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  • 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
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  • 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
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  • 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
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  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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  • 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
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  • H10K85/649—Aromatic compounds comprising a hetero atom
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  • H10K85/649—Aromatic compounds comprising a hetero atom
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  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring

Definitions

• the present invention relates to a photoelectric conversion element, an imaging element, an optical sensor, and a compound.
• Patent Document 1 discloses a compound having a specific structure as a material for use in photoactive organic electronic components.
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S, represented by R Z2, may have a halogen atom or an etheric oxygen atom.
• the acyl group having 2 to 5 carbon atoms, represented by R Z2 may have a halogen atom.
• Substituent group S linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms, halogen atoms, and groups represented by -Si(R Si2 ) 3 .
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent group S may have a halogen atom or an etheric oxygen atom.
• R Si2 each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group S.
• the linear aliphatic hydrocarbon having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above substituent group S, represented by R Si2, may have a halogen atom or may have an etheric oxygen atom.
• R Z2 represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, an acyl group having 2 or 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from Substituent Group T, an aromatic ring group which may have a substituent selected from Substituent Group T, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group T, or a group represented by -Si(R Si3 ) 3 .
• Substituent group T linear aliphatic hydrocarbon groups having 1 or 2 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, halogen atoms, and groups represented by -Si(R Si3 ) 3 .
• R Si3 each independently represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the above-mentioned substituent group T, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group T.
• the photoelectric conversion film further contains an n-type organic semiconductor, The photoelectric conversion element according to any one of [1] to [7], wherein the photoelectric conversion film has a bulk heterostructure formed by mixing a compound represented by formula (1) described below with the n-type organic semiconductor.
• R Z2 represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from substituent group S, an acyl group having 2 to 5 carbon atoms, an aromatic ring group which may have a substituent selected from substituent group S, an aliphatic heterocyclic group which may have a substituent selected from substituent group S, or a group represented by -Si(R Si2 ) 3 .
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S, represented by R Z2, may have a halogen atom or an etheric oxygen atom.
• the acyl group having 2 to 5 carbon atoms, represented by R Z2 may have a halogen atom.
• Substituent group S linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms, halogen atoms, and groups represented by -Si(R Si2 ) 3 .
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent group S may have a halogen atom or an etheric oxygen atom.
• R Si2 each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above-mentioned substituent group S, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group S.
• the linear aliphatic hydrocarbon having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above substituent group S, represented by R Si2, may have a halogen atom or may have an etheric oxygen atom.
• R Z2 represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, an acyl group having 2 or 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from Substituent Group T, an aromatic ring group which may have a substituent selected from Substituent Group T, an aliphatic heterocyclic group which may have a substituent selected from Substituent Group T, or a group represented by -Si(R Si3 ) 3 .
• Substituent group T linear aliphatic hydrocarbon groups having 1 or 2 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, halogen atoms, and groups represented by -Si(R Si3 ) 3 .
• R Si3 each independently represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the above-mentioned substituent group T, or an aromatic ring group which may have a substituent selected from the above-mentioned substituent group T.
• the present invention it is possible to provide a photoelectric conversion element that is excellent in quantum efficiency and also in manufacturability. 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 is, 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 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 alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a secondary or
• Examples of the primary amino group (including anilino group), alkylthio group, arylthio group, heterocyclic thio group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, aryl or heterocyclic azo group, imido group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, carboxy group, phosphoric acid group, sulfonic acid group, hydroxy group, thiol group, acylamino group, carbamoyl group, ureido group, boronic acid group and primary amino group.
• each of the above groups may further have a substituent (for example, one or more groups among the above groups, etc.) if possible.
• a substituent for example, one or more groups among the above groups, etc.
• an alkyl group that 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, 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) aromatic ring structures condensed 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
• thienothiazole ring for example, thieno[2,3-d]thiazole ring, etc.
• benzothiadiazole ring benzodithiophene ring (for example, benzo[1,2-b:4,5-b']dithiophene ring, etc.), thienothiophene ring (for example, thieno[3,2-b]thiophene ring, etc.), thiazolothiazole ring (for example, thiazolo[5,4-d]thiazole ring, etc.), naphthodithiophene ring (for example, naphtho[2,3 [2,1-b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring, 1,8-dithiadicyclopenta[
• the type of substituent that the aromatic ring may have is, for example, the group exemplified as the substituent W.
• the number of the substituents may be 1 or more (for example, 1 to 4, etc.).
• aromatic ring group includes, for example, groups in which one or more (eg, 1 to 5, etc.) hydrogen atoms have been removed from the above-mentioned aromatic ring.
• aryl group includes, for example, a group obtained by removing one hydrogen atom 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 that is not aromatic, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic hetero ring.
• 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 a ⁇ -butyrolactone ring.
• aliphatic hydrocarbon ring group includes, for example, a group in which one or more hydrogen atoms (for example, 1 to 5, etc.) have been removed from a ring corresponding to an aliphatic hydrocarbon ring.
• aliphatic heterocyclic group includes, for example, a group in which one or more hydrogen atoms (for example, 1 to 5, etc.) have 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 photoelectric conversion film and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) described below (hereinafter also referred to as a "specific compound").
• the specific compound has one or more specific substituents represented by R Z2 at the donor site, and at least one of X 1 to X 3 is an oxygen atom, so that the intermolecular interaction of the specific compound is appropriately controlled, thereby suppressing excessive aggregation between the specific compounds, and allowing charge separation in the photoelectric conversion film to proceed efficiently, resulting in excellent quantum efficiency of the photoelectric conversion element.
• the acceptor moiety of the specific compound has a specific ring structure
• the donor moiety has a specific substituent represented by R Z2
• at least one of X 1 to X 3 is an oxygen atom, so that the heat resistance and sublimation temperature of the specific compound are appropriately controlled, thereby suppressing decomposition of the specific compound even when the deposition rate is increased, and as a result, the manufacturing suitability is also excellent.
• superiority in at least one of the quantum efficiency and manufacturability of the photoelectric conversion element is also 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).
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• X 1 to X 3 each independently represent a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, provided that at least one of X 1 to X 3 is an oxygen atom.
• R Z2 represents an aliphatic hydrocarbon group which may have a substituent, an acyl group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or a group represented by -Si(R Si ) 3 .
• the aliphatic hydrocarbon group represented by R 2 may contain a halogen atom or an etheric oxygen atom.
• the acyl group represented by R 2 may contain a halogen atom.
• Each R 4 Si independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent.
• the aliphatic hydrocarbon group represented by R 3 Si may contain a halogen atom or an etheric oxygen atom.
• A1 and A2 each independently represent a group represented by formula (A-1).
• C1 represents a ring containing at least two carbon atoms which may have a substituent.
• R W1 represents a hydrogen atom or a substituent.
• R W2 and R W3 each independently represent a cyano group, -SO 2 R W4 , -COOR W5 , or -COR W6 .
• R W4 , R W5 , and R W6 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 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.
• X 1 to X 3 each independently represent a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, provided that at least one of X 1 to X 3 is an oxygen atom.
• X 1 to X 3 are preferably a sulfur atom or an oxygen atom, and more preferably an oxygen atom.
• at least one is an oxygen atom, and it is preferable that two or more are oxygen atoms.
• the compound represented by formula (1) is preferably a compound represented by formula (1-1) to formula (1-5), more preferably a compound represented by formula (1-1) to formula (1-4), even more preferably a compound represented by formula (1-1) or a compound represented by formula (1-4), and particularly preferably a compound represented by formula (1-1).
• R 1 , R 2 , Z 1 to Z 6 , A 1 and A 2 have the same meanings as R 1 , R 2 , Z 1 to Z 6 , A 1 and A 2 in formula (1).
• X4 and X5 each independently represent a sulfur atom, a selenium atom, or a tellurium atom.
• X4 and X5 are preferably a sulfur atom.
• R Z1 represents a hydrogen atom or a substituent. Examples of the substituent represented by R Z1 include the substituents exemplified as the substituent W described above.
• the groups represented by the plurality of R 2 may be the same or different.
• the ring formed by combining two R 1 and Z2 with each other includes an aliphatic hydrocarbon ring and an aliphatic hetero ring.
• the number of ring members in the ring is not particularly limited, but is preferably 3 to 12, more preferably 4 to 6, and even more preferably 5.
• Examples of the heteroatom contained in the aliphatic heterocycle 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, with a sulfur atom, an oxygen atom or a nitrogen atom being preferred.
• R represents an aliphatic hydrocarbon group which may have a substituent, an acyl group which may have a substituent, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, or a group represented by -Si(R Si ) 3 .
• the aliphatic hydrocarbon group represented by R 2 may contain a halogen atom or an etheric oxygen atom.
• the acyl group represented by R 2 may contain a halogen atom.
• the aliphatic hydrocarbon group may have an etheric oxygen atom means that the aliphatic hydrocarbon group may have a divalent linking group represented by -O- in or at an end thereof.
• the aliphatic hydrocarbon group represented by R Z2 includes a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.
• the number of carbon atoms in the linear aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2.
• Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, a vinyl group, an allyl group, an ethynyl group, and a propargyl group, of which a methyl group, an ethyl group, an n-propyl group, a vinyl group, an ethynyl group, or a propargyl group is preferred, a methyl group, an ethyl group, or an ethynyl group is more preferred, and a methyl group or an ethyl group is even more preferred.
• the number of carbon atoms in the branched aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, even more preferably 3 to 6, and particularly preferably 3 or 4.
• Specific examples include an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-butyloctyl group, a 2-hexyloctyl group, a 2-hexyldodecyl group, and a 2-octyldodecyl group, with an isopropyl group or a tert-butyl group being preferred.
• the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic.
• the number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6.
• Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a dicyclobutanyl group, a bicyclo[1.1.1]pentyl group, and a bicyclo[2.2.2]pentyl group, of which a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group is preferable, and a cyclopropyl group is more preferable.
• the aliphatic hydrocarbon group may have a halogen atom.
• the halogen atom that the aliphatic hydrocarbon group may have 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 aliphatic hydrocarbon group may have an etheric oxygen atom. Examples of the aliphatic hydrocarbon group having an etheric oxygen atom include a methoxy group, an ethoxy group, an isopropoxy group, a cyclopropoxy group, and a methoxyethyl group.
• Examples of the substituent that the aliphatic hydrocarbon group may have include the substituents exemplified by the above-mentioned substituent W. Of these, a substituent selected from the below-mentioned substituent group S is preferable, and a substituent selected from the below-mentioned substituent group T is more preferable.
• the hydrocarbon group contained in the acyl group which may have the above substituent and is represented by R Z2 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group contained in the acyl group may be linear, branched or cyclic.
• the number of carbon atoms in the aliphatic hydrocarbon group of the acyl group is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 4, and particularly preferably 1 or 2.
• the carbon atom include linear aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups, isopropyl, sec-butyl, iso-butyl, tert-butyl, neopentyl, 1-ethylpentyl, 2,6-dimethylheptyl, 1-butylheptyl, 1-hexylheptyl, 1-hexylundecyl, and and 1-octylundecyl group; and cyclic aliphatic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group
• a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
• the number of carbon atoms in the aromatic hydrocarbon group of the acyl group is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6.
• Specific examples include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, and a fluorenyl group, with a phenyl group being preferred.
• the acyl group preferably has 2 to 21 carbon atoms, more preferably 2 to 11 carbon atoms, further preferably 2 to 5 carbon atoms, and particularly preferably 2 or 3 carbon atoms.
• Examples of the acyl group 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 acyl group may have a halogen atom.
• Examples of the halogen atom that the acyl group may have include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
• Examples of the substituent that the acyl group may have include the substituents exemplified by the above-mentioned substituent W. Of these, a substituent selected from the substituent group S described below is preferable, and a substituent selected from the substituent group T described below is more preferable.
• the aromatic ring group which may have a substituent and is represented by R Z2 may be either a monocyclic ring or a polycyclic ring.
• 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 preferably has 5 to 20 ring members, more preferably 5 to 12 ring members, and even more preferably 5 to 8 ring members.
• the number of carbon atoms in the aromatic ring group 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, with a sulfur atom, an oxygen atom or a nitrogen atom being preferred.
• aromatic ring group examples include aromatic hydrocarbon ring 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 a
• 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.
• the substituent that the aromatic ring group may have include the substituents exemplified by the above-mentioned substituent W. Of these, a substituent selected from the substituent group S described below is preferable, and a substituent selected from the substituent group T described below is more preferable.
• 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 Z2 which may have a substituent may be either a monocyclic or polycyclic ring.
• the aliphatic heterocyclic group preferably has 6 to 20 ring members, more preferably 6 to 12 ring members, and even more preferably 6 to 8 ring members.
• the aliphatic heterocyclic group preferably has 1 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 4 to 10 carbon atoms.
• heteroatom contained in the aliphatic 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, with a sulfur atom, an oxygen atom or a nitrogen atom being preferred.
• Examples of the aliphatic heterocyclic group include a pyrrolidine ring group, an oxolane ring group, a thiolane ring group, a piperidine ring group, a tetrahydrofuran ring group, a tetrahydropyran ring group, a thiane ring group, a piperazine ring group, a morpholine ring group, a quinuclidine ring group, a pyrrolidine ring group, an azetidine ring group, an oxetane ring group, an aziridine ring group, a dioxane ring group, a pentamethylene sulfide ring group, and a ⁇ -butyrolactone ring group, and a piperidine ring group is preferable.
• Examples of the substituent that the aliphatic heterocyclic group may have include the substituents exemplified by the above-mentioned substituent W. Of these, a substituent selected from the below-mentioned substituent group S is preferable, and a substituent selected from the below-mentioned substituent group T is more preferable.
• the number of the substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3.
• R.sub.Si each independently represents an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent.
• the aliphatic hydrocarbon group which may have a substituent and is represented by R 3 Si may have a halogen atom or an etheric oxygen atom.
• the definition and preferred embodiments of the aliphatic hydrocarbon group represented by R Si which may have a substituent are the same as those of the aliphatic hydrocarbon group represented by R Z2 which may have a substituent
• the definition and preferred embodiments of the aromatic ring group represented by R Si which may have a substituent are the same as those of the aromatic ring group represented by R Z2 which may have a substituent.
• the group represented by -Si(R Si ) 3 is preferably a group represented by -Si(R Si2 ) 3.
• R Si2 each independently represent a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the substituent group S described below, or an aromatic ring group which may have a substituent selected from the substituent group S described below.
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above substituent group S, represented by R Si2, may have a halogen atom or may have an etheric oxygen atom.
• the group represented by -Si(R Si ) 3 is more preferably a group represented by -Si(R Si3 ) 3.
• R Si3 each independently represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the substituent group T described below, or an aromatic ring group which may have a substituent selected from the substituent group T described below.
• Specific examples of the group represented by -Si(R Si ) 3 include a trimethylsilyl group, a triethylsilyl group, a dimethylisopropylsilyl group, a diethylisopropylsilyl group, a cyclohexyldimethylsilyl group, a dimethylphenylsilyl group, and a tert-butyldimethylsilyl group, with a trimethylsilyl group or a triethylsilyl group being preferred, and a trimethylsilyl group being more preferred.
• R Z2 is preferably a group selected from the substituent group R1.
• Substituent group R1 linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms which may have a substituent selected from substituent group S described later, acyl groups having 2 to 5 carbon atoms, aromatic ring groups which may have a substituent selected from substituent group S described later, aliphatic heterocyclic groups which may have a substituent selected from substituent group S described later, and groups represented by -Si(R Si2 ) 3 .
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the substituent group S may have a halogen atom or an etheric oxygen atom.
• R Z2 is more preferably a group selected from the substituent group R2.
• Substituent group R2 linear aliphatic hydrocarbon groups having 1 or 2 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, acyl groups having 2 or 3 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms which may have a substituent selected from substituent group T described later, aromatic ring groups which may have a substituent selected from substituent group T described later, aliphatic heterocyclic groups which may have a substituent selected from substituent group T described later, and groups represented by -Si(R Si3 ) 3 .
• Substituent group S linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms, halogen atoms, and groups represented by -Si(R Si2 ) 3 .
• linear aliphatic hydrocarbon group having 1 to 3 carbon atoms in the substituent group S include a methyl group, an ethyl group, an n-propyl group, a vinyl group, an allyl group, an ethynyl group, and a propargyl group, and a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
• branched aliphatic hydrocarbon group having 3 or 4 carbon atoms in the substituent group S include an isopropyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.
• the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the above-mentioned Substituent Group S may be either a monocyclic or polycyclic ring, and is preferably a monocyclic ring.
• cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, with a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group being preferred, and a cyclopropyl group being more preferred.
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the above-mentioned Substituent Group S may have a halogen atom.
• the halogen atom which the aliphatic hydrocarbon group in the above-mentioned substituent group S may have include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom or a chlorine atom being preferred.
• the aliphatic hydrocarbon group in the above-mentioned Substituent Group S may have an etheric oxygen atom.
• Examples of the aliphatic hydrocarbon group in the Substituent Group S having an etheric oxygen atom include a methoxy group, an ethoxy group, a methoxyethyl group, an isopropoxy group, and a cyclopropoxy group, and a methoxy group is preferable.
• 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 Si2 each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from Substituent Group S, or an aromatic ring group which may have a substituent selected from Substituent Group S.
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent selected from the above substituent group S, represented by R Si2, may have a halogen atom or may have an etheric oxygen atom.
• R Si2 substituent selected from the above substituent group S
• R Si2 may have a halogen atom or may have an etheric oxygen atom.
• the definition and preferred embodiments of the group represented by -Si(R Si2 ) 3 in the above-mentioned substituent group S are the same as those of the group represented by -Si(R Si2 ) 3 in R Z2 .
• the substituent selected from the substituent group S is a substituent selected from the substituent group T.
• Substituent group T linear aliphatic hydrocarbon groups having 1 or 2 carbon atoms, branched aliphatic hydrocarbon groups having 3 or 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, halogen atoms, and groups represented by -Si(R Si3 ) 3 .
• linear aliphatic hydrocarbon group having 1 or 2 carbon atoms in the above-mentioned substituent group T include a methyl group and an ethyl group, with a methyl group being preferred.
• branched aliphatic hydrocarbon group having 3 or 4 carbon atoms in the substituent group T include an isopropyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group, with an isopropyl group or a tert-butyl group being preferred, and an isopropyl group being more preferred.
• the cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms in the above-mentioned substituent group T may be either a monocyclic or polycyclic ring, and is preferably a monocyclic ring.
• Specific examples of the cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and a cyclopropyl group is preferred.
• the halogen atoms in the above-mentioned substituent group T include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom or a chlorine atom being preferred.
• R Si3 each independently represents a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from Substituent Group T, or an aromatic ring group which may have a substituent selected from Substituent Group T.
• the definition and preferred embodiments of the group represented by -Si(R Si3 ) 3 in the above-mentioned substituent group T are the same as those of the group represented by -Si(R Si3 ) 3 in R Z2 .
• a 1 and A 2 each independently represent a group represented by formula (A-1).
• W 1 represents an oxygen atom, a sulfur atom, ⁇ NR W1 or ⁇ CR W2 R W3 .
• R W1 represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified as the substituent W above.
• R W4 to R W6 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 W4 to R W6 may have include the groups exemplified for the substituent W above.
• the aliphatic hydrocarbon group may be linear, branched or cyclic, and preferably has 1 to 3 carbon atoms.
• the aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and is preferably a phenyl 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.
• heteroatom contained in the aliphatic 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, with a sulfur atom, an oxygen atom or a nitrogen atom being preferred.
• Examples of the aliphatic heterocycle constituting the aliphatic heterocyclic group include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydrofuran ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, a pyrrolidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, a pentamethylene sulfide ring, and ⁇ -butyrolactone.
• W 1 is preferably an oxygen atom, a sulfur atom or ⁇ CR W2 R W3 , more preferably an oxygen atom or a sulfur atom, and even more preferably an oxygen atom.
• C1 represents a ring containing at least two carbon atoms which may have a substituent.
• the two carbon atoms contained in the above 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 contained in the ring is preferably 0 to 10, and more preferably 0 to 5.
• Examples of the substituent that the ring may have include the groups exemplified as the substituent W above.
• a halogen atom, an alkyl group, an aromatic ring group or a silyl group is preferable, and a halogen atom or 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 10 carbon atoms, and more preferably has 1 to 3 carbon atoms.
• 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, etc.
• 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, 3-phenyl-2,4-thiazolidinedione, and the like.
• 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, 3,3-dimethyl-1-indanone, and the like.
• Benzofuran-3-(2H)-one nucleus for example, benzofuran-3-(2H)-one, etc.
• a 1 and A 2 are each independently a group represented by formula (A-2).
• W2 and W3 each independently represent an oxygen atom, a sulfur atom, ⁇ NR W1 or ⁇ CR W2 R W3 .
• the definitions and preferred embodiments of R W1 , R W2 and R W3 are as described above.
• 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.
• A1 and A2 are each preferably a group represented by the following formula (C-1) or a group represented by the following formula (C-2), and further preferably a group represented by the following formula (C-2).
• R X1 represents a hydrogen atom or a substituent. Examples of the substituent represented by R X1 include the groups exemplified as the substituent W above.
• R 1 X2 and R 1 X3 each independently represent a cyano group, —SO 2 R 1 X4 , —C( ⁇ O)OR 1 X5 or —C( ⁇ O)R 1 X6 .
• R X4 to R X6 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 definitions and preferred embodiments of each of the groups represented by R X4 to R X6 are the same as those of each of the groups represented by R W4 to R W6 described above.
• At least one of R 1 X2 and R 1 X3 is preferably a cyano group, and it is more preferable that R 1 X2 and R 1 X3 are a cyano group.
• Xc1 and Xc2 are an oxygen atom, and it is more preferable that Xc1 and Xc2 are an oxygen atom.
• C3 represents an aromatic ring which may have a substituent.
• 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 a monocyclic ring or a polycyclic ring.
• 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 particularly 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, a sulfur atom, ⁇ NR 2 X1 or ⁇ CR 2 R 2 X3 .
• the definitions and preferred embodiments of R X1 to R X3 are as described above.
• X c3 to X c5 are preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom. Of these, it is preferable that at least two of X c3 to X c5 are oxygen atoms, and it is more preferable that all of them are oxygen atoms.
• R c1 and R c2 each independently represent a hydrogen atom or a substituent.
• substituents include the groups exemplified as the above-mentioned substituent W, 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, but 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 carbon atom.
• the aryl group may be either a monocyclic or polycyclic ring, and is preferably a phenyl group.
• the phenyl group may further have a substituent, and examples of the substituent include the groups exemplified by the substituent W.
• the specific compound is preferably a compound represented by formula (1-A2), more preferably a compound represented by formula (1-C1) or a compound represented by formula (1-C2), and even more preferably a compound represented by formula (1-C2).
• formula (1-A2), formula (1-C1), and formula (1-C2) a plurality of groups represented by the same symbol may be the same or different, but are preferably the same.
• a in the specific compounds exemplified above represents one of the following groups.
• the molecular weight of the specific compound is preferably from 400 to 1,400, more preferably from 480 to 1,000, and even more preferably from 520 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 700 nm, and more preferably in the range of 450 to 650 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.,
• Examples of the compounds include 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'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl ( ⁇ -NPD), the compounds described in paragraphs [0128] to [0148] of JP-A No. 2011-228614, the compounds described in paragraphs [0052] to [0063] of JP-A No. 2011-176259, the compounds described in paragraphs [0052] to [0063] of JP-A No.
• TPD N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
• ⁇ -NPD 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl
• 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,
• 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); metal thin 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, and nanocarbon materials such as carbon nanotubes and graphene. 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. Furthermore, polymeric materials can also be used as the electron blocking film. Examples of the polymeric material 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 specific compounds used in the photoelectric conversion film and the comparative compounds used as comparative examples are shown below.
• the compounds (1-1) to (1-28), (2-1) to (2-8), (3-1) to (3-7), (4-1) to (4-6) and (5-1) to (5-9) are all specific compounds of the present invention, and the compounds (C-1) to (C-11) are all comparative compounds for comparison.
• the obtained compound was used to prepare a photoelectric conversion element (A) having the configuration shown in Fig. 2.
• 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).
• 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) (film thickness: 10 nm).
• an aluminum oxide (Al 2 O 3 ) layer was formed thereon by atomic layer chemical vapor deposition (ALCVD) to produce each photoelectric conversion element (A).
• the dark current was measured by the following method. A voltage was applied to the lower and upper electrodes of each photoelectric conversion element (A) so as to obtain 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 in each photoelectric conversion element (A) was 50 nA/cm 2 or less, which is a sufficiently low dark current.
• the quantum efficiency of each photoelectric conversion element (A) was evaluated by the following method. A voltage was applied to each photoelectric conversion element (A) so that the electric field intensity was 2.0 ⁇ 10 5 V/cm. Then, light was irradiated from the upper electrode (transparent conductive film) side to perform IPCE (incident photon-to-current conversion efficiency) measurement, and the values of each photoelectric conversion efficiency (external quantum efficiency) at wavelengths of 460 nm and 600 nm were extracted. The photoelectric conversion efficiency was measured using a constant energy quantum efficiency measurement device manufactured by Optel. The amount of light irradiated was 50 ⁇ W/cm 2 . Using the photoelectric conversion efficiency of each photoelectric conversion element (A) thus obtained, the relative ratio of quantum efficiency was calculated at each wavelength according to formula (S1). From the obtained values, the quantum efficiency was evaluated according to the following evaluation criteria.
• the values of the photoelectric conversion efficiency at the same wavelength were used as the numerator and denominator.
• each photoelectric conversion element (A) was evaluated by the following method. A voltage was applied to each photoelectric conversion element (A) so that the intensity was 2.0 ⁇ 10 5 V/cm. Then, the LED (light emitting diode) was turned on instantaneously to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 580 nm was measured with an oscilloscope, and the rise time from 0% signal intensity to 97% signal intensity was measured. Using the rise time at a wavelength of 580 nm of each obtained photoelectric conversion element (A), the relative response speed was calculated according to formula (S2). From the obtained value, the response speed was evaluated according to the following evaluation criteria.
• 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 and less than 2.5
• E Relative response speed is 2.5 or more
• ⁇ Evaluation of the response speed dependence on electric field strength> For each photoelectric conversion element (A), the dependence of the response speed on the electric field strength was evaluated by the following method. In ⁇ Evaluation of response speed>, the rise time at an applied voltage of 7.5 ⁇ 10 4 V/cm was measured in the same manner as above, except that the voltage applied to each photoelectric conversion element (A) was changed to 7.5 ⁇ 10 4 V/cm. The rise time of each photoelectric conversion element (A) at a wavelength of 580 nm at each applied voltage was used to calculate the relative rise time according to formula (S3). From the obtained values, the electric field strength dependency of the response speed was evaluated according to the following evaluation criteria.
• Photoelectric conversion elements (B) of each Example or Comparative Example were produced in the same manner as for the photoelectric conversion element (A), except that the deposition rate of the photoelectric conversion film 12 was set to 3.0 ⁇ /sec.
• the photoelectric conversion efficiency of the obtained photoelectric conversion element (B) was measured in the same manner as in ⁇ Evaluation of quantum efficiency (external quantum efficiency)>.
• the relative ratio B/A of the photoelectric conversion efficiencies at 600 nm of the photoelectric conversion element (A) and the photoelectric conversion element (B) having the same configuration as the example or comparative example was calculated according to the formula (S4).
• the manufacturability was evaluated from the obtained value according to the following evaluation criteria.
• Example 1-11 From a comparison of Example 1-11 with Examples 1-1 to 1-10, it was confirmed that when A 1 and A 2 in formula (1) are groups represented by formula (C-2), the production efficiency is superior.
• Examples 1-13, 1-23 to 1-25, and 1-59 with other Examples it was confirmed that when R Z2 in formula (1) is a group selected from the above-mentioned substituent group R1, the quantum efficiency, response speed, the electric field strength dependence of the response speed, and production suitability are more excellent, and when R Z2 is a group selected from the substituent group R2, the production suitability is further excellent.
• Equation (S5): Relative ratio of quantum efficiency (Photoelectric conversion efficiency of each photoelectric conversion element (C)) / (Photoelectric conversion efficiency of photoelectric conversion element (C) of Comparative Example 2-10)
• AA The relative ratio of quantum efficiency is 1.6 or more.
• A The relative ratio of quantum efficiency is 1.4 or more and less than 1.6.
• B The relative ratio of quantum efficiency is 1.2 or more and less than 1.4.
• C The relative ratio of quantum efficiency is 1.0 or more and less than 1.2.
• D The relative ratio of quantum efficiency is 0.8 or more and less than 1.0.
• E The relative ratio of quantum efficiency is less than 0.8.
• ⁇ Response speed evaluation> The rise time of the obtained photoelectric conversion element (C) at a wavelength of 580 nm was measured in the same manner as in ⁇ Evaluation of response speed> in [Test X]. The rise time at a wavelength of 580 nm of each of the obtained photoelectric conversion elements (C) was used to calculate the relative response speed according to formula (S6). From the obtained value, the response speed was evaluated according to the following evaluation criteria.
• 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 and less than 2.5
• E Relative response speed is 2.5 or more
• Photoelectric conversion elements having the configurations of the respective Examples and Comparative Examples were evaluated for manufacturability by the following method.
• Photoelectric conversion elements (D) of each Example or Comparative Example were produced in the same manner as for the photoelectric conversion element (C), except that the deposition rate of the photoelectric conversion film 12 was set to 3.0 ⁇ /sec.
• the photoelectric conversion efficiency of the obtained photoelectric conversion element (D) was measured in the same manner as in ⁇ Evaluation of quantum efficiency (external quantum efficiency)>.
• the photoelectric conversion efficiency ratio D/C was calculated according to the formula (S8) using the measured values of the photoelectric conversion efficiency at 600 nm of the photoelectric conversion element (C) and the photoelectric conversion element (D) having the same configuration as the example or comparative example.
• the manufacturability was evaluated from the obtained value according to the following evaluation criteria. The closer the value of the relative ratio D/C is to 1, the less the characteristics of the photoelectric conversion element are likely to deteriorate when the film formation rate is increased, that is, the more excellent the manufacturability is.
• Example 2-28 From a comparison of Example 2-28 with Examples 2-20 to 2-25, it was confirmed that when R Z2 is a group selected from the above-mentioned substituent group R1, the quantum efficiency, response speed, electric field strength dependency of the response speed, and production suitability are more excellent.

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