WO2025205379A1 - Composition - Google Patents

Composition

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Publication number
WO2025205379A1
WO2025205379A1 PCT/JP2025/010844 JP2025010844W WO2025205379A1 WO 2025205379 A1 WO2025205379 A1 WO 2025205379A1 JP 2025010844 W JP2025010844 W JP 2025010844W WO 2025205379 A1 WO2025205379 A1 WO 2025205379A1
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WO
WIPO (PCT)
Prior art keywords
ring
group
formula
substituent
atom
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Pending
Application number
PCT/JP2025/010844
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English (en)
Japanese (ja)
Inventor
優子 鈴木
寛記 杉浦
晃逸 佐々木
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Fujifilm Corp
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Fujifilm Corp
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Publication of WO2025205379A1 publication Critical patent/WO2025205379A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • 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
    • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight

Definitions

  • the present invention relates to a composition.
  • Patent Document 1 discloses a photoelectric conversion element having a photoelectric conversion film containing a compound having a specific structure represented by formula (1).
  • the present invention therefore aims to provide a composition that can be used to produce a compound that can be used to manufacture a photoelectric conversion element whose response speed has minimal dependence on electric field strength.
  • the alkenyl group may be linear, branched, or cyclic.
  • the number of carbon atoms in the alkenyl group is preferably 2 to 20.
  • examples of the substituent which the alkenyl group may have include the same as the substituents in the alkyl group which may have a substituent.
  • the alkynyl group may be linear, branched, or cyclic.
  • the number of carbon atoms in the alkynyl group is preferably 2 to 20.
  • examples of the substituent which the alkynyl group may have are the same as those of the substituent in the alkyl group which may have a substituent.
  • the composition includes a specific compound.
  • the specific compound is a compound selected from the group consisting of compounds represented by formula (1) and compounds represented by formula (2).
  • the composition may contain both the compound represented by formula (1) and the compound represented by formula (2).
  • the conjugated structure represented by D1 is not particularly limited as long as it is the above-mentioned conjugated structure.
  • the conjugated structure represented by D1 is preferably a monocyclic ring having a conjugated structure (hereinafter also simply referred to as a "conjugated monocyclic ring”), a fused ring having a conjugated structure (hereinafter also simply referred to as a “conjugated fused ring”), or two rings linked by a chain-like conjugated linking group described below (hereinafter also simply referred to as a "linked ring").
  • it may be a ring formed by combining two or more rings selected from the group consisting of a conjugated monocycle, a conjugated fused ring, and a linked ring.
  • a conjugated monocycle a conjugated fused ring
  • a linked ring As the ring formed by combining two or more rings, -(Ar k1 ) k1 - is preferred.
  • Ar k1 represents a conjugated monocycle, a conjugated fused ring, or a linked ring.
  • k1 represents an integer of 2 or more (preferably an integer of 2 to 6).
  • Ar k 's may be the same or different.
  • the conjugated monocyclic ring, the conjugated fused ring, and the linked ring may have a substituent.
  • substituents include the groups exemplified above for the substituent W, and preferred are an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, an aryl group which may have a substituent, a halogen atom, a cyano group, or a primary, secondary, or tertiary amino group.
  • the number of substituents that the conjugated single ring, the conjugated fused ring, and the connecting ring may have is preferably 1 to 6, and more preferably 1 to 3.
  • the conjugated monocyclic ring is a monocyclic aromatic ring.
  • the conjugated monocycle may be either a monocyclic aromatic hydrocarbon ring or a monocyclic aromatic heterocycle.
  • the number of ring atoms in the monocyclic aromatic ring is preferably 5 to 10, and more preferably 5 or 6.
  • the monocyclic aromatic ring preferably has 1 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 4 to 12 carbon atoms.
  • heteroatoms contained in the monocyclic aromatic heterocycle include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, a boron atom, and a germanium atom, and a sulfur atom, an oxygen atom, or a nitrogen atom is preferred.
  • Examples of the monocyclic aromatic ring include a monocyclic aromatic hydrocarbon ring such as a benzene ring; and a monocyclic aromatic heterocycle such as a furan ring, a thiophene ring, a selenophene ring, a pyrrole ring, a thiazole ring, an isothiazole ring, a germole ring, a silole ring, an oxazole ring, an isoxazole ring, a thiadiazole ring, an oxadiazole ring, an imidazole ring, a pyrazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, and a tetrazine ring; and a benzene ring
  • the conjugated fused ring includes a fused ring formed by combining two or more single rings.
  • the two rings linked by a chain-like conjugated linking group are rings formed by linking two rings together by a chain-like conjugated linking group.
  • the conjugated fused ring itself may or may not exhibit aromaticity.
  • Examples of the monocyclic ring constituting the conjugated fused ring include a monocyclic aromatic ring and a monocyclic ring other than a monocyclic aromatic ring.
  • Examples of the monocyclic aromatic ring include the monocyclic aromatic rings constituting the above-mentioned conjugated monocycles.
  • Examples of the other monocyclic ring include a non-aromatic ring and an anti-aromatic ring, and a cyclopentadiene ring, a cyclohexadiene ring, a cycloheptadiene ring, a cyclooctadiene ring, a silacyclopentadiene ring, a germacyclopentadiene ring, or a cyclopentane-1,3-dione ring is preferred.
  • an aromatic ring is a ring having a ⁇ electron system with 4n+2 electrons (n is an integer of 0 or more)
  • an anti-aromatic ring is a ring having a ⁇ electron system with 4n electrons (n is an integer of 1 or more)
  • a non-aromatic ring is a ring that does not satisfy the requirements of an aromatic ring or an anti-aromatic ring.
  • conjugated fused rings having another single ring include a fluorene ring and a dibenzopentalene ring.
  • Preferred conjugated fused rings include fused rings formed by combining two or more (preferably, 2 to 4) monocyclic aromatic rings, fused rings formed by combining one or more (preferably, 1 to 3) monocyclic aromatic rings with one or more (preferably, 1 to 3) rings other than the monocyclic aromatic ring, and fused rings formed by combining two or more (preferably, 2 to 4) rings other than the monocyclic aromatic ring.
  • the type of the substituent represented by R c2 is not particularly limited, and examples thereof include the groups exemplified as the substituent W described below, and an alkyl group, an aryl group, or a heteroaryl group, which may have a substituent, is preferred.
  • the ring may be either a monocycle or a polycycle, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring.
  • the number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10.
  • carbon atoms other than the carbon atom at the bonding position marked with * in formula (A-1) and the carbon atom bonded to Y1 may be carbonyl carbons or thiocarbonyl carbons.
  • the ring represented by C1 above is preferably a ring used as an acidic nucleus (for example, an acidic nucleus in a merocyanine dye), and examples thereof include the following nuclei: (a) 1,3-dicarbonyl nucleus: for example, a 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-4,6-dione.
  • an acidic nucleus for example, an acidic nucleus in a merocyanine dye
  • examples thereof include the following nuclei: (a) 1,3-dicarbonyl nucleus: for example, a 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-4,6-di
  • (e) 2,4,6-trioxohexahydropyrimidine nucleus for example, barbituric acid, 2-thiobarbituric acid, and derivatives thereof.
  • the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl, and 1,3-dibutyl, 1,3-diaryl compounds such as 1,3-diphenyl, 1,3-di(p-chlorophenyl), and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, and 1,3-diheteroaryl compounds such as 1,3-di(2-pyridyl).
  • rhodanine 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and its derivatives.
  • the derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-allylrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and 3-heteroarylrhodanines such as 3-(2-pyridyl)rhodanine.
  • 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus for example, 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione.
  • Imidazolin-5-one nucleus for example, 2-propylmercapto-2-imidazolin-5-one.
  • 3,5-pyrazolidinedione nucleus for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione.
  • Benzothiophen-3(2H)-one nucleus for example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, and dioxobenzothiophen-3(2H)-one.
  • Indanone nucleus for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, and 3,3-dimethyl-1-indanone.
  • Benzofuran-3-(2H)-one nucleus for example, benzofuran-3-(2H)-one.
  • the ring formed by bonding R Y1 and a substituent carried by the ring represented by C 1 together may be either a monocyclic ring or a polycyclic ring. Furthermore, when R Y1 and a substituent carried by the ring represented by C 1 together form a group represented by formula (A-1), the group is preferably a fused ring of 2 to 5 rings, more preferably a fused ring of 2 or 3 rings.
  • the fused ring is preferably a fused ring formed by condensing a plurality of rings selected from aromatic rings and non-aromatic rings, more preferably a fused ring formed by condensing an aromatic ring with one or more rings selected from aromatic rings and non-aromatic rings.
  • the group represented by formula (A-1) is preferably a group represented by formula (Q1).
  • Q and Y represent a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified for the substituent W.
  • B2 represents a ring which may have a substituent and which contains two carbon atoms and QB .
  • the two carbon atoms refer to the two carbon atoms specified in the formula.
  • Examples of B2 include the ring represented by C1 .
  • R Y2 and R Y3 each independently represent a cyano group, —SO 2 R Y4 , —COOR Y5 or —COR Y6 .
  • R Y4 to R Y6 each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.
  • the aliphatic hydrocarbon group is as defined above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred.
  • the aromatic ring group is as defined above, and is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
  • R A1 and R A2 each independently represent a cyano group, —SO 2 R X1 , —COOR X2 or —COR X3 .
  • R X1 to R X3 each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.
  • R A1 and R A2 are preferably a cyano group or —COR X3 .
  • a 1 is preferably a group represented by formula (A-1) above, more preferably a group represented by formula (A-3), and even more preferably a group represented by formula (C-1) or a group represented by formula (C-2).
  • C2 represents a ring containing 3 or more carbon atoms and which may have a substituent.
  • the three carbon atoms contained in the above C2 are the three carbon atoms clearly shown in formula (A-3), and C2 may further contain carbon atoms other than the above three carbon atoms.
  • the number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10.
  • the number of carbon atoms in the ring is the number including the three carbon atoms specified in the formula.
  • the ring may be either an aromatic ring or a non-aromatic ring.
  • the ring may have a heteroatom, such as a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, or a boron atom, and is preferably a sulfur atom, a nitrogen atom, or an oxygen atom.
  • the number of heteroatoms contained in the ring is preferably 0 to 10, and more preferably 0 to 5.
  • the carbon atoms other than the carbon atom at the bonding position marked with * in formula (A-3) and the carbon atom bonded to W2 or W3 may be carbonyl carbons or thiocarbonyl carbons.
  • Preferred embodiments of the substituent that the ring may have are the same as the substituent that the ring C1 may have.
  • W2 and W3 each independently represent an oxygen atom, a sulfur atom, ⁇ NR Y1 , or ⁇ CR Y2 R Y3 .
  • R Y1 to R Y3 have the same meanings as R Y1 to R Y3 in formula (A-1), and preferred embodiments are also the same.
  • W2 and W3 are preferably each independently an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
  • R C1 represents a hydrogen atom or a substituent. Examples of the substituent include the substituents exemplified for the substituent W above.
  • R C2 and R C3 each independently represent a cyano group, —SO 2 R C4 , —COOR C5 or —COR C6 .
  • C3 represents an aromatic ring containing two or more carbon atoms and which may have a substituent.
  • the aromatic ring may be either a monocyclic ring or a polycyclic ring, but is preferably a monocyclic ring.
  • the number of ring members in the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 5 to 8.
  • the number of ring members in the aromatic ring is the number including the two carbon atoms specified in the formula.
  • the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred.
  • the aromatic ring represented by C3 is preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, a pyridine ring, a thienothiophene ring, a benzothiophene ring, a benzofuran ring, a pyrazine ring, a pyrimidine ring, a thienothiophene ring, or a pyridazine ring, more preferably a benzene ring, a naphthalene ring, or a thiophene ring, and even more preferably a benzene ring.
  • substituents that the aromatic ring may have include the groups exemplified as the substituent W, and an alkyl group or a halogen atom is preferred.
  • the number of substituents that the aromatic ring may have is not particularly limited, but is preferably 0 to 8, and more preferably 0 to 4.
  • X c3 to X c5 each independently represent an oxygen atom, a sulfur atom, ⁇ NR C1 , or ⁇ CR C2 R C3 .
  • X c3 and X c4 are preferably oxygen atoms
  • X c3 to X c5 are more preferably oxygen atoms.
  • the definitions and preferred embodiments of R C1 to R C3 are as described above.
  • a compound represented by formula (1) is preferably a compound represented by formula (1-1).
  • ring A and ring B each independently represent a conjugated monocyclic ring, a conjugated fused ring, or a linked ring.
  • the conjugated monocyclic ring and the conjugated fused ring include conjugated monocyclic rings and conjugated fused rings that constitute the conjugated structure represented by D1 , respectively.
  • the conjugated monocyclic ring is preferably an aromatic six-membered ring, a conjugated five-membered ring, or a non-aromatic conjugated six-membered ring.
  • the conjugated five-membered ring is a five-membered ring having a conjugated structure
  • the non-aromatic conjugated six-membered ring is a non-aromatic six-membered ring having a conjugated structure
  • the aromatic six-membered ring is preferably a six-membered ring exhibiting aromaticity among the conjugated monocyclic rings constituting the conjugated structure represented by D1 , and more preferably an aromatic six-membered ring having an atom selected from the group consisting of carbon atoms and nitrogen atoms as a ring member atom.
  • the number of nitrogen atoms is preferably 1 to 5, and more preferably 1 to 3.
  • R D1 to R D5 have the same meanings as R D1 to R D5 in formula (a2), and the preferred embodiments are also the same.
  • a more specific structure of the conjugated five-membered ring is a monocycle represented by formula (a2).
  • the non-aromatic conjugated 6-membered ring is preferably a conjugated 6-membered ring exhibiting non-aromaticity among the conjugated monocycles constituting the conjugated structure represented by D1 , and more preferably a non-aromatic conjugated 6-membered ring in which -Y D1 -Y D2 - constitutes the ring.
  • Y D1 and Y D2 represent an oxygen atom, a sulfur atom, a selenium atom, or -NR D6 -, and the other represents -CR c2 2 -, R D6 represents a hydrogen atom or a substituent, and R c2 represents a hydrogen atom or a substituent.
  • Y D1 , Y D2 , R D6 , and R c2 have the same meanings as V 181 , V 182 , R D6 , and R c2 in formula (a3), respectively, and the preferred embodiments are also the same.
  • the rings B may be the same or different.
  • a more specific example of the structure of the non-aromatic conjugated six-membered ring is a monocycle represented by formula (a3).
  • the conjugated fused ring is preferably a conjugated fused ring that constitutes a conjugated structure represented by D1 , and more preferably a fused ring formed by condensing a plurality of rings selected from the group consisting of the above-mentioned aromatic six-membered ring, the above-mentioned aromatic five-membered ring, and the above-mentioned non-aromatic six-membered ring.
  • the linked ring is preferably a linked ring forming a conjugated structure represented by D1 .
  • a 1 's each independently represent a group represented by formula (A-1) or a group represented by formula (A-2).
  • a 1 has the same meaning as A 1 in formula (1), and the preferred embodiments are also the same.
  • Each m1 independently represents 0 or 1.
  • o1 represents an integer of 0 to 2.
  • o1 is preferably 0 or 1.
  • D2 represents a structure having at least one ring structure.
  • the structure represented by D2 may be either a conjugated structure or a non-conjugated structure, and a conjugated structure is preferred.
  • the conjugated structure represented by D2 includes the conjugated structure represented by D1 .
  • n2 is 2 or 3
  • the conjugated structure represented by D2 has the same definition as the conjugated structure represented by D1 .
  • n2 is 1
  • the non-conjugated structure represented by D2 is not particularly limited as long as it has at least one ring structure and is a structure other than a conjugated structure.
  • non-conjugated structure examples include a non-conjugated structure formed by combining rings that constitute the conjugated structure represented by D1 , and a monocyclic ring having a non-conjugated structure or a fused ring having a non-conjugated structure is preferred.
  • the monocyclic ring having a non-conjugated structure examples include other monocyclic rings that can constitute the conjugated structure represented by D1 .
  • Examples of the fused ring having a non-conjugated structure include fused rings formed by combining other monocyclic rings and monocyclic aromatic rings that can constitute the conjugated structure represented by D1 .
  • D2 Specific examples of the structure represented by D2 include the conjugated structure represented by D1 above and the following structure: * represents a bonding position.
  • n2 represents an integer of 1 to 3. n2 is preferably 1 or 2. m2 represents 0 or 1. m2 is preferably 0. Each m2 may be the same or different.
  • A2 represents a group represented by formula (A-1) or a group represented by formula (A-2).
  • A2 has the same meaning as A1 , and the preferred embodiments are also the same. A2 may be the same or different.
  • A2 represents a group represented by formula (A-1) or a group represented by formula (A-2).
  • A2 has the same meaning as A1 , and the preferred embodiments are also the same.
  • m2 represents 0 or 1.
  • One of X1 and X2 represents -NR N -, and the other represents a sulfur atom, an oxygen atom, a selenium atom, -NR N - or -CR c1 2 -.
  • R N represents a hydrogen atom or a substituent.
  • R c1 represents a hydrogen atom or a substituent.
  • the specific compounds are particularly useful as materials for photoelectric conversion films used in imaging devices, optical sensors, or photovoltaic cells.
  • the specific compounds often function as dyes within the photoelectric conversion films.
  • the specific compounds can also be used as coloring materials, liquid crystal materials, organic semiconductor materials, charge transport materials, pharmaceutical materials, and fluorescent diagnostic materials.
  • the content of the specific compound in the composition of the present invention is preferably 0.1 to 30% by mass, and more preferably 0.3 to 25% by mass, relative to the total mass of the composition.
  • the composition includes a specific alcohol.
  • the specific alcohol is an alcohol having an acid dissociation constant pKa of 13.0 or less.
  • the acid dissociation constant pKa of the specific alcohol is 13.0 or less, and is preferably 10.0 or less in terms of better effects of the present invention.
  • the lower limit of the acid dissociation constant pKa of the specific alcohol is preferably 0 or more, more preferably 4.0 or more, even more preferably 5.0 or more, and particularly preferably 6.0 or more.
  • the lowest acid dissociation constant pKa among the multiple acid dissociation constants pKa may be 13.0 or less.
  • one functional group in a certain alcohol has three acid dissociation constants pKa, namely, a first acid dissociation constant pKa: 1.0, a second acid dissociation constant pKa: 5.0, and a third acid dissociation constant pKa: 15.0
  • the lowest first acid dissociation constant pKa among them is 13.0 or less, and therefore the alcohol corresponds to a specific alcohol.
  • the specific alcohol is a compound having a hydroxy group.
  • the number of hydroxy groups that the specific alcohol has is not particularly limited and may be 1 or 2 or more, preferably 1 to 3, and more preferably 1.
  • the specific alcohol may have a substituent other than a hydroxy group.
  • the number of substituents (preferably the number of halogen atoms) other than the hydroxy group that the specific alcohol may have is not particularly limited and may be 1 or 2 or more, preferably 1 to 15, and more preferably 3 to 10.
  • substituents include the groups exemplified for the substituent W above, and are preferably an alkyl group, an alkenyl group, a halogen atom, a carboxy group, an aryl group, or a cyano group, more preferably an aryl group or a halogen atom, more preferably a fluorine atom or a chlorine atom, and even more preferably a fluorine atom.
  • the specific alcohol has a halogen atom, since this makes it easier to adjust the acid dissociation constant pKa to 13 or less, and it is more preferable that at least one carbon atom at the ⁇ -position of the hydroxy group of the specific alcohol has a halogen atom.
  • the specific alcohol preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 3 to 10 carbon atoms, in terms of achieving better effects of the present invention.
  • the specific alcohol is preferably an alcohol represented by formula (S1), more preferably an alcohol represented by formula (S2), and even more preferably an alcohol represented by formula (S3).
  • R S1 to R S6 examples include the groups exemplified above as the substituent W, and a halogen atom is preferred, with a chlorine atom or a fluorine atom being more preferred. It is preferred that at least one (preferably, two or three) of R S1 to R S3 represents a fluorine atom, and at least one (preferably, two or three) of R S4 to R S6 represents a fluorine atom, and more preferred that all of R S1 to R S6 represent fluorine atoms.
  • R S7 examples include the groups exemplified as the substituent W described above.
  • R S7 is preferably a hydrogen atom, an alkyl group which may have a halogen atom, or an aryl group.
  • R S1 to R S3 in formula (S2) have the same meanings as R S1 to R S3 in formula (S1), respectively, and the preferred embodiments are also the same.
  • R S7 in formula (S2) has the same meaning as R S7 in formula (S1), and the preferred embodiments are also the same.
  • Specific alcohols include, for example, hexafluoroisopropanol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, nonafluoro-tert-butyl alcohol, and 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol.
  • alcohols include the following alcohols:
  • the specific alcohol may be used alone or in combination of two or more.
  • the content of the specific alcohol is preferably from 0.01 to 99% by mass, more preferably from 0.1 to 90% by mass, and even more preferably from 1 to 50% by mass, based on the total mass of the composition.
  • the composition may contain an organic solvent other than the above-mentioned specific alcohol.
  • the organic solvent is preferably a hydrocarbon which may have a substituent.
  • the hydrocarbon may be either an aliphatic hydrocarbon or an aromatic hydrocarbon.
  • the hydrocarbon preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms.
  • Examples of the substituent that the hydrocarbon may have include the groups exemplified above for the substituent W, and a halogen atom or an alkoxy group is preferred, with a halogen atom being more preferred.
  • the number of substituents is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
  • Hydrocarbons which may have a substituent include, for example, halogenated aliphatic hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, tetrachloroethane, pentachloroethane, hexachloroethane, hexachloropropane, bromomethane, dibromomethane, tribromomethane, tetrabromoethane, pentabromoethane, and hexabromoethane; halogenated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, dichlorotoluene, trichlorobenzene, ethylchlorobenzene, and
  • Saturated aliphatic hydrocarbons such as hexane, methylcyclohexane, octane, nonane, decane, undecane, dodecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, and decahydronaphthalene; aromatic hydrocarbon solvents such as mesitylene, cumene, pseudocumene, 1,2,4,5-tetramethylbenzene, p-cymene, toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, 1-chloronaphthalene, and 1-methylnaphthalene; benzothiophene and benzo
  • the organic solvent is preferably composed only of atoms selected from the group consisting of hydrogen atoms, carbon atoms, oxygen atoms, and halogen atoms, and is even more preferably composed only of atoms selected from the group consisting of hydrogen atoms, carbon atoms, and halogen atoms, in order to achieve better effects of the present invention.
  • the organic solvent may be used alone or in combination of two or more kinds.
  • the content of the organic solvent is preferably from 0 to 99% by mass, more preferably from 1 to 90% by mass, and even more preferably from 10 to 80% by mass, based on the total mass of the composition.
  • the content of the specific alcohol relative to the total content of the specific alcohol and the organic solvent is preferably 0.01% by volume or more, more preferably 1% by volume or more, and from the viewpoint of more excellent effects of the present invention, is even more preferably 10% by volume, particularly preferably 15% by volume or more.
  • the upper limit is preferably less than 100% by volume, more preferably 99% by volume or less, and even more preferably 95% by volume or less.
  • the total content of the specific alcohol and the organic solvent other than the specific alcohol in the composition of the present invention is preferably 70 to 99.9% by mass, and more preferably 75 to 99.7% by mass, based on the total mass of the composition.
  • composition may contain other components in addition to the various components described above.
  • other components include known additives.
  • composition of the present invention is preferably used in the production of photoelectric conversion elements, and more preferably used in the formation of a photoelectric conversion film that the photoelectric conversion element has.
  • the photoelectric conversion element 10b shown in Fig. 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in Figs. 1 and 2 may be changed as appropriate depending on the application and characteristics.
  • the photoelectric conversion element 10 a it is preferable that light be incident on the photoelectric conversion film 12 through the upper electrode 15 . Furthermore, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and it is preferable to apply a voltage of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 7 V/cm between this pair of electrodes. In terms of performance and power consumption, the applied voltage is more preferably 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 7 V/cm, and even more preferably 1 ⁇ 10 ⁇ 3 to 5 ⁇ 10 6 V/cm.
  • the voltage is preferably applied so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode.
  • the photoelectric conversion element 10a (or 10b) is used as an optical sensor or incorporated into an imaging element, a voltage can be applied in a similar manner.
  • the photoelectric conversion element 10a (or 10b) can be suitably used as an imaging element. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.
  • the photoelectric conversion element preferably has a photoelectric conversion film.
  • the photoelectric conversion film is preferably formed using the specific compound obtained from the composition of the present invention.
  • the photoelectric conversion film contains the specific compound described above, and may also contain at least one selected from the group consisting of the specific alcohol described above, the organic solvent described above, and the other components described above.
  • the specific compound may be used alone or in combination of two or more. When two or more types are used, the total amount thereof is preferably within the above range.
  • the photoelectric conversion film preferably further contains an n-type organic semiconductor in addition to the specific compound.
  • the n-type organic semiconductor is a compound different from the above-mentioned specific compound.
  • An n-type organic semiconductor is an acceptor organic semiconductor material (compound) that has the property of readily accepting electrons.
  • an n-type organic semiconductor is the organic compound that has the greater electron affinity when two organic compounds are used in contact with each other.
  • any organic compound that has electron-accepting properties can be used as an acceptor organic semiconductor.
  • n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and derivatives thereof; fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); and 5- to 7-membered heterocyclic compounds having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole
  • polyarylene compounds fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic acid anhydride; 1,4,5,8-naphthalenetetracarboxylic acid diimide derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and derivatives thereof; triazole compounds; distyrylarylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silole compounds; 3,4,9,10-perylenetetracarboxylic acid dianhydride; 3,4,9,10-perylenetetracarboxylic acid diimide derivatives; and the compounds described in paragraphs [0056] to [0057] of JP-A No. 2006-100767.
  • fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferred.
  • fullerenes include fullerene C 60 , fullerene C 70 , fullerene C 76 , fullerene C 78 , fullerene C 80 , fullerene C 82 , fullerene C 84 , fullerene C 90 , fullerene C 96 , fullerene C 240 , fullerene C 540 , and mixed fullerenes.
  • fullerene derivatives include compounds in which a substituent is added to the above-mentioned fullerene. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group.
  • Preferred fullerene derivatives are the compounds described in JP-A-2007-123707.
  • the n-type organic semiconductor may be an organic dye.
  • organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, a
  • the molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.
  • the maximum absorption wavelength of the n-type organic semiconductor is preferably in the wavelength range of 400 nm to 600 nm.
  • the difference in electron affinity between the specific compound and the n-type organic semiconductor be 0.1 eV or more.
  • the n-type organic semiconductor may be used alone or in combination of two or more.
  • the content of the n-type organic semiconductor in the photoelectric conversion film is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 20 to 50 vol%.
  • the content of the specific compound is preferably 15 to 75 vol%, more preferably 30 to 75 vol%. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, the n-type organic semiconductor, and optionally a p-type organic semiconductor.
  • the total content of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume, based on the total mass of the photoelectric conversion film.
  • Examples of p-type organic semiconductors include triarylamine compounds (e.g., N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl ( ⁇ -NPD), compounds described in paragraphs [0128] to [0148] of JP-A No. 2011-228614, compounds described in paragraphs [0052] to [0063] of JP-A No.
  • TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
  • TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
  • JP-A-2015-153910 compounds described in paragraphs [0119] to [0158] of JP-A-2015-153910, the compounds described in paragraphs [0044] to [0051] of JP-A-2015-153910, and the compounds described in paragraphs [0086] to [0090] of JP-A-2012-094660, etc.
  • pyrazoline compounds for example, thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b][ 1] Benzothiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivatives, compounds described in paragraphs [0031] to [0036] of JP-A-2018-014474, compounds described in paragraphs
  • Examples of p-type organic semiconductors include benzoxazole compounds (for example, compounds described in Figures 3 to 7 of JP-A No. 2022-123944), dicarbazole compounds (for example, compounds described in Figures 2 to 5 of JP-A No. 2022-122839), benzoquinazoline compounds (for example, compounds described in paragraphs [0053] to [0056] of JP-A No. 2022-120323), azine compounds (for example, compounds described in paragraphs [0041] to [0042] of JP-A No. 2022-120273), compounds described in Figures 2 to 10 of JP-A No. 2022-115832, indolotriphenylene ...0323), and the like.
  • benzoxazole compounds for example, compounds described in Figures 3 to 7 of JP-A No. 2022-123944
  • dicarbazole compounds for example, compounds described in Figures 2 to 5 of JP-A No. 2022-122839
  • Examples of p-type organic semiconductors include compounds having a smaller ionization potential than n-type organic semiconductors, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductors are listed below.
  • the difference in ionization potential between the specific compound and the p-type organic semiconductor be 0.1 eV or more.
  • the p-type organic semiconductor may be used alone or in combination of two or more.
  • the content of the p-type organic semiconductor in the photoelectric conversion film is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 25 to 50 vol%.
  • Photoelectric conversion films containing specific compounds are non-luminescent films and have characteristics that differ from organic electroluminescent devices (OLEDs: Organic Light-Emitting Diodes).
  • a non-luminescent film is a film with a luminescent quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less. The lower limit is often 0% or more.
  • the photoelectric conversion film may further contain a dye in addition to the specific compound.
  • the dye is a compound different from the above-mentioned specific compound.
  • the dye is preferably an organic dye.
  • organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothi
  • the maximum absorption wavelength of the dye is preferably in the visible light region, more preferably 400 to 700 nm, and even more preferably 400 to 650 nm.
  • the dyes may be used alone or in combination of two or more.
  • the photoelectric conversion film may further contain optional components in addition to the components described above.
  • optional components include antioxidants, dispersants, and ultraviolet absorbers.
  • the optional component may also be an impurity derived from a specific compound, an n-type organic semiconductor, a p-type organic semiconductor, or a dye.
  • the content of the optional component in the photoelectric conversion film is preferably 0.01 to 10% by volume, and more preferably 0.01 to 1% by volume.
  • Examples of the method for forming the photoelectric conversion film include a dry film formation method and a coating film formation method.
  • dry film formation methods include physical vapor deposition methods such as vapor deposition (particularly vacuum deposition), sputtering, ion plating, and molecular beam epitaxy (MBE), as well as chemical vapor deposition (CVD) methods such as plasma polymerization. Vacuum deposition is preferred.
  • the manufacturing conditions such as the degree of vacuum and the deposition temperature, can be set according to conventional methods.
  • a photoelectric conversion film may be formed by a dry film formation method using a specific compound obtained by recrystallizing the composition of the present invention, or by a coating film formation method in which the composition of the present invention is applied.
  • the thickness of the photoelectric conversion film is preferably 10 to 1,000 nm, more preferably 50 to 800 nm, and even more preferably 50 to 500 nm.
  • the photoelectric conversion element preferably has an electrode.
  • the electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected.
  • Examples of materials constituting the upper electrode 15 include conductive metal oxides such as antimony- or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine-doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO: Indium Zinc Oxide); metal thin films such as gold, silver, copper, chromium, aluminum, and nickel; mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and nanocarbon materials such as carbon nanotubes and graphene. Among these, conductive metal oxides are preferred in terms of high conductivity and transparency.
  • the sheet resistance may be 100 to 10,000 ⁇ / ⁇ , and there is a large degree of freedom in the range of the film thickness that can be reduced.
  • An increase in light transmittance is preferable because it increases light absorption in the photoelectric conversion film and enhances photoelectric conversion performance.
  • the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.
  • the bottom electrode 11 may be transparent or non-transparent and light-reflective.
  • materials that can be used to form the bottom electrode 11 include conductive metal oxides such as antimony- or fluorine-doped tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, copper, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and graphene.
  • conductive metal oxides such as antimony- or fluorine-doped tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin
  • the method for forming the electrodes can be appropriately selected depending on the electrode material, and specific examples include wet methods such as printing and coating, physical methods such as vacuum deposition, sputtering, and ion plating, and chemical methods such as CVD and plasma CVD.
  • wet methods such as printing and coating
  • physical methods such as vacuum deposition, sputtering, and ion plating
  • chemical methods such as CVD and plasma CVD.
  • the electrode material is ITO
  • methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), and coating of a dispersion of indium tin oxide can be used.
  • the photoelectric conversion element preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.
  • the intermediate layer may be, for example, a charge-blocking film.
  • the charge-blocking film include an electron-blocking film and a hole-blocking film.
  • the electron blocking film may be made up of multiple films.
  • the electron blocking film may be composed of an inorganic material.
  • inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher quantum efficiency.
  • examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.
  • the photoelectric conversion element may further include a substrate.
  • the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate.
  • the substrate is usually positioned such that a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated in this order on the substrate.
  • Photoelectric conversion elements are used, for example, as imaging elements.
  • An imaging element is an element that converts the optical information of an image into an electrical signal, and typically has multiple photoelectric conversion elements arranged in a matrix on the same plane, with each photoelectric conversion element (pixel) converting the optical signal into an electrical signal and outputting the electrical signal pixel by pixel from the imaging element.
  • each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
  • the method for manufacturing the imaging element is not particularly limited, but examples thereof include a method including the step of manufacturing the photoelectric conversion element described above.
  • compositions containing each of compounds (D-2) to (D-20), an "alcohol” shown in Table 1, and an "organic solvent other than alcohol” shown in Table 1 were prepared, and recrystallization was carried out by distilling off the solvent in the composition in the same manner as in the synthesis of compound (D-1).
  • the precipitated crystals were collected by filtration, dried under reduced pressure, and then purified by sublimation to obtain each compound.
  • photoelectric conversion elements were produced using the compounds (D-1) to (D-20) obtained by the above procedure, and the properties thereof were evaluated.
  • the content of the specific compound in the composition containing the specific compound such as compounds (D-1) to (D-20) produced above, and various solvents ("alcohol” shown in Table 1 and "organic solvent other than alcohol” shown in Table 1) varied depending on the type of specific compound used.
  • the content of the specific compound relative to the total mass of the composition was as follows. For example, in the example in which compound (D-1) was used, the content of compound (D-1) relative to the total mass of the composition was 1 mass%.
  • Compound (D-1) 1% by mass, Compound (D-2): 2% by mass, Compound (D-3): 5% by mass, Compound (D-4): 2% by mass, Compound (D-5): 1% by mass, Compound ( D-6): 2% by mass, Compound (D-7): 0.5% by mass, Compound (D-8): 5% by mass, Compound (D-9): 15% by mass, Compound (D-10): 3% by mass, Compound ( D-11): 20% by mass, Compound (D-12): 20% by mass, Compound (D-13): 5% by mass, Compound (D-14): 1% by mass, Compound (D-15): 1% by mass, Compound (D-16): 3% by mass, Compound (D-17): 5% by mass, Compound (D-18): 5% by mass, Compound (D-19): 10% by mass, Compound (D-20): 1% by mass.
  • the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15.
  • amorphous ITO was formed on a glass substrate by sputtering to form a film of the lower electrode 11 (thickness: 30 nm), and compound (EB-1) was further formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm).
  • a specific compound shown in Table 1 an n-type organic semiconductor (fullerene (C 60 )), and a p-type organic semiconductor (compound (P-1)) were co-deposited by vacuum deposition on the electron blocking film 16A to form a film of 80 nm in monolayer equivalent thickness.
  • a photoelectric conversion film 12 having a bulk heterostructure of 240 nm was formed.
  • the film formation rate of the photoelectric conversion film 12 was 1.0 ⁇ /sec.
  • a compound (EB-2) was deposited on the photoelectric conversion film 12 to form a hole-blocking film 16B (thickness: 10 nm).
  • Amorphous ITO was deposited on the hole-blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm).
  • An SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, and then an aluminum oxide (Al 2 O 3 ) layer was formed thereon by atomic layer chemical vapor deposition (ALCVD).
  • ACVD atomic layer chemical vapor deposition
  • the dark current of each photoelectric conversion element was measured using the following method. A voltage was applied to the lower electrode and upper electrode of each photoelectric conversion element to achieve an electric field strength of 2.5 ⁇ 10 5 V/cm, and the current value (dark current) in a dark place was measured. As a result, it was confirmed that the dark current of each photoelectric conversion element was 50 nA/cm 2 or less, indicating a sufficiently low dark current.
  • Quantum efficiency (relative ratio) (quantum efficiency at a wavelength of 500 nm of each Example or Comparative Example) / (quantum efficiency at a wavelength of 500 nm of Comparative Example 1-1)
  • Quantum efficiency (relative ratio) is greater than 1.1.
  • B Quantum efficiency (relative ratio) is greater than 1.0 and less than 1.1.
  • C Quantum efficiency (relative ratio) is greater than 0.9 and less than 1.0.
  • D Quantum efficiency (relative ratio) is less than 0.9.
  • ⁇ Response speed> The response speed of each photoelectric conversion element obtained was evaluated by the following method. A voltage of 1.0 ⁇ 10 5 V/cm was applied to the photoelectric conversion element. Thereafter, an LED (light emitting diode) was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 500 nm at that time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity. The value obtained according to formula (Z2) was used to evaluate the response speed in accordance with the following criteria. A response speed rating of B or higher is preferable. Formula (Z2): Relative response speed (rise time at a wavelength of 500 nm for each Example or Comparative Example) / (rise time at a wavelength of 500 nm for Comparative Example 1-1)
  • the composition of the present invention can provide a compound that can be used to produce a photoelectric conversion element having a response speed that is less dependent on the electric field strength. It was confirmed that when the content of alcohol relative to the total content of alcohol and organic solvent was 10% by volume or more, the electric field strength dependency of the response speed was better (e.g., comparison of Examples 1-1 to 1-7, 1-9, 1-14 to 1-17, and 1-20 with Examples 1-8 and 1-21).
  • the acid dissociation constant pKa of the specific alcohol is 10.0 or less, or when the specific alcohol is an alcohol represented by formula (S1), it was confirmed that the quantum efficiency, response speed, and electric field strength dependence of the response speed were all superior (e.g., comparison of Examples 1-1 to 1-7, 1-9, 1-14 to 1-17, and 1-20 with Examples 1-11 and 1-12). It was confirmed that when an organic solvent other than the specific alcohol is contained and the organic solvent is composed only of atoms selected from the group consisting of hydrogen atoms, carbon atoms, and halogen atoms, the electric field strength dependence of the response speed is superior (e.g., comparison of Examples 1-1 to 1-7, 1-9, 1-14 to 1-17, and 1-20, etc., with Example 1-10).

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Abstract

La présente invention concerne une composition qui permet d'obtenir un composé avec lequel il est possible de produire un élément de conversion photoélectrique qui a une faible dépendance de la vitesse de réponse à l''intensité du champ électrique. Une composition selon la présente invention contient : un composé qui est choisi dans le groupe constitué par un composé représenté par la formule (1) et un composé représenté par la formule (2) ; et un alcool qui a une constante de dissociation acide pKa de 13,0 ou moins.
PCT/JP2025/010844 2024-03-27 2025-03-19 Composition Pending WO2025205379A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011082421A (ja) * 2009-10-09 2011-04-21 Konica Minolta Holdings Inc 有機光電変換素子の製造方法及び有機光電変換素子
JP2019212702A (ja) * 2018-06-01 2019-12-12 コニカミノルタ株式会社 太陽電池及びその製造方法
US20200067003A1 (en) * 2017-02-23 2020-02-27 Eni S.P.A. Polymer Photovoltaic Cell with an Inverted Structure and Process for its Preparation
WO2020218293A1 (fr) * 2019-04-24 2020-10-29 富士フイルム株式会社 Composition
WO2023219033A1 (fr) * 2022-05-11 2023-11-16 富士フイルム株式会社 Transducteur photo-électrique, élément d'imagerie, capteur optique, et composé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011082421A (ja) * 2009-10-09 2011-04-21 Konica Minolta Holdings Inc 有機光電変換素子の製造方法及び有機光電変換素子
US20200067003A1 (en) * 2017-02-23 2020-02-27 Eni S.P.A. Polymer Photovoltaic Cell with an Inverted Structure and Process for its Preparation
JP2019212702A (ja) * 2018-06-01 2019-12-12 コニカミノルタ株式会社 太陽電池及びその製造方法
WO2020218293A1 (fr) * 2019-04-24 2020-10-29 富士フイルム株式会社 Composition
WO2023219033A1 (fr) * 2022-05-11 2023-11-16 富士フイルム株式会社 Transducteur photo-électrique, élément d'imagerie, capteur optique, et composé

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