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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
  • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
  • C07D333/56—Radicals substituted by oxygen 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
  • C07D403/14—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 three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom 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
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
  • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
  • C07D513/04—Ortho-condensed systems
• • 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
  • C09B23/14—Styryl dyes
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
  • H10F39/10—Integrated devices
  • H10F39/12—Image sensors
• • 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
  • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
  • H10K39/30—Devices controlled by radiation
  • H10K39/32—Organic image sensors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight

Definitions

• the present invention relates to a photoelectric conversion element, an imaging element, an optical sensor, and a compound.
• Patent Document 1 discloses a dye compound having a specific structure as a compound that can be applied to organic semiconductor materials such as transistors.
• Photoelectric conversion elements that exhibit excellent characteristics are required to meet the demand for improved performance of image sensors, optical sensors, etc.
• the characteristics required for photoelectric conversion elements include, for example, excellent quantum efficiency and response speed when receiving blue light.
• the present inventors have produced and investigated a photoelectric conversion element containing the compound disclosed in Patent Document 1, and have found that it is not possible to achieve both quantum efficiency and response speed when blue light is received, and there is room for further improvement.
• blue light refers to light with a wavelength of 400 to 500 nm.
• D is a group represented by formula (2) described below.
• the photoelectric conversion element according to [10] wherein the n-type organic semiconductor contains a fullerene selected from the group consisting of fullerenes and derivatives thereof.
• the present invention it is possible to provide a photoelectric conversion element that is excellent in quantum efficiency and response speed when blue light is received. Furthermore, according to the present invention, there can be provided an imaging element, an optical sensor, and a compound relating to the above-mentioned photoelectric conversion element.
• FIG. 2 is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element.
• FIG. 2 is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element.
• a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower and upper limits.
• the hydrogen atom may be either a protium atom (normal hydrogen atom) or a deuterium atom (for example, a deuterium atom, etc.).
• substituents, linking groups, etc. hereinafter also referred to as "substituents, etc." represented by specific symbols, or when a plurality of substituents, etc. are simultaneously specified, it means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc.
• the substituent W in this specification will be described.
• the substituent W can be, for example, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (a heteroaryl group, or an aliphatic heterocyclic group), a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyl
• substituent W examples include an aryloxy group, a primary, secondary or tertiary amino group (including an anilino group), an alkylthio group, an arylthio group, a heterocyclic thio group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a carboxy group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, and a
• each of the above groups may further have a substituent (e.g., one or more of the above groups, etc.) if possible.
• a substituent e.g., one or more of the above groups, etc.
• an alkyl group which may have a substituent is also included as one form of the substituent W.
• the substituent W has a carbon atom
• the number of carbon atoms contained in the substituent W is, for example, 1 to 20.
• the number of atoms other than hydrogen atoms contained in the substituent W is, for example, 1 to 30.
• the specific compound described later does not have a carboxy group, a salt of a carboxy group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH) 2 ), and/or a primary amino group as a substituent.
• halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
• the aliphatic hydrocarbon group may be any of linear, branched, and cyclic.
• the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
• the alkyl group may be linear, branched, or cyclic.
• alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclopropyl group, and a cyclopentyl group.
• the alkyl group may be any one of a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group, and may have these ring structures as partial structures.
• examples of the substituent which the alkyl group may have examples of the substituent which the alkyl group may have include the groups exemplified as the substituent W.
• an aryl group preferably having 6 to 18 carbon atoms, more preferably having 6 carbon atoms
• a heteroaryl group preferably having 5 to 18 carbon atoms, more preferably having 5 to 6 carbon atoms
• a halogen atom preferably a fluorine atom or a chlorine atom
• the alkyl group moiety in the alkoxy group is preferably the above-mentioned alkyl group
• the alkyl group moiety in the alkylthio group is preferably the above-mentioned alkyl group.
• examples of the substituent which the alkoxy group may have include the same substituents as those in the alkyl group which may have a substituent.
• examples of the substituent which the alkylthio group may have include the same substituents as those in the alkyl group which may have a substituent.
• the alkenyl group may be any of linear, branched, and 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 those of the substituent in the alkyl group which may have a substituent.
• the alkynyl group may be any of linear, branched, and cyclic.
• the number of carbon atoms in the alkynyl group is preferably 2 to 20.
• an aromatic ring or an aromatic ring constituting an aromatic ring group may be either a monocyclic ring or a polycyclic ring (e.g., 2 to 6 rings).
• a monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as a ring structure.
• a polycyclic (e.g., 2 to 6 rings) aromatic ring is an aromatic ring having a plurality of (e.g., 2 to 6 rings) condensed aromatic ring structures as ring structures.
• the aromatic ring preferably has 5 to 15 ring members.
• the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle.
• the number of heteroatoms contained as ring member atoms is, for example, 1 to 10.
• the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.
• the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a phenanthrene ring, and a fluorene ring.
• Examples of the aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (e.g., a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring), a tetrazine ring (e.g., a 1,2,4,5-tetrazine ring), a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a
• aromatic ring group includes, for example, groups obtained by removing one or more (eg, 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic ring.
• aryl group includes, for example, a group in which one hydrogen atom has been removed from a ring that corresponds to an aromatic hydrocarbon ring among the above aromatic rings.
• heteroaryl group includes, for example, a group in which one hydrogen atom has been removed from a ring corresponding to an aromatic heterocycle among the above aromatic rings.
• arylene group includes, for example, a group formed by removing two hydrogen atoms from a ring corresponding to an aromatic hydrocarbon ring among the above aromatic rings.
• heteroarylene group includes, for example, a group formed by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the above aromatic rings.
• the types of the substituents which these groups may have include, for example, the groups exemplified for the substituent W.
• the number of the substituents may be 1 or more (for example, 1 to 4, etc.).
• non-aromatic ring refers to a ring structure that is not aromatic, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic heterocycle.
• examples of the aliphatic hydrocarbon ring include cycloalkanes, cycloalkenes, and cycloalkynes.
• Examples of the aliphatic heterocycle include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, and ⁇ -butyrolactone.
• aliphatic hydrocarbon ring group includes, for example, a group in which one hydrogen atom has been removed from a ring corresponding to an aliphatic hydrocarbon ring.
• aliphatic heterocyclic group includes, for example, a group in which one hydrogen atom has been removed from a ring corresponding to an aliphatic heterocycle.
• a formula showing a chemical structure contains a plurality of identical symbols showing the type or number of groups, unless otherwise specified, the contents of the plurality of identical symbols are independent of each other, and the contents of the plurality of identical symbols may be the same or different.
• a formula showing a chemical structure contains a plurality of groups of the same type (for example, alkyl groups, etc.), unless otherwise specified, the specific contents of the plurality of groups of the same type are independent of each other, and the specific contents of the groups of the same type may be the same or different.
• the bond direction of the divalent group is not limited unless otherwise specified.
• the compound may be either "X-O-CO-Z" or "X-CO-O-Z”.
• the general formula or structural formula representing the compound may be described in only one of the cis and trans forms for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form.
• the photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) (hereinafter also referred to as a "specific compound").
• the specific compound is a so-called ADA type dye compound having a donor portion (D) and an acceptor portion (A).
• the dye compound has a tendency that the longer the conjugation length of the donor portion, the greater the extinction coefficient, while the absorption wavelength shifts to a longer wavelength, and the more cohesive it becomes.
• the specific compound exhibits excellent quantum efficiency for the target blue light due to the structure of the donor portion in which the conjugation length is appropriately controlled, in which a specific two condensed rings and a single ring are linked by a single bond. Furthermore, due to the asymmetric structure of the donor portion, excessive cohesion between the specific compounds in the photoelectric conversion film is suppressed, which leads to efficient charge separation, and as a result, it is considered that the response speed is also excellent.
• superiority in at least one of the quantum efficiency and the response speed when blue light is received will also be referred to as "superior effect of the present invention.”
• FIG. 1 is a schematic cross-sectional view of one embodiment of a photoelectric conversion element of the present invention.
• the photoelectric conversion element 10a shown in Figure 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound, and a transparent conductive film (hereinafter also referred to as the "upper electrode”) 15 functioning as an upper electrode are stacked in this order.
• Fig. 2 shows a configuration example of another photoelectric conversion element.
• 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 laminated in this order on a lower electrode 11.
• the laminated 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 is 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 the 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 becomes the cathode and the photoelectric conversion film 12 side becomes the anode.
• the photoelectric conversion element 10a (or 10b) is used as an optical sensor or incorporated in 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 has a photoelectric conversion film.
• the photoelectric conversion film contains a specific compound, which is a compound represented by formula (1).
• D represents a group represented by formula (2) or a group represented by formula (3).
• Ar 1 represents a group represented by formula (Ar-1) or a group represented by formula (Ar-2).
• A1 and A2 each independently represent a group represented by formula (A-1).
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• * represents a bonding position.
• X21 and X31 each independently represent a sulfur atom, an oxygen atom, a selenium atom, -NRx1- , or -CRx2Rx3- .
• Rx1 to Rx3 each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent.
• Rx2 and Rx3 may be bonded to each other to form a ring which may have a substituent.
• Each R Y1 independently represents a hydrogen atom or a substituent.
• * indicates a bonding position.
• Each R Z1 independently represents a hydrogen atom or a substituent.
• * indicates a bonding position.
• X Ar2 represents a sulfur atom, an oxygen atom, a selenium atom, -NR Ar21 -, or -CR Ar22 R Ar23 -.
• R Ar21 to R Ar23 each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent.
• * indicates a bonding position.
• C1 represents an optionally substituted ring containing 2 or more carbon atoms.
• R W2 represents a hydrogen atom or a substituent.
• R W3 and R W4 each independently represent a cyano group, -SO 2 R W5 , -COOR W6 , or -COR W7 .
• R W5 to R W7 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.
• D represents a group represented by formula (2) or a group represented by formula (3), and it is preferable that it is a group represented by formula (2) in that the effect of the present invention is superior and the response speed has a smaller electric field strength dependency.
• X 21 and X 31 each independently represent a sulfur atom, an oxygen atom, a selenium atom, -NR X1 -, or -CR X2 R X3 -.
• X 21 and X 31 are preferably a sulfur atom, an oxygen atom, a selenium atom or —CR X2 R X3 —, and more preferably a sulfur atom or an oxygen atom, in terms of superior effects of the present invention.
• R X1 to R X3 each independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or an optionally substituted aromatic ring group.
• the aliphatic hydrocarbon group represented by R X1 to R X3 may be any one of linear, branched, and cyclic.
• the linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• the branched aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 7 carbon atoms, and even more preferably 3 to 5 carbon atoms.
• the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic.
• the cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms.
• substituents exemplified as the substituent W described above and a substituent selected from the substituent group S described below is preferable, and a halogen atom is more preferable.
• the aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred.
• the aromatic ring group may be either a monocyclic or polycyclic group.
• the aromatic ring group preferably has 5 to 20 ring members, more preferably 5 to 12 ring members, further preferably 5 to 10 ring members, and particularly preferably 5 to 8 ring members.
• the number of carbon atoms in the aromatic ring group which may have a substituent is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
• the lower limit is preferably 1 or more, more preferably 3 or more, and even more preferably 4 or more.
• heteroatom contained in the aromatic heterocyclic group examples include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, an oxygen atom, or a nitrogen atom is preferable.
• aromatic ring group examples include aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, and a fluorenyl group; and aromatic heterocyclic groups such as a pyridine ring group, a pyrimidine ring group, a pyridazine ring group, a pyrazine ring group, a triazine ring group, a tetrazine ring group, a quinoxaline ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a pyrazole ring group, a thiazole ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a benzimi
• a phenyl group, a thiophene ring group, a furan ring group, or a pyridine ring group is preferred, a phenyl group or a thiophene ring group is more preferred, and a phenyl group is even more preferred.
• substituents exemplified as the substituent W described above and the substituents selected from the substituent group S described below are preferred.
• the number of the substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.
• R 1 X2 and R 1 X3 may be bonded to each other to form a ring which may have a substituent.
• the ring may be either an aromatic ring or a non-aromatic ring, and may be either a monocyclic ring or a polycyclic 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 ring preferably has 3 to 20 ring members, and more preferably 5 to 12 ring members. Examples of the substituent that the ring may have include the substituents exemplified for the substituent W described above, and a substituent selected from the substituent group S is preferable.
• it is also preferable that at least one of Y 21 to Y 24 represents -CRs .
• R and Y1 independently represents a hydrogen atom or a substituent.
• substituent represented by R Y1 include the substituents exemplified for the substituent W described above, and an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an acyl group which may have a substituent, a halogen atom, an amino group, or a cyano group is preferable, an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a halogen atom is more preferable, and a substituent represented by Rs described below is even more preferable.
• Examples of the substituent that may be possessed by each group exemplified as the substituent represented by R Y1 include the substituents exemplified as the substituent W described above, and a substituent selected from the substituent group S described below is preferable.
• the aliphatic hydrocarbon group represented by R Y1 may be any one of a straight chain, a branched chain, and a cyclic group.
• the linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• the branched aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 7 carbon atoms, and even more preferably 3 to 5 carbon atoms.
• the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic.
• the cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms.
• the aromatic ring group represented by R Y1 may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred.
• the aromatic ring group may be either a monocyclic or polycyclic group.
• the aromatic ring group preferably has 5 to 20 ring members, more preferably 5 to 12 ring members, further preferably 5 to 10 ring members, and particularly preferably 5 to 8 ring members.
• heteroatom contained in the aromatic heterocyclic group examples include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, an oxygen atom, or a nitrogen atom is preferable.
• aromatic ring group examples are as described above, and are preferably a phenyl group, a thiophene ring group, a furan ring group, a thiazole ring group, an oxazole ring group, a benzothiophene ring group, a benzothiazole ring group, a benzimidazole ring group, or a pyridine ring group, more preferably a phenyl group or a thiophene ring group, and even more preferably a phenyl group.
• the number of the substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.
• the aliphatic heterocyclic group represented by R Y1 may be either a monocyclic or polycyclic group.
• the aliphatic heterocyclic group preferably has 5 to 20 ring members, more preferably 5 to 12 ring members, and even more preferably 6 to 8 ring members.
• Examples of the heteroatom contained in the aliphatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, an oxygen atom, or a nitrogen atom is preferable.
• Examples of the aliphatic heterocyclic group include a pyrrolidine ring group, an oxolane ring group, a thiolane ring group, a piperidine ring group, a tetrahydropyran ring group, a thiane ring group, a piperazine ring group, a morpholine ring group, a quinuclidine ring group, an azetidine ring group, an oxetane ring group, an aziridine ring group, a dioxane ring group, and a ⁇ -butyrolactone ring group, and a piperidine ring group is preferable.
• the number of the substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3.
• the alkyl group contained in the alkoxy group represented by R Y1 may be linear, branched, or cyclic.
• the alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a cyclopropoxy group.
• the aryl group contained in the aryloxy group represented by R Y1 may be either a monocyclic or polycyclic group, and is preferably a monocyclic group.
• the aryl group preferably has 5 to 10 carbon atoms, and more preferably has 6 carbon atoms.
• the aryloxy group includes, for example, a phenoxy group.
• the hydrocarbon group contained in the acyl group represented by R Y1 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon ring group, with an aliphatic hydrocarbon group being preferred. Preferred embodiments of the aliphatic hydrocarbon group and aromatic hydrocarbon group contained in the acyl group are the same as the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by R Y1 , respectively.
• the acyl group preferably has 2 to 11 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2 or 3 carbon atoms.
• acyl group examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, and a benzoyl group, and an acetyl group or a propionyl group is preferable.
• the halogen atom represented by R Y1 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
• the amino group represented by R Y1 may be any of a primary amino group, a secondary amino group, and a tertiary amino group, with a tertiary amino group being preferred.
• the group substituting the amino group is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group.
• * represents a bonding position.
• the bonding directions of the group represented by formula (2) and the group represented by formula (3) are not particularly limited.
• Ar 1 represents a group represented by formula (Ar-1) or a group represented by formula (Ar-2).
• R and Z1 independently represents a hydrogen atom or a substituent.
• substituents represented by R Z1 include the substituents exemplified for the substituent W described above, and are preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an acyl group which may have a substituent, a halogen atom, an amino group, or a cyano group, more preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a halogen atom, and further preferably a substituent represented by Rs described below.
• the definitions and preferred embodiments of each group exemplified as the substituent represented by R Z1 are the same as those of each group exemplified as the substituent represented by R Y
• X Ar2 represents a sulfur atom, an oxygen atom, a selenium atom, -NR Ar21 -, or -CR Ar22 R Ar23 -.
• X Ar2 is preferably a sulfur atom, an oxygen atom, a selenium atom or --CR Ar22 R Ar23 --, and more preferably a sulfur atom or an oxygen atom, in terms of superior effects of the present invention.
• R Ar21 to R Ar23 each independently represent a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or an optionally substituted aromatic ring group.
• the definitions and preferred embodiments of the optionally substituted aliphatic hydrocarbon groups and optionally substituted aromatic ring groups represented by R Ar21 to R Ar23 are the same as those of the optionally substituted aliphatic hydrocarbon groups and optionally substituted aromatic ring groups represented by R X1 to R X3 .
• R 1 Ar22 and R 1 Ar23 may be bonded to each other to form a ring which may have a substituent.
• the ring may be either an aromatic ring or a non-aromatic ring, and may be either a monocyclic ring or a polycyclic 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 ring preferably has 3 to 20 ring members, and more preferably 5 to 12 ring members. Examples of the substituent that the ring may have include the substituents exemplified for the substituent W described above, and a substituent selected from the substituent group S is preferable.
• it is also preferable that at least one of Z 21 and Z 22 is -CRs .
• R and Z2 independently represents a hydrogen atom or a substituent.
• the definition and preferred embodiments of the substituent represented by R Z2 are the same as those of the substituent represented by R Z1 described above.
• the specific compound preferably satisfies the following requirement X.
• the specific compound does not contain a nitrogen atom as a ring member atom of the two fused rings shown in formula (2) and formula (3) and the monocyclic ring shown in formula (Ar-1) and formula (Ar-2).
• the specific compound preferably satisfies at least one of the following requirements R1 and R2, and more preferably satisfies requirement R1, in that the effects of the present invention are more excellent and the response speed has a smaller electric field intensity dependency.
• Rs each independently represent a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a halogen atom, or an aromatic ring group having 5 to 10 ring members which may have a substituent.
• linear aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by Rs include a methyl group, an ethyl group, an n-propyl group, an ethynyl group, a propargyl group, and an allyl group.
• a methyl group, an ethyl group, or an n-propyl group is preferable, and a methyl group or an ethyl group is more preferable.
• branched aliphatic hydrocarbon group having 3 to 5 carbon atoms represented by Rs include a sec-butyl group, an iso-butyl group, an isopropenyl group, a tert-butyl group, and a neopentyl group, with an isopropyl group or a tert-butyl group being preferred.
• cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms represented by Rs include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bicyclo[1.1.1]pentyl group, and a bicyclo[2.2.2]heptyl group, with a cyclopropyl group being preferred.
• Examples of the halogen atom which may be contained in the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, represented by Rs, include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
• the aromatic ring group having 5 to 10 ring members represented by Rs may be either a monocyclic ring or a polycyclic ring, and is preferably a monocyclic ring.
• the aromatic ring group having 5 to 10 ring members may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon ring being preferred.
• aromatic ring group having 5 to 10 ring members include aromatic hydrocarbon groups such as a phenyl group and a naphthyl group; and aromatic heterocyclic groups such as a pyridine ring group, a pyrimidine ring group, a pyridazine ring group, a pyrazine ring group, a triazine ring group, a tetrazine ring group, a quinoxaline ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a pyrazole ring group, a thiazole ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a benzimidazole ring group, a benzoxazole ring group, and a benzothiazole
• a phenyl group, a pyrrole ring group, a furan ring group, a thiophene ring group, or a pyridine ring group is preferred, and a phenyl group is more preferred.
• substituents exemplified for the substituent W described above and a substituent selected from the substituent group S described below is preferable.
• the number of the substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.
• Substituent group S linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 5 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms, aromatic ring groups having 5 to 10 ring members which may have a substituent, and halogen atoms.
• linear aliphatic hydrocarbon group having 1 to 3 carbon atoms the branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent group S are the same as the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms represented by Rs.
• the aromatic ring group in the above-mentioned Substituent Group S may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, and is preferably an aromatic hydrocarbon group.
• the aromatic ring group in the above-mentioned Substituent Group S may be either a monocyclic or polycyclic group, and is preferably a monocyclic group.
• Specific examples and preferred embodiments of the aromatic ring group having 5 to 10 ring members in the substituent group S are the same as those of the aromatic ring group having 5 to 10 ring members represented by Rs, and among them, a phenyl group is preferred.
• the substituent that the aromatic ring group in the above-mentioned substituent group S may have is preferably a substituent selected from the substituent group S, and more preferably a methyl group, an ethyl group, an isopropyl group or a halogen atom.
• Halogen atoms in the above-mentioned substituent group S include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms and chlorine atoms being preferred.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• substituents include the substituents exemplified for the substituent W described above.
• R 1 and R 2 are preferably hydrogen atoms.
• A1 and A2 each independently represent a group represented by formula (A-1).
• C1 represents a ring containing two or more carbon atoms and which may have a substituent.
• the two carbon atoms contained in C1 are the two carbon atoms clearly shown in formula (A-1).
• 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 two carbon atoms specified in the formula.
• the ring may be either an aromatic ring or a non-aromatic ring.
• 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.
• 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 in the ring is preferably 0 to 10, and more preferably 0 to 5.
• 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.
• (b) Pyrazolinone nucleus for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one, and the like.
• (c) Isoxazolinone nucleus for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, and the like.
• (d) Oxindole nucleus for example, 1-alkyl-2,3-dihydro-2-oxindole, etc.
• (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).
• 2-thio-2,4-thiazolidinedione nucleus for example, rhodanine and its derivatives, etc.
• the derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3-heteroarylrhodanine such as 3-(2-pyridyl)rhodanine, etc.
• 2-thio-2,4-oxazolidinedione nucleus (2-thio-2,4-(3H,5H)-oxazoledione nucleus): for example, 3-ethyl-2-thio-2,4-oxazolidinedione.
• Thianaphthenone nucleus for example, 3(2H)-thianaphthenone-1,1-dioxide.
• 2-thio-2,5-thiazolidinedione nucleus for example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc.
• (j) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, and 3-phenyl-2,4-thiazolidinedione.
• 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, etc.
• 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, dioxobenzothiophen-3(2H)-one, and the like.
• 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, etc.
• W 1 represents a sulfur atom, an oxygen atom, ⁇ NR W2 , or ⁇ CR W3 R W4 .
• W1 is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom, in that the response speed has a smaller dependency on the electric field strength.
• R W2 represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified for the substituent W above.
• R W3 and R W4 each independently represent a cyano group, —SO 2 R W5 , —COOR W6 or —COR W7 .
• R W5 to R W7 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.
• the aliphatic heterocyclic group is as defined above, and the heteroatom contained in the aliphatic heterocyclic group is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. Examples of the substituent that may be possessed by each of the groups represented by R W5 to R W7 include the substituents exemplified for the above-mentioned substituent W.
• the group represented by formula (A-1) is preferably a group represented by formula (A-2), since the response speed has a smaller electric field strength dependency.
• C2 represents a ring containing at least 3 carbon atoms which may have a substituent.
• the three carbon atoms included in the above C2 are the three carbon atoms clearly shown in formula (A-2).
• 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 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.
• 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.
• Preferred embodiments of the substituent that the above ring may have are the same as the substituent that the above ring C1 may have.
• W 2 and W 3 each independently represent an oxygen atom or a sulfur atom, and an oxygen atom is preferred in that the response speed has a smaller dependency on the electric field strength.
• the group represented by formula (A-2) is preferably a group represented by formula (C-1) or a group represented by formula (C-2) in that it has better quantum efficiency and response speed.
• Xc1 and Xc2 each independently represent an oxygen atom or a sulfur atom.
• Xc1 or Xc2 is an oxygen atom
• Xc1 and Xc2 are oxygen atoms.
• “manufacturability” refers to a property in which the performance of a photoelectric conversion element is unlikely to change even when the deposition rate of the photoelectric conversion film is changed during the production of the photoelectric conversion element, and from the viewpoint of production efficiency, excellent manufacturability is preferable.
• C3 represents an aromatic ring which may have a substituent.
• the aromatic ring may be either a monocyclic ring or a polycyclic 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 heterocycle, with an aromatic hydrocarbon ring being preferred.
• the aromatic ring represented by C3 is as described above, and 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, 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 above, 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 or a sulfur atom.
• X c3 and X c4 are oxygen atoms
• X c3 to X c5 are oxygen atoms.
• R c1 and R c2 each independently represent a hydrogen atom or a substituent.
• substituents include the groups exemplified as the substituent W above, and an alkyl group or an aryl group is preferable, and an alkyl group is more preferable.
• the alkyl group may be linear, branched, or cyclic, and is preferably linear.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
• the aryl group may be either a monocyclic or polycyclic ring, and is preferably a phenyl group.
• the aryl group may further have a substituent, and examples of the substituent include the groups exemplified by the substituent W.
• the compound represented by formula (1) is a compound represented by any one of formulas (1-1) to (1-4).
• a 1 , A 2 , R 1 , R 2 , Z 11 to Z 14 , Z 21 , Z 22 , XAr2 and Y 21 have the same meanings as A 1 , A 2 , R 1 and R 2 in formula (1), Z 11 to Z 14 in formula (Ar-1), Z 21 , Z 22 and XAr2 in formula (Ar-2), and Y 21 in formula (2).
• X 11 to X 14 each independently represent a sulfur atom or an oxygen atom.
• R 11 to R 13 , R 21 to R 23 , R 31 to R 33 , and R 41 to R 43 each independently represent a hydrogen atom or a substituent, provided that at least one of R 11 to R 13 is Rs, at least one of R 21 to R 23 is Rs, at least one of R 31 to R 33 is Rs, and at least one of R 41 to R 43 is Rs.
• R 11 to R 13 , R 21 to R 23 , R 31 to R 33 , and R 41 to R 43 include the groups exemplified for the above-mentioned substituent W, and the substituent represented by Rs is preferred. Rs is as described above.
• the molecular weight of the specific compound is preferably from 300 to 1,200, more preferably from 350 to 1,000, and even more preferably from 400 to 800. When the molecular weight is within the above range, the sublimation temperature of the specific compound is lowered, and it is presumed that the compound has excellent suitability for production.
• the specific compound has an ionization potential of -5.0 to -6.0 eV in a single film.
• the maximum absorption wavelength of the specific compound is preferably in the range of 400 to 600 nm, and more preferably in the range of 400 to 500 nm.
• the maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) by adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1.0.
• solvent chloroform
• the specific compound is evaporated and the value measured using the specific compound in a film state is regarded as the maximum absorption wavelength of the specific compound.
• the specific compounds are particularly useful as materials for photoelectric conversion films used in imaging devices, photosensors, 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, medicinal materials, and fluorescent diagnostic materials.
• the particular compound may be purified if necessary.
• methods for purifying the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, purification using an adsorbent such as activated carbon, and recrystallization purification.
• 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 contains an n-type organic semiconductor in addition to the specific compound.
• the n-type organic semiconductor is a compound different from the above specific compound.
• An n-type organic semiconductor is an acceptor organic semiconductor material (compound) that is an organic compound that has the property of easily accepting electrons.
• an n-type organic semiconductor is an organic compound that has a larger electron affinity when two organic compounds are used in contact with each other. In other words, 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; condensed aromatic carbon ring compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having at least one selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyridine ...
• condensed aromatic carbon ring compounds e.g.,
• Suitable aryl groups include arylazoles, imidazoles, thiazoles, etc.; polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives and oxadiazole 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; and the compounds described in paragraphs [0056] to [0057] of JP2006-100767A.
• fullerenes selected from the group consisting of fullerene and derivatives thereof are preferred.
• fullerenes include fullerene C60 , fullerene C70 , fullerene C76 , fullerene C78 , fullerene C80 , fullerene C82 , fullerene C84 , fullerene C90 , fullerene C96 , fullerene C240 , fullerene C540 , and mixed fullerenes.
• the fullerene derivative may be, for example, a compound in which a substituent is added to the fullerene.
• the substituent is preferably an alkyl group, an aryl group, or a heterocyclic group.
• the fullerene derivative is preferably a compound described in JP-A-2007-123707.
• 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 400 nm or less or in the range of 500 to 600 nm.
• the photoelectric conversion film preferably has a bulk heterostructure formed by mixing a specific compound with an n-type organic semiconductor.
• the bulk heterostructure is a layer in the photoelectric conversion film in which a specific compound and an n-type organic semiconductor are mixed and dispersed.
• a photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. The bulk heterostructure is described in detail in paragraphs [0013] to [0014] of JP 2005-303266 A.
• the difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 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 even more preferably 20 to 50 vol%.
• the content of fullerenes relative to the total content of n-type organic semiconductors is preferably 50 to 100 volume %, more preferably 80 to 100 volume %.
• Fullerenes may be used alone or in combination of two or more types.
• the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor is preferably 20 to 80 vol%, and more preferably 40 to 80 vol%.
• the content of the specific compound is preferably 10 to 75 vol%, and more preferably 15 to 50 vol%. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor contained as desired.
• the total content of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor relative to the total mass of the photoelectric conversion film is 90 to 100 volume %, preferably 95 to 100 volume %, and more preferably 99 to 100 volume %.
• the photoelectric conversion film preferably contains a p-type organic semiconductor in addition to the specific compound.
• the p-type organic semiconductor is a compound different from the above specific compound.
• a p-type organic semiconductor is a donor organic semiconductor material (compound) that has the property of easily donating electrons.
• a p-type organic semiconductor is an organic compound that has a smaller ionization potential when two organic compounds are used in contact with each other.
• the p-type organic semiconductor may be used alone or in combination of two or more.
• 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. 2011-176259, compounds described in paragraphs [0064] to [0065] of JP-A No.
• TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
• TPD 4,4'-bis[N-(naphthyl)-N-phen
• pyrazoline compounds e.g., thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothi eno[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 JP2018-014474A, compounds described in paragraphs [0043] to [0045] of WO2016/194630, compounds described in paragraphs [0025] to [0037] and [0099] to [0109] of WO2017/159684, compounds described in paragraphs [0025] to [0037] and [0099] to [0109] of JP
• the p-type organic semiconductor includes compounds described in JP-A-2022-123944, compounds described in JP-A-2022-122839, compounds described in JP-A-2022-120323, compounds described in JP-A-2022-120273, compounds described in JP-A-2022-115832, compounds described in JP-A-2022-108268, compounds described in JP-A-2023-005703, compounds described in JP-A-2022-100258, compounds described in JP-A-2022-181226, compounds described in JP-A-2022-27575, and compounds described in JP-A-2021-163968.
• Examples of p-type organic semiconductors include compounds having a smaller ionization potential than n-type organic semiconductors. If this condition is satisfied, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as the p-type organic semiconductor compound are given below.
• the difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.
• the p-type organic semiconductor material 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 even more preferably 25 to 50 vol%.
• the photoelectric conversion film containing a specific compound is a non-luminescent film, and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode).
• a non-luminescent film means 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 preferably contains a dye in addition to the specific compound.
• the dye is a compound different from the above 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, phenothiazine dyes,
• acridinone dyes diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complexes, WO2020/013246, WO2022/168856, JP2023-10305A, and JP2023-10299A described imidazoquinoxaline dyes, acceptor-donor-acceptor type dyes in which two acidic nuclei are bonded to a donor, and donor-acceptor-donor type dyes in which two donors are bonded to an acceptor, etc. Among them, in terms of maximum absorption wavelength, cyanine dyes, imidazoquinoxaline dyes, or acceptor-donor-acceptor type dyes are preferred.
• the maximum absorption wavelength of the dye is preferably in the visible light region, more preferably in the wavelength range of 400 to 650 nm, and even more preferably in the wavelength range of 450 to 650 nm.
• the dyes may be used alone or in combination of two or more.
• the photoelectric conversion film may be formed, for example, by a dry film formation method.
• the dry film formation method include physical vapor deposition methods such as vapor deposition (particularly vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), and CVD (Chemical Vapor Deposition) methods such as plasma polymerization, and the vacuum deposition method is preferred.
• the manufacturing conditions such as the degree of vacuum and the deposition temperature can be set according to a conventional method.
• the thickness of the photoelectric conversion film is preferably 10 to 1000 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); thin metal films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, nanocarbon materials such as carbon nanotubes and graphene, and the like. In terms of high conductivity and transparency, conductive metal oxides are preferred.
• 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 thinned.
• An increase in light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability.
• the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.
• the lower electrode 11 may be made transparent or may be made non-transparent and reflect light.
• Materials constituting the lower electrode 11 include, for example, conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (for example, 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 tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and in
• the method for forming the electrodes can be appropriately selected depending on the electrode material. 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 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 between the conductive film and the transparent conductive film in addition to the photoelectric conversion film.
• the intermediate layer may be, for example, a charge blocking film.
• the charge blocking film may be, for example, an electron blocking film or a hole blocking film.
• the electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used.
• polymeric materials can also be used as the electron blocking film. Examples of polymeric materials include polymers of phenylenevinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.
• the electron blocking film may be made up of multiple films.
• the electron blocking film may be made 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, and the quantum efficiency is increased.
• examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, copper chromium oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, copper gallium oxide, copper strontium oxide, niobium oxide, molybdenum oxide, copper indium oxide, silver indium oxide, and iridium oxide.
• the hole blocking film is an acceptor organic semiconductor material (compound), and the above-mentioned n-type organic semiconductor can be used.
• the hole blocking film may be made up of multiple films.
• Methods for manufacturing the charge blocking film include, for example, a dry film formation method and a wet film formation method.
• dry film formation methods include a vapor deposition method and a sputtering method.
• the vapor deposition method may be either a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method, with physical vapor deposition methods such as vacuum vapor deposition being preferred.
• wet film formation methods include an inkjet method, a spray method, a nozzle print method, a spin coat method, a dip coat method, a cast method, a die coat method, a roll coat method, a bar coat method, and a gravure coat method, with the inkjet method being preferred in terms of high-precision patterning.
• each of the charge blocking films is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm.
• the photoelectric conversion element may further include a substrate.
• the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate.
• the conductive film, the photoelectric conversion film, and the transparent conductive film are usually laminated in this order on the substrate.
• the photoelectric conversion element may further include a sealing layer.
• the performance of photoelectric conversion materials may be significantly deteriorated in the presence of deterioration factors such as water molecules, etc. Therefore, the deterioration can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer such as ceramics such as dense metal oxide, metal nitride, or metal nitride oxide, which does not allow water molecules to penetrate, or diamond-like carbon (DLC).
• a sealing layer such as ceramics such as dense metal oxide, metal nitride, or metal nitride oxide, which does not allow water molecules to penetrate, or diamond-like carbon (DLC).
• the sealing layer is described, for example, in paragraphs [0210] to [0215] of JP-A-2011-082508, the contents of which are incorporated herein by reference.
• 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 is usually configured with 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. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
• the photoelectric conversion element include, for example, a photocell and an optical sensor, and the photoelectric conversion element of the present invention is preferably used as an optical sensor.
• the photoelectric conversion element may be used alone, or the photoelectric conversion element may be used as a line sensor in which the photoelectric conversion elements are arranged in a straight line, or as a two-dimensional sensor in which the photoelectric conversion elements are arranged on a plane.
• the photoelectric conversion element was evaluated for quantum efficiency when receiving light having a wavelength of 460 nm (blue light), response speed, the electric field strength dependency of the response speed, and manufacturability by the following methods.
• 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 lower electrode 11 (thickness: 30 nm), and a 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).
• each specific compound or each comparative compound shown in Table 1 an n-type organic semiconductor (fullerene (C 60 )), and a p-type organic semiconductor were co-evaporated by vacuum evaporation onto the electron blocking film 16A so as to have a thickness of 80 nm in terms of a single layer, thereby forming a photoelectric conversion film 12 having a bulk heterostructure of 240 nm.
• the film formation speed of the photoelectric conversion film 12 was set to 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 aluminum oxide (Al 2 O 3 ) layer was formed thereon by atomic layer chemical vapor deposition (ALCVD), and the resulting laminate was heated at 150° C. for 30 minutes in a glove box to obtain a photoelectric conversion element.
• the dark current was measured by the following method. A voltage was applied to the lower and upper electrodes of each photoelectric conversion element to obtain an electric field strength of 2.5 ⁇ 10 5 V/cm, and the current value in a dark place (dark current) was measured. As a result, it was confirmed that the dark current in each photoelectric conversion element was 50 nA/cm 2 or less, which is a sufficiently low dark current.
• Quantum efficiency (relative ratio) is 1.6 or more.
• Relative response speed is less than 0.5
• B Relative response speed is 0.5 or more and less than 1.0
• C Relative response speed is 1.0 or more and less than 1.5
• D Relative response speed is 1.5 or more
• the photoelectric conversion element (B) and the photoelectric conversion element (A) in the numerator and denominator are photoelectric conversion elements prepared using the same material. The closer the value of the relative ratio B/A is to 1, the less the performance of the photoelectric conversion element is likely to deteriorate even when the film formation speed is increased, that is, the more excellent the manufacturability.
• Formula (S4): Relative ratio B/A (photoelectric conversion efficiency of photoelectric conversion element (B))/(photoelectric conversion efficiency of photoelectric conversion element (A))
• the column “Formula (A-2)” indicates that, for a specific compound, when A 1 and A 1 are a group represented by formula (A-2), "A” is entered, and otherwise, "B” is entered.
• the column “Formula (C-1) or Formula (C-2)” indicates that, for a specific compound, when A 1 and A 1 are groups represented by formula (C-1), they are marked as "A(C-1),” when A 1 and A 1 are groups represented by formula (C-2), they are marked as "A(C-2),” and when they are not, they are marked as "B.”
• the "Requirement X” column indicates that a specific compound satisfies the above-mentioned requirement X, and indicates "B” otherwise.
• the column “Formula (1-1) to Formula (1-4)” indicates the formula number to which the specific compound corresponds if the specific compound is represented by any of Formulas (1-1) to (1-4), and indicates "B” otherwise.

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