb represents an integer of 0 to 4, and ma and mc each independently represents 0 or 1.
  • Z b is —C (R 1Z ) (R 2Z ) —, —C [ ⁇ C (R 3Z ) (R 4Z )] —, —Si (R 1Z ) (R 2Z ) —, —Ge (R 1Z ) (R 2Z ) — or —N (R a ) — is represented.
  • R 1Z and R 2Z each independently represent an alkyl group, an alkenyl group, or an alkynyl group.
  • R 3Z and R 4Z each independently represents an alkyl group, an alkenyl group, an alkynyl group, an acyl group or an alkoxycarbonyl group.
  • R a represents a hydrogen atom or a hydrocarbon group.
  • W 1 and W 2 are each independently synonymous with W 1 and W 2 in formula (1).
  • the plurality of W 1 , W 2 and me in the above formulas (1), (D2) and (D3) may be the same or different.
  • the arylene group or heteroarylene group in L 1A to L 1C and L 2 includes a corresponding group in Ar, and is preferably thienylene, furylene, thiazolylene, oxazolylene, selenophenylene, pyrrolylene, imidazolylene, pyrazolylene, and thienylene, furylene, thiazolylene.
  • Oxazolylene is more preferable, and thienylene is particularly preferable.
  • L 1A to L 1C and L 2 are preferably a single bond, —O—, —S—, —N (R a ) —, more preferably a single bond, —O—, —S—, a single bond, —O -Is more preferable.
  • the hydrocarbon group for R a is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group.
  • the alkyl group, alkenyl group, alkynyl group, and aryl group are preferably the corresponding groups listed for R 1 to R 3 .
  • the cycloalkyl group is a 3- to 6-membered ring and preferably has 3 to 18 carbon atoms, and examples thereof include cyclopropyl, cyclopentyl, and cyclohexyl.
  • R a is preferably a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, and more preferably an alkyl group.
  • the alkyl group, alkenyl group, and alkynyl group in R 1A to R 1D are preferably the corresponding groups listed for R 1 to R 3 .
  • R 1A to R 1D are preferably a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 24 carbon atoms, and more preferably 6 to 24 carbon atoms.
  • ma and mc are preferably 0, and mb is preferably an integer of 0 to 2, more preferably an integer of 1 or 2.
  • W 1 is preferably a sulfur atom, a selenium atom, or an oxygen atom, and more preferably a sulfur atom.
  • W 2 is preferably ⁇ C (L 2 —R 1D ) —.
  • the alkyl group, alkenyl group and alkynyl group in R 1Z , R 2Z , R 3Z and R 4Z are preferably corresponding groups in R 1 to R 3 .
  • the acyl group in R 3Z and R 4Z is preferably an acyl group having 1 to 18 carbon atoms, more preferably an alkylcarbonyl group or an arylcarbonyl group, such as formyl, acetyl, propionyl, butanoyl, pentanoyl, pivaloyl, hexanoyl, heptanoyl, Octanoyl, 2-ethylhexanoyl, nonanoyl, decanoyl, 3,7-dimethyloctanoyl, undecanoyl, dodecanoyl, 2-butyloctanoyl, tridecanoyl, 2-hexyldecanoyl, 2-decyltetradecanoyl, my
  • the alkoxycarbonyl group in R 3Z and R 4Z is preferably an alkoxycarbonyl group having 2 to 18 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butyloxycarbonyl, s-butyloxycarbonyl, t-butyloxycarbonyl.
  • R 1Z , R 2Z , R 3Z and R 4Z are preferably alkyl groups, and the alkyl group preferably has 1 to 24 carbon atoms, and more preferably 6 to 24 carbon atoms.
  • Z b represents —C (R 1Z ) (R 2Z ) —, —Si (R 1Z ) (R 2Z ) —, —N (R a ) —, —C [ ⁇ C (R 3Z ) (R 4Z )] — Is preferred, and —C (R 1Z ) (R 2Z ) —, —Si (R 1Z ) (R 2Z ) —, and —C [ ⁇ C (R 3Z ) (R 4Z )] — are more preferred.
  • Ring B is preferably formula (B-1) or (B-3), more preferably formula (B-1).
  • D is preferably a group represented by the formula (D1).
  • Ar is more preferably a group represented by any of the following formulas (2) to (6).
  • Z a has the same meaning as Z b in the formula (B-1).
  • L 2 and R 1D are the formula (1) have the same meanings as L 2 and R 1D in (D2) and (D3).
  • L 1B and R 1B has the same meaning as L 1B and R 1B in Formula (D1).
  • the compound represented by the formula (I) is more preferably a compound represented by any one of the following formulas (II) to (VI).
  • X, Y and n have the same meanings as X, Y and n in the formula (I).
  • Z a has the same meaning as Z b in formula (B-1).
  • L 2 and R 1D are the formula (1) have the same meanings as L 2 and R 1D in (D2) and (D3).
  • the compound represented by the formula (I) of the present invention particularly the polymer, has a mass average molecular weight of preferably 10,000 or more, more preferably 10,000 to 1,000,000. In particular, by increasing the mass average molecular weight in this way, the photoelectric conversion efficiency is improved.
  • the mass average molecular weight is a value measured using a GPC (gel filtration chromatography) method unless otherwise specified, and the molecular weight is a polystyrene equivalent mass average molecular weight.
  • the gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. Two to six columns are preferably connected and used.
  • the solvent used examples include halogen solvents such as chloroform, aromatic solvents such as toluene, chlorobenzene, 1,2-dichlorobenzene and trichlorobenzene, ether solvents such as tetrahydrofuran, and amide solvents such as N-methylpyrrolidone.
  • An aromatic solvent is preferable from the viewpoint of solubility of the polymer.
  • the measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and more preferably in the range of 0.5 to 1.5 mL / min.
  • the measurement temperature is appropriately changed depending on the boiling point of the solvent, but it is preferably 10 to 200 ° C., more preferably 20 to 150 ° C.
  • the column and carrier to be used can be selected according to the physical properties of the polymer compound to be measured.
  • column TSK-GEL SUPER H-RC 6.0 * 150 + TSK-GEL BMHHR-H (20) 7.8 * 300 (two), solvent: 1,2-dichlorobenzene, temperature: 145 ° C.
  • Flow rate sample side: 1 mL / min, reference side: determined at 0.5 mL / min.
  • the polymer terminal is a hydrogen atom, a trialkyltin group (for example, trimethyltin group, tributyltin group, etc.), a halogen atom (fluorine, chlorine, bromine, iodine), Fluoroalkanesulfonyloxy group (for example, trifluoromethanesulfonyloxy group, nonafluorobutanesulfonyloxy group, etc.), -B (OH) 2 , -B (OR x ) 2 , trialkylsilyl group (for example, trimethylsilyl group, triethylsilyl group) Group), aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.), heteroaryl group (eg, thienyl group, 2-hexylthienyl group, 3-hexylthienyl group, thiazolyl group,
  • the polymer in the compound represented by the formula (I) of the present invention may be obtained by any polymerization form of block, random or alternating, but in the present invention, the same including a substituent and a skeleton. What consists of repetition of a unit structure is preferable, and what is specifically the repetition of n of this same unit structure is preferable.
  • the compound represented by the formula (I) of the present invention can be used in coupling reactions, for example, Chemical Reviews, 2002, 102, 1359, Chemical Reviews, 2011, 111, 1493, Journal of Materials of Chemistry, Using the method described in 2004, 14th volume, 11th page etc., it can synthesize
  • Negishi coupling using transition metal catalyst zinc reactive agent, right-Kosugi-Still coupling using tin reactant, Suzuki-Miyaura coupling using boron reactant, magnesium reactant It can be synthesized using Kumada-Tamao-Coriu coupling, cross coupling such as Ulsan coupling using a silicon reagent, Ullmann reaction using copper, Yamamoto polymerization using nickel, and the like. In the present invention, it is more preferable to use the Ueda-Kosugi-Still coupling and the Suzuki-Miyaura coupling.
  • the transition metal catalyst metals such as palladium, nickel, copper, cobalt, and iron (Journal of the American Chemical Society, 2007, Vol.
  • the metal may have a ligand, such as PPh 3 , P (t-Bu) 3 , P (o-tol) 3 , P (2-furyl) 3 , S-Phos, X-Phos, etc.
  • a phosphorus ligand, an N-heterocyclic carbene ligand (Angewandte Chemie International Edition, 2002, 41, 1290) and the like are preferably used.
  • the reaction may be performed under microwave irradiation as described in Macromolecular Rapid Communications, 2007, 28, 387.
  • Z 1 and Z 2 are a halogen atom and a perfluoroalkanesulfonyloxy group
  • Z a and Z b are a trialkyltin group, a trialkylsilyl group, or —B (OR ⁇ ) 2
  • Z 1 and Z 2 When 2 is a trialkyltin group, a trialkylsilyl group or —B (OR ⁇ ) 2
  • Z a and Z b are a halogen atom or a perfluoroalkanesulfonyloxy group.
  • capping may be performed by adding a compound represented by Ar—V 1 after polymerization and reacting with a polymer terminal.
  • Ar represents an aryl group (for example, phenyl group, naphthyl group, tolyl group, etc.) or a heteroaryl group (for example, thienyl group, thiazolyl group, furyl group, pyridyl group, etc.).
  • Ar may have a substituent such as an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, or a halogen atom.
  • V 1 is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), perfluoroalkanesulfonyloxy group (eg, trifluoromethanesulfonyloxy group, nonafluorobutanesulfonyloxy group), trialkyltin A group (for example, trimethylstannyl group, tributylstannyl group, etc.), a trialkylsilyl group (for example, trimethylsilyl group, triethylsilyl group, etc.), and —B (OR x ) 2 .
  • R x represents a hydrogen atom or an alkyl group.
  • R x may be linked to form a ring.
  • the metal reactants such as tin reactant and boron reactant as raw materials
  • they can be synthesized according to various known methods.
  • the tin reactant is Journal of the American Chemistry, 2009, 131, 7792, the Journal of the American Chemistry, 2008, 130, 16144, the European Patent Application Publication No. 2407465
  • the boron reactant is J It can be synthesized with reference to American Chemistry, 2012, 134, 539 pages.
  • the compound represented by the formula (IV) of the present invention is, for example, Chemistry of Materials, 2010, vol. 22, p. 2325-2332 and Journal of Polymer Science, Part A: Polymer Chemistry, 2013, vol. 51, p. It can be synthesized by synthesizing monomers as described below with reference to 424 to 434 and polymerizing them.
  • the compound represented by the formula (V) of the present invention is, for example, Tetrahedron Letters, 2010, vol. 51, # 16, p. 2089-2091, Advanced. Materials, 2011, 23, p.
  • the monomers can be synthesized by referring to the synthesis of 1409 to 1413 and polymerizing them.
  • the compound represented by the formula (VI) of the present invention is, for example, Journal of American Chemical Society, 2012, 134, p.
  • the monomer can be synthesized by referring to the method described in 3498-3507 and polymerized.
  • the compound of the present invention is a compound represented by the following formula (M1).
  • the compound of the present invention is useful and preferred as a synthesis raw material for synthesizing the compound represented by the formula (I) of the present invention.
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may be bonded to each other to form a ring structure.
  • Y 1 represents an electron-attracting group having a Hammett's substituent constant ⁇ m of greater than 0.50.
  • Z 1 and Z 2 each independently represents a halogen atom, a perfluoroalkanesulfonyloxy group, a trialkyltin group, a trialkylsilyl group or —B (OR ⁇ ) 2 .
  • R ⁇ represents a hydrogen atom, an alkylsulfonyl group, an alkyl group, or an aryl group. Two R ⁇ s may be bonded to each other to form a ring.
  • the compound represented by the formula (M1) is a monomer, and the groups and symbols other than Z 1 and Z 2 are the same as those in the formula (I), and the preferred range is also The same.
  • the alkylsulfonyl group for R ⁇ in Z 1 and Z 2 is preferably a perfluoroalkanesulfonyl group, and particularly preferably a trifluoromethanesulfonyl group.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably 6 to 10 carbon atoms.
  • Y 1 represents an electron-attracting group having a Hammett's substituent constant ⁇ m of greater than 0.50.
  • Y 1 has the same meaning as the electron-withdrawing group having a Hammett substituent constant ⁇ m of Y in the general formula (I) larger than 0.50, and the preferred range is also the same.
  • M1 represents a metal cation
  • Me represents methyl
  • Et represents ethyl
  • i-Pr isopropyl
  • the synthesis method of these compounds is not particularly limited, and can be synthesized according to various known methods.
  • Z 1 and Z 2 are a halogen atom or a perfluoroalkanesulfonyloxy group and Y 1 is a nitro group
  • the compound (M4) is represented by the following reaction formula, for example, Organic Letters, 2011, 13, p. It can be synthesized by nitration with reference to the method described in 2338 to 2341.
  • a compound of an atom or a perfluoroalkaneoxy group (M1) can be synthesized.
  • Z 3 , Z 4 , and Z 5 each independently represent a halogen atom or a perfluoroalkanesulfonyloxy group.
  • Z 5 is a chlorine atom, bromine atom, iodine atom, or perfluoroalkanesulfonyloxy group
  • Z 3 and Z 4 are both chlorine atoms
  • Z 5 is a bromine atom or an iodine atom
  • Z 3 and Z 4 are both bromine atoms
  • Z 5 is an iodine atom.
  • Y 1 is a cyano group and Z 1 and Z 2 are halogen atoms among the compounds represented by the formula (M1)
  • a method for synthesizing the formula (M2 ′) is not particularly limited. For example, Journal of the American Chemical Society, 2012, 134, p. It can be synthesized with reference to the method described in 14932-14944.
  • (M1) can be synthesized by cyanating the formula (M2 ′) by an aromatic nucleophilic substitution reaction (see, for example, the method described in Journal of Medicinal Chemistry, 2007, 50, p. 566-584). .
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may combine with each other to form a ring.
  • Z 6 , Z 7 and Z 8 each independently represent a halogen atom.
  • Z 8 is a fluorine atom
  • Z 6, Z 7 is chlorine atom, a bromine atom, an iodine atom
  • Z 8 is a chlorine atom
  • Z 6, Z 7 is a bromine atom, an iodine atom
  • Z 8 and Z 7 are iodine atoms.
  • Z 8 is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.
  • Z 6 and Z 7 are preferably a bromine atom or an iodine atom.
  • Z 1 and Z 2 are a trialkyltin group or —B (OR ⁇ ) 2
  • the halogen atom of Z 1 and Z 2 or the perfluoroalkanesulfonyloxy group of the compound (M1) described above is added according to a known method.
  • Alkyl tin groups see, eg, Journal of the American Chemical Society, 1990, 112, p. 8024-8034
  • —B (OR ⁇ ) 2 see, eg, Organic Letters, 2012, 14, p. 600-603.
  • the second compound of the present invention is a compound represented by the following formula (M2).
  • the second compound of the present invention is useful and preferred as a synthesis raw material for the compound represented by the formula (M1) of the present invention.
  • X represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, —N (R 1 ) — or —C (R 2 ) (R 3 ) —.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.
  • R 2 and R 3 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.
  • R 2 and R 3 may combine with each other to form a ring.
  • Z 3 , Z 4 and Z 5 each independently represent a halogen atom or a perfluoroalkanesulfonyloxy group.
  • Z 5 is a chlorine atom, bromine atom, iodine atom or perfluoroalkanesulfonyloxy group
  • Z 3 and Z 4 are both chlorine atoms or per atoms.
  • Z 5 is a bromine atom or an iodine atom
  • Z 5 is an iodine atom.
  • X, R 1 , R 2 and R 3 have the same meanings as X, R 1 , R 2 and R 3 of the compound represented by the formula (I), and preferred ranges thereof are also the same. .
  • Z 3 and Z 4 are preferably a fluorine atom, a chlorine atom, a perfluoroalkanesulfonyloxy group or a bromine atom, more preferably a chlorine atom, a perfluoroalkanesulfonyloxy group or a bromine atom, and particularly preferably a bromine atom.
  • Z 5 is a chlorine atom, bromine atom, iodine atom, or perfluoroalkanesulfonyloxy group, and Z 3 and Z 4 are both chlorine atoms or perfluoroalkanesulfonyl.
  • Z 5 is a bromine atom or an iodine atom
  • Z 3 and Z 4 are both bromine atoms
  • Z 5 is an iodine atom
  • Z 5 is a bromine atom or an iodine atom. Is preferable, and an iodine atom is more preferable.
  • the composition of the present invention contains at least the compound represented by the formula (I) and an organic solvent.
  • the composition of the present invention may be used for any purpose and purpose, but is preferably used as a composition for organic semiconductors.
  • the organic solvent contained in the composition is not particularly limited, but ether solvents such as tetrahydrofuran, 1,4-dioxane, cyclopentylmethyl ether, benzene, toluene, ethylbenzene, xylene, mesitylene, anisole, thioanisole, pyridine, picoline, lutidine
  • Aromatic solvents such as chloroform, dichloromethane, 1,2-dichloroethane, halogen solvents such as 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, bromobenzene, Aromatic halogen solvents such as i
  • Tetrahydrofuran, toluene, chloroform, dichloromethane, chlorobenzene, o-dichloro Robenzen and 1,3,5-trichlorobenzene are mentioned.
  • Tetrahydrofuran, toluene, chloroform, dichloromethane, chlorobenzene, o-dichloro Robenzen and 1,3,5-trichlorobenzene are preferred.
  • These solvents may be used alone or as a mixed solvent of two or more.
  • an additive of 0% by mass to 10% by mass may be added to the solvent.
  • additives include diiodoalkanes (for example, 1,8-diiodooctane, 1,6-diiodohexane, 1,10-diiododecane, etc.), alkanedithiols (for example, 1,8-octanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.) and 1-chloronaphthalene.
  • diiodoalkanes for example, 1,8-diiodoctane, 1,6-diiodohexane, 1,10-diiododecane, etc.
  • alkanedithiols for example, 1,8-octanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.
  • 1-chloronaphthalene 1-chloronaphthalene
  • composition of the present invention is formed by dissolving or dispersing the compound represented by the formula (I) of the present invention in the above organic solvent, and is particularly useful as a p-type organic semiconductor polymer among organic semiconductor polymers.
  • the composition of the present invention may contain the compound represented by the above formula (I) alone, but a p-type organic semiconductor compound other than the compound represented by the above formula (I), for example, poly-3 -Hexylthiophene (P3HT), poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene (MEH-PPV), poly [2-methoxy-5- (3 ', 7' -Dimethyloctyloxy) -1,4-phenylenevinylene] (MDMO-PPV), poly [(9,9-di-n-octylfluorenyl-2,7-diyl) -alt- (benzo [2,1 , 3] thiadiazole-4,
  • the compound or polymer to be used in combination is an n-type semiconductor (n-type semiconductor compound).
  • n-type semiconductor compound those described later are preferable.
  • Use of an n-type semiconductor (n-type semiconductor compound) in combination is preferable for forming a photoelectric conversion layer of an organic photoelectric conversion element.
  • the content of the compound represented by the formula (I) of the present invention is not particularly limited, but is preferably 0.01 to 90% by mass when the total mass of the composition is 100, preferably 0.1 to 70%. It is more preferable to make it contain by mass%.
  • the n-type organic semiconductor (n-type organic semiconductor compound) should be contained in an amount of 0.01 to 90% by mass when the total mass of the composition is 100.
  • the content is preferably 0.1 to 70% by mass.
  • Any p-type organic semiconductor compound other than the compound represented by the formula (I) of the present invention is preferably contained in an amount of 0 to 50% by mass, and more preferably 0 to 30% by mass.
  • a compound other than a semiconductor may be contained in an amount of about 0 to 50% by mass, depending on the component.
  • the content contained in the composition is 100% by mass in total although each component is within the above range.
  • composition of the present invention is not particularly limited, and may be a fluid liquid or a paste.
  • the composition of the present invention is preferably used for forming a coating film, and particularly used as a coating film for an organic semiconductor material, particularly a photoelectric conversion layer of an organic photoelectric conversion element.
  • a coating film it is preferable to apply the composition of the present invention by a spin coating method, a casting method, a spray method, a bar coating method, an ink jet method or the like.
  • the thickness of the coating film is preferably 0.01 to 1 ⁇ m, more preferably 0.05 to 0.3 ⁇ m.
  • FIG. 1 is a side view schematically showing an example of the organic photoelectric conversion device of the present invention and an organic thin film solar cell using the organic photoelectric conversion device (hereinafter, referred to as an organic thin film solar cell or a solar cell as a representative).
  • the solar cell 10 of the present embodiment includes a photoelectric conversion layer (bulk hetero-coupling layer) 3 containing the compound represented by the formula (I).
  • Organic thin-film solar cells are generally classified into pn bilayer junction or pin three-layer junction type organic thin film solar cells and bulk heterojunction type organic thin film solar cells, and any of them may be used in the present invention. Absent. Since high power generation efficiency can be easily obtained, it is particularly preferably applied to a bulk heterojunction organic thin film solar cell as shown in FIG.
  • the photoelectric conversion layer 3 is composed of a p-type semiconductor phase that is an electron donating compound and is an n-type semiconductor phase that is an electron-accepting compound. is doing.
  • the photoelectric conversion layer 3 is provided between the first electrode 11 and the second electrode 12.
  • the hole transport layer 21 is preferably provided between the first electrode and the photoelectric conversion layer
  • the electron transport layer 22 is preferably provided between the second electrode and the photoelectric conversion layer.
  • the distinction between the upper and lower sides is not particularly important, but if necessary for convenience, the first electrode 11 side is positioned as the “up” or “top” side, and the second electrode 12 side is defined as “ Position it as “bottom” or “bottom”.
  • the configuration of the substrate, the positive electrode, the hole transport layer, the photoelectric conversion layer, the electron transport layer, and the negative electrode is referred to as the forward configuration
  • the substrate, the negative electrode, the electron transport layer, the photoelectric conversion layer, and the hole transport in order from the upper layer.
  • the configuration of the layer and the positive electrode is referred to as a reverse configuration, and in the present invention, both the forward configuration and the reverse configuration are preferably applied.
  • the p-type semiconductor phase and the n-type semiconductor phase are mixed in a specific form as described above, and photoelectric conversion (charge separation) is performed at the interface.
  • the form is not particularly limited, but as an ideal example, a state in which the phases are interdigitated in the order of nanometers as illustrated is preferable.
  • the p-type semiconductor polymer preferably has a specific compatibility or incompatibility with the n-type semiconductor polymer.
  • the material that becomes the p-type semiconductor is not determined only by the specific physical properties, but is specified by the relative relationship with the material that becomes the n-type semiconductor. For example, when a typical fullerene is taken as an example of an n-type semiconductor material, a material having a higher electron donating property can be a p-type semiconductor material.
  • n-type organic semiconductor (n-type organic semiconductor compound) is not particularly limited, but is generally a ⁇ -electron conjugated system whose lowest orbital (LUMO) level is ⁇ 3.5 to ⁇ 4.5 eV.
  • LUMO lowest orbital
  • Perfluoro compounds in which hydrogen atoms of p-type organic semiconductor compounds are substituted with fluorine atoms for example, perfluoropentacene or perfluorophthalocyanine
  • naphthalenetetracarboxylic anhydride etc.
  • aromatic compounds such as naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, and polymer compounds containing the imidized product thereof as a skeleton.
  • fullerene or its compounds can be efficiently and rapidly separated from the compound represented by the formula (I) of the present invention, particularly an organic semiconductor (p-type organic semiconductor compound) which is a polymer.
  • organic semiconductor p-type organic semiconductor compound
  • fullerenes and derivatives thereof C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene, C 84 fullerene, C 240 fullerene, C 540 fullerene, mixed fullerene, fullerene nanotube, and some of them are hydrogen atoms.
  • Fullerene derivatives substituted by halogen atoms substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, amino groups, silyl groups, etc. Can be mentioned.
  • Preferred fullerene derivatives are phenyl-C 61 -butyric acid ester, diphenyl-C 62 -bis (butyric acid ester), phenyl-C 71 -butyric acid ester, phenyl-C 85 -butyric acid ester or thienyl-C 61 -butyric acid ester,
  • the preferred number of carbon atoms in the alcohol portion of the butyric acid ester is 1-30, more preferably 1-8, even more preferably 1-4, and most preferably 1.
  • Examples of preferred fullerene derivatives include phenyl-C 61 -butyric acid methyl ester ([60] PCBM), phenyl-C 61 -butyric acid n-butyl ester ([60] PCBnB), phenyl-C 61 -butyric acid isobutyl ester ([60 PCBiB), phenyl-C 61 -butyric acid n-hexyl ester ([60] PCBH), phenyl-C 61 -butyric acid n-octyl ester ([60] PCBO), diphenyl-C 62 -bis (butyric acid methyl ester) ( Bis [60] PCBM), phenyl-C 71 -butyric acid methyl ester ([70] PCBM), phenyl-C 85 -butyric acid methyl ester ([84] PCBM), thienyl-C 61 -butyric acid methyl ester (
  • P-type organic semiconductor compound In the present invention, the compound represented by the formula (I) is used, but other p-type semiconductor compounds (for example, condensed polycyclic aromatic low molecular weight compounds, oligomers or polymers) may be contained.
  • p-type semiconductor compounds for example, condensed polycyclic aromatic low molecular weight compounds, oligomers or polymers
  • Examples of the condensed polycyclic aromatic low-molecular compound that is a p-type semiconductor compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumcam Compounds such as anthracene, bisanthene, zeslen, heptazesulene, pyranthrene, violanthene, isoviolanthene, sacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bis Examples thereof include ethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, and derivative
  • the composition for an organic semiconductor material is preferably used as a coating composition for a photoelectric conversion layer (particularly a bulk hetero layer).
  • the mixing ratio of the p-type organic semiconductor compound that is an electron-donating material and the n-type semiconductor compound that is an electron-accepting material is preferably adjusted so as to increase the photoelectric conversion efficiency. It is selected from the range of ⁇ 90: 10, preferably 20:80 to 80:20.
  • a co-evaporation method is used.
  • a coating method is preferable in order to increase the area of the interface where holes and electrons are separated by charge and to have high photoelectric conversion efficiency.
  • the method for the purpose of promoting the phase separation of the electron donating region (donor) and the electron accepting region (acceptor) in the photoelectric conversion layer, crystallization of the organic material contained in the photoelectric conversion layer, and transparency of the electron transport layer, etc.
  • You may heat-process (anneal) by the method.
  • a dry film formation method such as vapor deposition
  • the substrate temperature during film formation is heated to 30 ° C. to 150 ° C.
  • a wet film forming method such as printing or coating
  • there is a method of setting the drying temperature after coating to 30 ° C. to 250 ° C. Further, it may be heated to 30 ° C. to 250 ° C.
  • the formation of the metal negative electrode is completed.
  • a charge transport path may be formed, and the photoelectric conversion efficiency may be improved.
  • a plurality of photoelectric conversion layers may be provided, but one photoelectric conversion layer is preferable.
  • the photoelectric conversion element according to the present invention has at least a first electrode and a second electrode.
  • One of the first electrode and the second electrode is a positive electrode, and the rest is a negative electrode.
  • the tandem configuration can be achieved by using an intermediate electrode.
  • an electrode through which holes mainly flow is referred to as a positive electrode
  • an electrode through which electrons mainly flow is referred to as a negative electrode.
  • an electrode having translucency is referred to as a transparent electrode
  • an electrode having no translucency is referred to as a counter electrode or a metal electrode.
  • the positive electrode is a translucent transparent electrode
  • the negative electrode is a non-translucent counter electrode or metal electrode.
  • the negative electrode is a translucent transparent electrode
  • the positive electrode is a non-translucent counter electrode or metal electrode.
  • Both the first electrode and the second electrode can be transparent electrodes.
  • the first electrode is a positive electrode. In the case of a solar cell having a forward configuration, it is preferably a transparent electrode that transmits light from visible light to near infrared light (380 to 800 nm).
  • the material include transparent conductive metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), indium tungsten oxide (IWO), tin oxide, zinc oxide, and indium oxide, magnesium, aluminum, calcium, Ultrathin films of metal and metal alloys such as titanium, chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, and bismuth, metal nanowires, and carbon nanotubes can be used.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • IWO indium tungsten oxide
  • tin oxide zinc oxide
  • magnesium aluminum, calcium
  • Ultrathin films of metal and metal alloys such as titanium, chromium, manganese, iron, copper, zinc, strontium
  • a mesh electrode in which a metal such as silver is meshed to ensure light transmission.
  • a conductive material selected from the group consisting of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene.
  • a functional polymer can also be used.
  • a plurality of these conductive compounds can be combined to form a positive electrode.
  • the transmittance of the positive electrode is the thickness used for solar cells (for example, 0.2 ⁇ m thickness), and the average light transmittance in the wavelength region of 380 nm to 800 nm is 75% or more. It is preferably some 85% or more.
  • metals such as chromium, cobalt, nickel, copper, molybdenum, palladium, silver, tantalum, tungsten, platinum, and gold, alloys thereof, transparent conductive oxide, polyaniline
  • the positive electrode can be formed of a conductive polymer such as polythiophene or polypyrrole.
  • Suitable conductive polymer layers are disclosed in JP 2012-43835 A, polythiophene derivatives are preferable, and polyethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) is more preferable.
  • PEDOT-PSS polyethylenedioxythiophene-polystyrene sulfonic acid
  • These metals, transparent conductive oxides, and conductive polymers may be used alone, or two or more kinds may be mixed or laminated.
  • the second electrode is a negative electrode.
  • the negative electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination.
  • a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material is used.
  • Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of these metals and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the negative electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the second electrode is a transparent electrode.
  • a transparent electrode that transmits light from visible light to near infrared light (380 to 800 nm) is preferable, and examples thereof include metals, metal oxides, conductive polymers, mixtures thereof, and laminated structures.
  • tin oxide zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), transparent conductive oxides such as indium tungsten oxide (IWO), magnesium, aluminum, calcium, titanium
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • IWO transparent conductive oxides
  • IWO indium tungsten oxide
  • ultrathin films of metals and metal alloys such as chromium, manganese, iron, copper, zinc, strontium, silver, indium, tin, barium, and bismuth
  • conductive polymers such as polyaniline, polythiophene, and polypyrrole.
  • the transparent conductive oxide is ITO, IZO, tin oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), zinc oxide, antimony-doped zinc oxide (AZO), and gallium-doped oxide.
  • Zinc (GZO) can be used.
  • the transmittance of the negative electrode is the thickness used for solar cells (eg, 0.2 ⁇ m thickness), and the average light transmittance in the wavelength region of 380 nm to 800 nm is 75% or more. It is preferably some 85% or more.
  • the metal electrode may be a metal (eg, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure.
  • a dispersion is preferable because a transparent and highly conductive negative electrode can be formed by a coating method.
  • the metal electrode side is made light transmissive, for example, a conductive material suitable for the negative electrode such as aluminum and aluminum alloy, silver and silver compound is formed in a thin film thickness of about 1 to 20 nm, and then the positive electrode is formed.
  • a light-transmitting negative electrode can be obtained by providing the conductive light-transmitting material film mentioned in the description.
  • hole transport layer In the present invention, it is preferable to provide a hole transport layer between the first electrode and the photoelectric conversion layer.
  • the conductive polymer that forms the hole transport layer include polythiophene, polypyrrole, polyaniline, polyphenylene vinylene, polyphenylene, polyacetylene, polyquinoxaline, polyoxadiazole, polybenzothiadiazole, and polymers having a plurality of these conductive skeletons. Can be mentioned. Among these, polythiophene and its derivatives are preferable, and polyethylenedioxythiophene and polythienothiophene are particularly preferable. These polythiophenes are usually partially oxidized in order to obtain conductivity.
  • the electrical conductivity of the conductive polymer can be adjusted by the degree of partial oxidation (doping amount). The larger the doping amount, the higher the electrical conductivity.
  • polythiophene becomes cationic by partial oxidation, a counter anion for neutralizing the charge is required.
  • polythiophenes include polyethylene dioxythiophene (PEDOT-PSS) with polystyrene sulfonic acid as a counter ion and polyethylene dioxythiophene (PEDOT-TsO) with p-toluenesulfonic acid as a counter anion.
  • an electron transport layer is preferably provided between the second electrode and the photoelectric conversion layer, a hole transport layer is provided between the first electrode and the photoelectric conversion layer, and the photoelectric conversion layer and the second It is particularly preferable to provide an electron transport layer between the electrodes.
  • the electron transport material that can be used for the electron transport layer include an n-type semiconductor compound, which is the electron accepting material mentioned in the photoelectric conversion layer, and Electron in Chemical Review, Vol. 107, pages 953 to 1010 (2007). -Listed as Transporting and Hole-Blocking Materials.
  • alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride are preferable.
  • Various metal oxides are preferably used as materials for electron transport layers having high stability.
  • relatively stable aluminum oxide, titanium oxide, and zinc oxide are more preferable.
  • the film thickness of the electron transport layer is 0.1 to 500 nm, preferably 0.5 to 300 nm.
  • the electron transport layer can be suitably formed by any of a wet film formation method by coating or the like, a dry film formation method by PVD method such as vapor deposition or sputtering, a transfer method, or a printing method.
  • holes generated in the photoelectric conversion layer do not flow to the negative electrode side in the electron transport layer having a HOMO level deeper than the HOMO level of the p-type semiconductor compound used in the photoelectric conversion layer.
  • a hole blocking function having a rectifying effect is provided.
  • a material deeper than the HOMO level of the n-type semiconductor compound is used as the electron transport layer.
  • Such an electron transport layer is also referred to as a hole block layer, and it is preferable to use an electron transport layer having such a function.
  • Such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor compounds such as naphthalene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, perylene tetracarboxylic acid diimide, and titanium oxide.
  • n-type semiconductor compounds such as naphthalene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, perylene tetracarboxylic acid diimide, and titanium oxide.
  • N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.
  • the support constituting the photovoltaic cell includes at least a first electrode (positive electrode), a photoelectric conversion layer, a second electrode (metal negative electrode), and in a more preferred embodiment, a first electrode (positive electrode), a hole. It is not particularly limited as long as it can form and hold a transport layer, a photoelectric conversion layer, an electron transport layer, and a second electrode (metal negative electrode). For example, glass, plastic film, etc. You can choose.
  • a conventional layer may be applied to provide an easy adhesion layer / undercoat layer, functional layer, recombination layer, other semiconductor layer, protective layer, gas barrier layer, UV absorption layer, antireflection layer, etc. Good.
  • the compound represented by the formula (I) is used in other devices and systems.
  • field effect transistors eg, photodetectors (eg, infrared photodetectors), photovoltaic detectors, imaging devices (eg, RGB imaging devices for cameras or medical imaging systems), light emitting diodes (LEDs) (eg, Organic LEDs, or infrared or near-infrared LEDs), laser elements, conversion layers (eg, layers that convert visible emission into infrared emission), amplifiers and radiators for telecommunications (eg, fiber dopants),
  • LEDs light emitting diodes
  • conversion layers eg, layers that convert visible emission into infrared emission
  • amplifiers and radiators for telecommunications eg, fiber dopants
  • These compounds or polymers can be used in suitable organic semiconductor elements such as storage elements (eg holographic storage elements) as well as electrochromic elements (eg electrochromic displays).
  • PEDOT-PSS (CLEVIOSP VP.AI4083 made by Heraeus Precision Material) used as a hole transport layer on a glass-ITO substrate that has been cleaned and UV-ozone-treated. Heated at 140 ° C. for 30 minutes. A mixture of 4 mg of polymer P1 and 6 mg of PC 71 BM ([6,6] -phenyl-C 71 -butyric acid methyl ester) was dissolved in 1 mL of chlorobenzene containing 3% by mass of 1.8-diiodooctane.
  • This solution was applied onto the PEDOT-PSS layer by spin coating (400 rpm) and dried to prepare a photoelectric conversion layer.
  • LiF (1 nm) and aluminum (100 nm) were sequentially deposited on the photoelectric conversion layer to form an upper electrode, thereby obtaining an organic photoelectric conversion element.
  • the synthesis was performed in the same manner as in the synthesis of the polymer P1 of Example 1 except that the compound (1-3) was changed to the compound (3-1) to obtain 141 mg (yield 78.8%) of the polymer P3.
  • a polymer P5 was obtained in the same manner as in the synthesis of the polymer P4 of Example 4 except that the compound (2-1) was changed to the compound (5-1).
  • a polymer P6 was obtained in the same manner as in the synthesis of the polymer P4 of Example 4 except that the compound (2-1) was changed to the compound (6-1).
  • a polymer P7 was obtained in the same manner as in the synthesis of the polymer P4 of Example 4 except that the compound (2-1) was changed to the compound (7-1).
  • Example 8 [Creation of organic photoelectric conversion element using polymer P8] (1) Synthesis of Polymer P8 Monomer 8-3 was synthesized as follows.
  • PEDOT-PSS organic photoelectric conversion element
  • a hole transport layer is spin-coated (5000 rpm) on a glass-ITO substrate that has been cleaned and UV-ozone treated, and 200 Heated at 0 ° C. for 10 minutes.
  • a mixture of 10.0 mg of polymer P8 and 10.0 mg of PC 71 BM ([6,6] -phenyl-C 71 -butyric acid methyl ester) was dissolved in 1 mL of chlorobenzene. This solution was applied onto the PEDOT-PSS layer by spin coating (1000 rpm) and dried to prepare a photoelectric conversion layer.
  • Comparative Example 1 [Creation of organic photoelectric conversion element using F-PCPDTBT] As a comparative example of Examples 1 to 8, the following polymer F-PCPDTBT was used. In Example 8, the polymer P8 was changed to F-PCPDTBT, and 9.0 mg of polymer F-PCPDTBT and 27.0 mg of PC 71 BM ([6,6] -phenyl-C 71 -butyric acid methyl ester) were used. An organic photoelectric conversion device was obtained in the same manner except that 3% by mass of 1,8-diiodooctane-containing chlorobenzene was used as the solvent.
  • Example 8 As a comparative example of Examples 1 to 8, the following polymer CF 3 -PCPDTBT was used ( ⁇ m value of CF 3 group 0.43).
  • Example 8 by changing the polymer P8 to CF 3 -PCPDTBT, polymers of 9.0mg CF 3 -PCPDTBT and 18.0mg of PC 71 BM (the [6,6] - butyric acid methyl ester - phenyl -C 71)
  • PC 71 BM the [6,6] - butyric acid methyl ester - phenyl -C 71
  • An organic photoelectric conversion device was obtained in the same manner except that 3% by mass of 1,8-diiodooctane-containing chlorobenzene was used.
  • Comparative Example 3 [Creation of organic photoelectric conversion element using Z3] As a comparative example of Examples 9 and 10, the following polymer Z3 was used. In Example 9, the organic photoelectric conversion element was obtained similarly except having changed the polymer P9 into Z3.
  • Comparative Example 4 [Creation of organic photoelectric conversion element using P11] As a comparative example of Examples 9 and 10, the following polymer P11 was used ( ⁇ m value of chlorine atom 0.37). In Example 9, an organic photoelectric conversion element was obtained in the same manner except that the polymer P9 was changed to P11.
  • a single film was prepared by spin-coating a polymer chlorobenzene or o-dichlorobenzene solution, and the HOMO level was measured in the air using a photoelectron spectrometer (AC-3, manufactured by Riken Keiki Co., Ltd.). Further, the band gap was determined from the absorption edge of the single film, the LUMO level was calculated from HOMO + band gap (BG), and these data are shown in Tables 1 and 2.
  • IPCE characteristics Each organic photoelectric conversion element was evaluated for its element characteristics using a spectral sensitivity measuring device (CEP-2000 manufactured by Spectrometer Co., Ltd.) under a nitrogen atmosphere (AM1.5G of 100 mW / cm 2 ). . With the above apparatus, the long wavelength end of the photoelectric conversion wavelength was calculated from the output IPCE spectrum.
  • the short-circuit current density (mA / cm) was measured from the IPCE spectrum for 10 organic photoelectric conversion elements prepared by repeating the organic photoelectric conversion elements described in Table 5 below under the same conditions. 2 ) was calculated, the variation was evaluated, and the results are shown in Table 5 below together with the long wavelength end of the photoelectric conversion wavelength.
  • the organic thin film solar cell using the compound of the present invention can photoelectrically convert light having a longer wavelength and is useful not only as a solar cell but also as a photosensor in a long wavelength region.
  • the short-circuit current density has little variation and the production suitability is excellent. From the above, it is clear that the compound of the present invention is preferable as a p-type organic semiconductor for organic photoelectric conversion elements such as organic thin film solar cells.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Photovoltaic Devices (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un élément de conversion photoélectrique organique qui comporte une première électrode, une couche de conversion photoélectrique qui contient un composé représenté par la formule (I) et une seconde électrode ; une cellule solaire à pellicule mince organique ; une composition utilisée dans l'élément de conversion photoélectrique organique ; une pellicule de revêtement ; un composé ; et un procédé de production du composé. Dans la formule, Ar représente un groupe arylène, un groupe hétéroarylène ou une combinaison de ceux-ci ; X représente S, O, Se, Te, -N(R1)- ou -C(R2)(R3)- ; R1 représente un atome d'hydrogène, un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, ou un groupe hétéroaryle ; chacun des groupes R2 et R3 représente un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, ou un groupe hétéroaryle, ou R2 et R3 peuvent se combiner pour former une structure cyclique ; Y représente un groupe extracteur d'électrons qui a une constante de Hammett de substituant (σm) supérieure à 0,50 ; et n représente un entier compris entre 2 et 2 000.
PCT/JP2014/058811 2013-03-28 2014-03-27 Élément de conversion photoélectrique organique, cellule solaire à pellicule mince organique, composition utilisée dans ledit élément, pellicule de revêtement, composé utile pour ladite pellicule, et procédé de production du composé WO2014157497A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2013070452 2013-03-28
JP2013-070452 2013-03-28
JP2013-197373 2013-09-24
JP2013197373A JP6088954B2 (ja) 2013-03-28 2013-09-24 有機光電変換素子、有機薄膜太陽電池、これに用いる組成物、塗布膜およびこれに有用な化合物

Publications (1)

Publication Number Publication Date
WO2014157497A1 true WO2014157497A1 (fr) 2014-10-02

Family

ID=51624458

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/058811 WO2014157497A1 (fr) 2013-03-28 2014-03-27 Élément de conversion photoélectrique organique, cellule solaire à pellicule mince organique, composition utilisée dans ledit élément, pellicule de revêtement, composé utile pour ladite pellicule, et procédé de production du composé

Country Status (2)

Country Link
JP (1) JP6088954B2 (fr)
WO (1) WO2014157497A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105490642A (zh) * 2015-12-24 2016-04-13 合肥晶澳太阳能科技有限公司 一种光伏组件蜗牛纹的测试方法
WO2019030382A1 (fr) * 2017-08-11 2019-02-14 Merck Patent Gmbh Polymere semiconducteur organique

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104701207B (zh) * 2015-03-04 2017-06-23 通威太阳能（合肥）有限公司 一种用于太阳能电池组件的蜗牛纹预测方法
JP6788568B2 (ja) 2017-12-04 2020-11-25 株式会社東芝 光電変換素子及び放射線検出器
KR20210015311A (ko) 2019-08-01 2021-02-10 삼성전자주식회사 센서 및 전자 장치

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012054910A1 (fr) * 2010-10-22 2012-04-26 Polyera Corportion Polymères conjugués et leur utilisation dans des dispositifs optoélectroniques
JP2012107187A (ja) * 2010-04-28 2012-06-07 Sumitomo Chemical Co Ltd 高分子化合物、化合物およびその用途
WO2012153845A1 (fr) * 2011-05-12 2012-11-15 コニカミノルタホールディングス株式会社 Élément de conversion photoélectrique organique, son procédé de production et cellule solaire

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012107187A (ja) * 2010-04-28 2012-06-07 Sumitomo Chemical Co Ltd 高分子化合物、化合物およびその用途
WO2012054910A1 (fr) * 2010-10-22 2012-04-26 Polyera Corportion Polymères conjugués et leur utilisation dans des dispositifs optoélectroniques
WO2012153845A1 (fr) * 2011-05-12 2012-11-15 コニカミノルタホールディングス株式会社 Élément de conversion photoélectrique organique, son procédé de production et cellule solaire

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
J. J. VAN DAALEN ET AL.: "THE CHEMISTRY, HERBICIDAL AND FUNGICIDAL ACTIVITIES OF 2,1,3- BENZOTHIADIAZOLE", RECUEIL, vol. 86, no. ISSUE, 1967, pages 1159 - 1181 *
JINWOO KIM ET AL.: "Novel 4, 7-Dithien- 2-yl-2, 1, 3-benzothiadiazole-based Conjugated Copolymers with Cyano Group in Vinylene Unit for Photovoltaic Applications", BULLETIN OF THE KOREAN CHEMICAL SOCIETY, vol. 33, no. 2, 20 June 2012 (2012-06-20), pages 629 - 635 *
QIANG PENG ET AL.: "Synthesis and Photovoltaic Properties of Two-Dimensional Low-Bandgap Copolymers Based on New Benzothiadiazole Derivatives with Different Conjugated Arylvinylene Side Chains", CHEMISTRY A EUROPEAN JOURNAL, vol. 18, no. ISSUE, 17 September 2012 (2012-09-17), pages 12140 - 12151 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105490642A (zh) * 2015-12-24 2016-04-13 合肥晶澳太阳能科技有限公司 一种光伏组件蜗牛纹的测试方法
CN105490642B (zh) * 2015-12-24 2017-10-20 合肥晶澳太阳能科技有限公司 一种光伏组件蜗牛纹的测试方法
WO2019030382A1 (fr) * 2017-08-11 2019-02-14 Merck Patent Gmbh Polymere semiconducteur organique
CN110998888A (zh) * 2017-08-11 2020-04-10 默克专利股份有限公司 有机半导体聚合物
US11005043B2 (en) 2017-08-11 2021-05-11 Raynergy Tek Incorporation Organic semiconducting polymer
CN110998888B (zh) * 2017-08-11 2023-09-12 天光材料科技股份有限公司 有机半导体聚合物

Also Published As

Publication number Publication date
JP2014209535A (ja) 2014-11-06
JP6088954B2 (ja) 2017-03-01

Similar Documents

Publication Publication Date Title
Yan et al. Non-fullerene acceptors for organic solar cells
JP5848280B2 (ja) 有機薄膜太陽電池、これに用いられる組成物および単量体、ならびに膜の製造方法
JP5482973B1 (ja) 共役系重合体、これを用いた電子供与性有機材料、光起電力素子用材料および光起電力素子
JP6085236B2 (ja) 有機半導体デバイス、これに用いる化合物、組成物及び塗布膜
JP5869420B2 (ja) 有機薄膜太陽電池、これに用いられる組成物、単量体および半導体膜の製造方法
JP5859872B2 (ja) 有機光電変換素子組成物、これを含む薄膜、光電池、これに用いられる有機半導体ポリマー、化合物およびポリマーの製造方法
JP2014512100A (ja) 電気光学デバイスの活性物質および電気光学デバイス
JP6297891B2 (ja) 有機材料及び光電変換素子
JP6088954B2 (ja) 有機光電変換素子、有機薄膜太陽電池、これに用いる組成物、塗布膜およびこれに有用な化合物
WO2014042091A1 (fr) Polymère conjugué, et matériau organique donneur d'électrons, matériau pour élément photovoltaïque, et élément photovoltaïque le comprenant
JP5859911B2 (ja) 有機薄膜太陽電池、これに用いられる組成物および半導体膜の製造方法
JP5662916B2 (ja) 有機薄膜太陽電池、これに用いられる有機半導体ポリマーおよび有機半導体材料用組成物
Liu et al. PDI-based hexapod-shaped nonfullerene acceptors for the high-performance as-cast organic solar cells
JP6181318B2 (ja) 光電子工学用途のための高い導電性および吸収を有する小分子／オリゴマーの合成
JP6641692B2 (ja) 光電変換素子
JP6051102B2 (ja) 有機光電変換素子および有機薄膜太陽電池
JP6068729B2 (ja) 電子豊富な部位と電子不足の部位を有する化合物、および有機電子用途におけるその使用
JP5643735B2 (ja) 有機薄膜太陽電池、これに用いられる有機半導体ポリマーおよび有機半導体材料用組成物
JP2021100094A (ja) 有機半導体組成物、光起電力素子、光電変換デバイスおよび光起電力素子の製造方法
WO2014098094A1 (fr) Élément de conversion photoélectrique organique, cellule solaire à couche mince organique, composition, film de revêtement, polymère et composé utilisés
WO2014050902A1 (fr) Cellule solaire en couches minces organique
JP2016103570A (ja) 光起電力素子
Han Synthesis of a Fullerene Acceptor with Visible Absorption for Polymer Solar Cells

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14775914

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14775914

Country of ref document: EP

Kind code of ref document: A1