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  • 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
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  • 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
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  • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
  • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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  • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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  • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

• the present invention relates to a photoelectric conversion element, an image sensor, an optical sensor, and a compound.
• Patent Document 1 discloses a photoelectric conversion element containing a specific compound as an electron acceptor material.
• an object of the present invention is to provide a photoelectric conversion element that has excellent quantum efficiency when receiving blue light.
• Another object of the present invention is to provide an image sensor, an optical sensor, and a compound related to the photoelectric conversion element.
• Ar is a group represented by the below-mentioned formula (Ar-1) or the below-mentioned formula (Ar-2).
• Any of [1] to [3], wherein the compound represented by formula (1) above includes a compound represented by any of formulas (2-1) to (2-7) described below.
• Rs is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a halogen atom, or a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms which may have a halogen atom.
• the photoelectric conversion element according to [4] which is selected from the group consisting of an aromatic ring group having 4 to 10 carbon atoms which may have a group.
• the group represented by the above formula (A-1) is a group represented by the below-mentioned formula (C-1) or the below-mentioned formula (C-2), [1] to [6] ]
• the photoelectric conversion film further includes an n-type organic semiconductor, Any one of [1] to [7], wherein the photoelectric conversion film has a bulk heterostructure formed by a mixture of the compound represented by the formula (1) and the n-type organic semiconductor.
• the photoelectric conversion according to any one of [1] to [11] which has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. element.
• An imaging device comprising the photoelectric conversion element according to any one of [1] to [12].
• [15] A compound represented by formula (1) described below.
• [16] The compound according to [15], wherein the compound represented by formula (1) above is a compound represented by formula (2) described below.
• [17] The compound according to [15] or [16], wherein Ar is a group represented by the below-mentioned formula (Ar-1) or the below-mentioned formula (Ar-2).
• Ar is a group represented by the below-mentioned formula (Ar-1) or the below-mentioned formula (Ar-2).
• Any of [15] to [17], wherein the compound represented by the above formula (1) includes a compound represented by any of the formulas (2-1) to (2-7) described below.
• Rs is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a halogen atom, or a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms which may have a halogen atom; Aliphatic hydrocarbon group, cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a halogen atom, alkoxy group having 1 to 3 carbon atoms which may have a substituent, and substituted
• the compound according to [18] which is selected from the group consisting of aromatic ring groups having 4 to 10 carbon atoms which may have a group.
• a 1 and A 2 are groups represented by formula (A-1) described below.
• the group represented by the above formula (A-1) is a group represented by the below-mentioned formula (C-1) or the below-mentioned formula (C-2), [15] to [20] The compound according to any one of ].
• the present invention it is possible to provide a photoelectric conversion element that has excellent quantum efficiency when receiving blue light. Further, according to the present invention, it is possible to provide an image sensor, an optical sensor, and a compound related to the photoelectric conversion element.
• FIG. 1 is a schematic cross-sectional view showing one configuration example of a photoelectric conversion element.
• FIG. 1 is a schematic cross-sectional view showing one configuration example of a photoelectric conversion element.
• the hydrogen atom may be a light hydrogen atom (normal hydrogen atom) or a deuterium atom (eg, a double hydrogen atom).
• substituents, linking groups, etc. hereinafter also referred to as “substituents, etc." indicated by specific symbols, or when multiple substituents, etc. are specified at the same time, each This means that the substituents and the like may be the same or different. This point also applies to the definition of the number of substituents, etc.
• the "substituent” includes a group exemplified by the substituent W described below.
• the substituent W in this specification will be described.
• the substituent W is, for example, a halogen atom (for example, 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 (cycloalkenyl and bicycloalkenyl groups), alkynyl groups, aryl groups, heteroaryl groups (heterocyclic groups), cyano groups, nitro groups, alkoxy groups, aryloxy groups, silyl groups, silyloxy groups, heterocyclicoxy groups, acyloxy groups , carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, secondary or tertiary amino group (including anilino group), alkylthio group, aryl
• each of the above-mentioned groups may further have a substituent (for example, one or more of the above-mentioned groups), if possible.
• a substituent for example, one or more of the above-mentioned groups
• 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 in the substituent W is, for example, 1 to 20.
• the number of atoms other than hydrogen atoms in the substituent W is, for example, 1 to 30.
• the specific compounds mentioned below include a carboxy group, a salt of a carboxy group, a salt of a phosphoric acid group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, and a ureido group as substituents. , a boronic acid group (-B(OH) 2 ) and/or a primary amino group.
• the aliphatic hydrocarbon group may be linear, branched, or cyclic.
• Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.
• the alkyl group may be linear, branched or cyclic. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group and cyclopentyl group. Further, the alkyl group may be any of a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group, and may have a cyclic structure of these as a partial structure.
• examples of the substituent which the alkyl group may have include the groups exemplified by the substituent W, and an aryl group (preferably having 6 to 18 carbon atoms). , more preferably 6 carbon atoms), a heteroaryl group (preferably 5 to 18 carbon atoms, more preferably 5 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom).
• the alkyl group moiety in the alkoxy group is preferably the above alkyl group.
• the alkyl group moiety in the alkylthio group is preferably the above alkyl group.
• examples of the substituent which the alkoxy group may have are the same as those for the alkyl group which may have a substituent.
• examples of the substituent which the alkylthio group may have are the same as those for the alkyl group which may have a substituent.
• the alkenyl group may be linear, branched, or cyclic.
• the alkenyl group preferably has 2 to 20 carbon atoms.
• examples of the substituent which the alkenyl group may have are the same as those for the alkyl group which may have a substituent.
• an alkynyl group may be linear, branched, or cyclic.
• the number of carbon atoms in the alkynyl group is preferably 2 to 20.
• examples of the substituent which the alkynyl group may have are the same as those for the alkyl group which may have a substituent.
• the aromatic ring or the aromatic ring constituting the aromatic ring group may be either monocyclic or polycyclic (eg, 2 to 6 rings, etc.).
• a monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as a ring structure.
• a polycyclic (eg, 2-6 rings, etc.) aromatic ring is an aromatic ring in which a plurality of (eg, 2-6, etc.) aromatic ring structures are condensed as a ring structure.
• the number of ring members in the aromatic ring is preferably 5 to 15.
• the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle.
• the number of heteroatoms it has as ring member atoms is, for example, 1 to 10.
• the heteroatoms include nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, phosphorus atom, silicon atom, and 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.
• aromatic heterocycle examples include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and a triazine ring (for example, a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring).
• tetrazine ring e.g., 1,2,4,5-tetrazine ring, etc.
• quinoxaline ring pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, benzopyrrole ring, benzofuran ring, benzothiophene ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, naphtopyrrole ring, naphthofuran ring, naphthothiophene ring, naphthoimidazole ring, naphthoxazole ring, 3H-pyrrolidine ring, pyrroloimidazole ring (e.g., 5H- pyrrolo[1,2-a]imidazole ring, etc.), imidazoxazole ring (e.g., imidazo[2,
• examples of the type of substituent which the aromatic ring may have include the groups exemplified by the substituent W.
• the number of substituents may be 1 or more (eg, 1 to 4, etc.).
• the aromatic ring group includes, for example, a group obtained by removing one or more (eg, 1 to 5, etc.) hydrogen atoms from the above aromatic ring.
• the term aryl group includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic hydrocarbon ring among the above aromatic rings.
• heteroaryl group includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic heterocycle among the above-mentioned aromatic rings.
• the arylene group includes, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic hydrocarbon ring among the above aromatic rings.
• the term “heteroarylene group” includes, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the above-mentioned aromatic rings.
• Aromatic ring groups that may have substituents that may have substituents, aryl groups that may have substituents, heteroaryl groups that may have substituents, arylene groups that may have substituents, and
• examples of the types of substituents that these groups may have include the groups exemplified by the substituent W.
• the number of substituents may be 1 or more (eg, 1 to 4, etc.).
• the bonding direction of the divalent groups (eg, -CO-O-, etc.) described herein is not limited unless otherwise specified.
• Y in a compound represented by the formula "X-Y-Z" is -CO-O-
• the above compound has the formula "X-O-CO-Z" and "X-CO-O- Z" may be used.
• the general formula or structural formula representing the above compound is described only in the form of either the cis form or the trans form for convenience. There may be cases. Even in such a case, unless otherwise specified, the form of the above compound is not limited to either the cis form or the trans form, and the above compound may be either the cis form or the trans form. It may be a 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, wherein the photoelectric conversion film is a compound represented by formula (1) (hereinafter referred to as "specific compound”). (also called).
• specific compound a compound represented by formula (1)
• the inventors of the present invention speculate as follows.
• the compound disclosed in Patent Document 1 has a symmetrical structure in which thiophene, benzene, and thiophene are connected in the order of single bonds as donor sites, and therefore has a property of being easily aggregated by ⁇ - ⁇ stacking.
• FIG. 1 shows a schematic cross-sectional view of an embodiment of the photoelectric conversion element of the present invention.
• the photoelectric conversion element 10a shown in FIG. 1 includes a conductive film 11 functioning as a lower electrode (hereinafter also referred to as "lower electrode”), an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound, and an upper electrode. It has a structure in which a transparent conductive film (hereinafter also referred to as "upper electrode”) 15 that functions as an upper electrode is laminated in this order.
• FIG. 2 shows a configuration example of another photoelectric conversion element.
• FIGS. 1 and 2 has a structure 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. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 and 2 may be changed as appropriate depending on the application and characteristics.
• the photoelectric conversion element 10a it is preferable that light be incident on the photoelectric conversion film 12 via the upper electrode 15. Further, when using the photoelectric conversion element 10a (or 10b), a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 7 V/cm is applied 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. Regarding the voltage application method, in FIGS.
• the photoelectric conversion element 10a (or 10b) is used as a photosensor or incorporated into an image sensor, voltage can be applied in the same manner. As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably applied to an image sensor. Below, the form of each layer constituting the photoelectric conversion element of the present invention will be explained in detail.
• the photoelectric conversion element has a photoelectric conversion film.
• the photoelectric conversion film contains a compound (specific compound) represented by formula (1). Note that in formula (A-1), formula (A-2), and formulas (Ar-1) to (Ar-4), * represents a bonding position.
• R Z1 represents a hydrogen atom or a substituent. Examples of the substituent represented by R Z1 include the groups exemplified by the substituent W above.
• the substituent represented by R Z1 is preferably a group exemplified by the substituent S described below. The substituent S will be detailed later.
• X 1 represents a sulfur atom, an oxygen atom, or a selenium atom.
• X 1 is preferably a sulfur atom or an oxygen atom, and more preferably a sulfur atom, since the effects of the present invention are more excellent.
• R Y1 represents a hydrogen atom or a substituent. Examples of the substituent represented by R Y1 include the groups exemplified by the substituent W above. The substituent represented by R Y1 is preferably a group exemplified by the substituent S described below. The substituent S will be detailed later.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• substituents represented by R 1 and R 2 include the groups exemplified by the substituent W above.
• R 1 and R 2 are preferably hydrogen atoms, since the effects of the present invention are more excellent.
• Ar represents a group represented by any one of formulas (Ar-1) to (Ar-4).
• * represents the bonding position.
• the bonding direction of the groups represented by any of formulas (Ar-1) to (Ar-4) is not particularly limited, and the two bonds in formulas (Ar-1) to (Ar-4) Either position * may be on the side of the ring structure containing Y1 .
• Ar is preferably a group represented by formula (Ar-1) or formula (Ar-2) in that the effects of the present invention are more excellent, and Ar is preferably a group represented by formula (Ar-1). More preferably, it is a group.
• R Z2 represents a hydrogen atom or a substituent. Examples of the substituent represented by R Z2 include the substituents exemplified by the substituent W above.
• the substituent represented by R Z2 is preferably a group exemplified by the substituent S described below. The substituent S will be detailed later.
• R Z6 represents a hydrogen atom or a substituent.
• the substituent represented by R Z6 include the groups exemplified by the substituent W above.
• the substituent represented by R Z6 is preferably a group exemplified by the substituent S described below. The substituent S will be detailed later.
• the R Z6 's may be the same or different.
• X 2 represents a sulfur atom, an oxygen atom, or a selenium atom.
• a sulfur atom or an oxygen atom is preferable, and a sulfur atom is more preferable, since the effects of the present invention are more excellent.
• R Z8 represents a hydrogen atom or a substituent.
• Examples of the substituent represented by R Z8 include the groups exemplified by the substituent W above.
• R Z14 represents a hydrogen atom or a substituent.
• Examples of the substituent represented by R Z14 include the groups exemplified by the substituent W above.
• any one of Z 14 to Z 17 is a nitrogen atom, it is preferable that Z 17 is a nitrogen atom.
• X 3 represents a sulfur atom, an oxygen atom, or a selenium atom.
• X 3 is preferably a sulfur atom or an oxygen atom, more preferably a sulfur atom, since the effects of the present invention are more excellent.
• the bonding direction of the two bonding positions * is not particularly limited, and regardless of which of the two bonding positions * is on the side of the ring structure containing Y 1 . good. That is, in the above formula (1), when Ar is a group represented by formula (Ar-4), the above specific compound is represented by formula (1-a) or formula (1-b). means.
• Requirement 3: Ar represents a group represented by formula (Ar-1), at least one of Z 2 to Z 5 represents -CR Z2 , and R Z2 represents a substituent S.
• Requirement 4: Ar represents a group represented by formula (Ar-2), at least one of Z 6 and Z 7 represents -CR Z6 , and R Z6 represents a substituent S.
• the substituent S is an aliphatic hydrocarbon group that may have a substituent, an aromatic ring group that may have a substituent, a halogen atom, or an aliphatic heterocyclic group that may have a substituent.
• substituents that the aliphatic hydrocarbon group, the aromatic ring group, the aliphatic heterocyclic group, and the alkoxy group may have include the groups exemplified by the substituent W. .
• R represents an aliphatic hydrocarbon group or an aromatic ring group, and R may be the same or different.
• substituent S include, among others, an aliphatic hydrocarbon group that may have a substituent, an alkoxy group that may have a substituent, or an aromatic ring group that may have a substituent. is preferred.
• the number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, and is preferably 1 to 20.
• the aliphatic hydrocarbon group may be any of an alkyl group, an alkenyl group, and an alkynyl group.
• Examples of the aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.
• the number of carbon atoms in the linear aliphatic hydrocarbon group is not particularly limited, and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
• the number of carbon atoms in the branched aliphatic hydrocarbon group is not particularly limited, and is preferably 3 to 10, more preferably 3 to 5.
• the number of carbon atoms in the cyclic aliphatic hydrocarbon group is not particularly limited, and is preferably 3 to 10, more preferably 3 to 8.
• a halogen atom is preferable.
• the number of carbon atoms in the alkoxy group is not particularly limited, and is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
• the alkoxy group is preferably an alkoxy group obtained by substituting an oxygen atom for the hydrogen atom in each aliphatic hydrocarbon group of the above-mentioned preferred embodiments.
• the definition of the aromatic ring group is as described above, and it may be an aryl group or a heteroaryl group.
• the number of ring members in the aromatic ring is preferably 5 to 20, more preferably 5 to 10, and even more preferably 4 to 6.
• the number of carbon atoms in the aromatic ring group is not particularly limited, and is preferably from 4 to 20, more preferably from 4 to 10. Unless otherwise specified herein, "the number of carbon atoms in an aromatic ring group” refers to the number of carbon atoms that are ring member atoms in the aromatic ring group.
• the above aryl group is preferably a phenyl group which may have a substituent.
• the heteroaryl group is preferably a thiophene ring group which may have a substituent or a pyridine ring group which may have a substituent.
• substituent that the aromatic ring group may have, an alkyl group, an alkoxy group, or a halogen atom is preferable.
• the number of substituents is not particularly limited, and may be one or more.
• a 1 and A 2 each independently represent a group represented by formula (A-1) or formula (A-2).
• * represents the bonding position.
• a 1 and A 2 is a group represented by the formula (A-1)
• both A 1 and A 2 are a group represented by the formula (A-1)
• a group represented by -1) is more preferable.
• a 1 and A 2 may each have the same structure or different structures, but it is also preferable that A 1 and A 2 are mutually different groups. It is preferable that A 1 and A 2 are different from each other because aggregation of the specific compounds is less likely to occur.
• R W1 represents a hydrogen atom or a substituent.
• R W4 to R W6 are each independently an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent. Represents an aliphatic heterocyclic group.
• W 1 an oxygen atom is preferable since the effect of the present invention is more excellent.
• Examples of the substituent represented by R W1 include the groups exemplified by the substituent W above.
• the definition of the aliphatic hydrocarbon group is as described above.
• the aliphatic hydrocarbon group preferably has 1 to 3 carbon atoms.
• the definition of the aromatic ring group is as described above.
• the aromatic ring group may be either an aryl group or a heteroaryl group, but a phenyl group is particularly preferred.
• the number of ring members of the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 6 to 8.
• 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. preferable.
• 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, and a pyrrolidine ring.
• Examples of the substituents that the aliphatic hydrocarbon group, the aromatic ring group, and the aliphatic heterocyclic group may have include the groups exemplified by the substituent W above.
• C 1 represents a ring containing two or more carbon atoms and optionally having a substituent.
• 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. Note that the above carbon number is a number that includes two carbon atoms specified in the formula.
• the above-mentioned ring may be either aromatic or non-aromatic.
• the above-mentioned ring may be either a monocyclic ring or a polycyclic ring, 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 rings forming the above condensed ring is preferably 1 to 4, more preferably 1 to 3.
• the above ring may contain a heteroatom.
• the heteroatom include nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, phosphorus atom, silicon atom, and boron atom, with sulfur atom, nitrogen atom, or oxygen atom being preferred.
• the number of heteroatoms in the ring is preferably 0 to 10, more preferably 0 to 5.
• These are carbonyl carbon and thiocarbonyl carbon whose constituent elements are carbon atoms other than carbon atoms.
• Examples of the substituent that the ring may have include the groups exemplified by the substituent W above, preferably a halogen atom, an alkyl group, an aromatic ring group, or a silyl group, and a halogen atom or an alkyl group. group is more preferred.
• the alkyl group may be linear, branched, or cyclic, and preferably linear.
• the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 3.
• the ring represented by C 1 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 nuclei for example 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one and 1-(2-benzothiazolyl)-3-methyl-2- Pyrazolin-5-one etc.
• Isoxazolinone core for example, 3-phenyl-2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one.
• Oxindole nucleus For example, 1-alkyl-2,3-dihydro-2-oxindole.
• (e) 2,4,6-trioxohexahydropyrimidine core for example, barbituric acid, 2-thiobarbituric acid and its derivatives.
• Examples of the above derivatives include 1-alkyl derivatives such as 1-methyl and 1-ethyl; 1,3-dialkyl derivatives such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl; -diphenyl, 1,3-diaryls such as 1,3-di(p-chlorophenyl) and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1- such as 1-ethyl-3-phenyl Examples include aryl forms and 1,3-diheteroaryl forms such as 1,3-di(2-pyridyl).
• 2-thio-2,4-thiazolidinedione nucleus for example, rhodanine and its derivatives.
• examples of the above derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine and 3-allyrrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and 3-( Examples include 3-heteroarylrhodanine such as 2-pyridyl)rhodanine.
• 2-thio-2,4-oxazolidinedione nucleus (2-thio-2,4-(3H,5H)-oxazolidinedione nucleus): For example, 3-ethyl-2-thio-2,4-oxazolidinedione etc.
• 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.
• 2,4-thiazolidinedione nucleus for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, and 3-phenyl-2,4-thiazolidinedione.
• Thiazolin-4-one nucleus for example, 4-thiazolinone and 2-ethyl-4-thiazolinone.
• 2,4-imidazolidinedione (hydantoin) core for example, 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione.
• 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus for example, 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidine Zion et al.
• Imidazolin-5-one nucleus For example, 2-propylmercapto-2-imidazolin-5-one.
• 3,5-pyrazolidinedione nucleus for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione.
• Benzothiophen-3(2H)-one nucleus for example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, dioxobenzothiophen-3(2H)-one, etc.
• 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.
• R X1 represents a hydrogen atom or a substituent.
• substituent represented by R X1 include the groups exemplified by the substituent W above.
• R X4 to R X6 are each independently an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or a substituent optionally Represents an aliphatic heterocyclic group.
• the definition of each group represented by R X4 to R X6 is the same as the definition of each group represented by R W4 to R W6 .
• Examples of the substituents that the aliphatic hydrocarbon group, the aromatic ring group, and the aliphatic heterocyclic group may have include the groups exemplified by the substituent W above.
• C 3 represents an aromatic ring which may have a substituent.
• the number of carbon atoms in the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 6 to 8. Note that the above carbon number is a number that includes two carbon atoms specified in the formula.
• the aromatic ring may be either monocyclic or polycyclic. Further, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle, but an aromatic hydrocarbon ring is preferable. Examples of the aromatic ring represented by C3 include the rings exemplified in the description of the aromatic ring above.
• the aromatic ring is preferably a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring, and more preferably a benzene ring, since the effects of the present invention are more excellent.
• the substituent that the aromatic ring may have include the groups exemplified by the substituent W above.
• X c3 to X c5 are preferably oxygen atoms.
• R V1 represents a hydrogen atom or a substituent.
• substituent represented by R V1 include the groups exemplified by the substituent W above.
• R V4 to R V6 are each independently an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent. Represents an aliphatic heterocyclic group.
• R c1 and R c2 each independently represent a hydrogen atom or a substituent.
• substituents represented by R c1 and R c2 include the groups exemplified by the above-mentioned substituent W, and among them, an alkyl group or a phenyl group is preferable, and an alkyl group is more preferable.
• the above phenyl group may further have a substituent, such as the group exemplified by the above substituent W.
• Ar A represents an aromatic ring group which may have a substituent or an aliphatic hydrocarbon group which may have a substituent.
• the aromatic ring group which may have a substituent and which is represented by Ar A above may be either an aryl group or a heteroaryl group.
• a phenyl group which may have a substituent is particularly preferable.
• the optionally substituted aliphatic hydrocarbon group represented by Ar A above may be linear, branched, or cyclic.
• the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 5, and even more preferably 1 to 3.
• the above-mentioned specific compound is a compound represented by formula (2) in that the effects of the present invention are more excellent.
• R Y1 represents a hydrogen atom or a substituent. The aspect of R Y1 is as described above. As R Y1 , a substituent S is preferable.
• Y2 represents a sulfur atom, an oxygen atom, or a selenium atom.
• Y 2 is preferably a sulfur atom or an oxygen atom, and more preferably a sulfur atom, since the effects of the present invention are more excellent.
• Z 1 , X 1 , R 1 , R 2 , A 1 , A 2 , and Ar are Z 1 , X 1 , R 1 , R 2 , A 1 , A 2 and A 2 in the above formula (1), respectively. , is synonymous with Ar.
• the specific compound is preferably a compound represented by formula (2-1) to formula (2-7), and a compound represented by formula (2-1) or formula (2-4). It is more preferable that
• R Y1 represents a hydrogen atom or a substituent. The aspect of R Y1 is as described above. As R Y1 , a substituent S is preferable.
• Y2 represents a sulfur atom, an oxygen atom, or a selenium atom.
• Y 2 is preferably a sulfur atom or an oxygen atom, and more preferably a sulfur atom, since the effects of the present invention are more excellent.
• X 1 , X 2 , R 1 , R 2 , A 1 , A 2 , and Z 1 to Z 7 are respectively X 1 , X 2 , R 1 , R 2 , A 1 in the above formula (1), It has the same meaning as A 2 and Z 1 to Z 7 .
• it is more preferable that all of Y 1 and Z 1 to Z 7 specified in the formulas are -CH .
• Rs is an optionally substituted aliphatic hydrocarbon group, an optionally substituted alkoxy group, or a substituent Represents an aromatic ring group that may have.
• the number of carbon atoms in Rs is preferably 1 to 20, more preferably 1 to 10.
• the aliphatic hydrocarbon group may be any of an alkyl group, an alkenyl group, and an alkynyl group.
• Examples of the aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.
• the number of carbon atoms in the linear aliphatic hydrocarbon group is not particularly limited, and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
• Examples of the linear aliphatic hydrocarbon group include linear alkyl groups such as methyl group, ethyl group, and n-propyl group.
• the number of carbon atoms in the branched aliphatic hydrocarbon group is not particularly limited, and is preferably 3 to 10, more preferably 3 to 5.
• Examples of the branched aliphatic hydrocarbon group include branched alkyl groups such as isopropyl group, sec-butyl group, iso-butyl group, tert-butyl group, and neopentyl group.
• the number of carbon atoms in the cyclic aliphatic hydrocarbon group is not particularly limited, and is preferably 3 to 10, more preferably 3 to 8.
• Examples of the cyclic aliphatic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group.
• substituents that a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group may have include the groups exemplified for substituent W. and a halogen atom is preferred.
• the number of carbon atoms in the alkoxy group is not particularly limited, and is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
• the alkoxy group is preferably an alkoxy group obtained by substituting an oxygen atom for the hydrogen atom in each aliphatic hydrocarbon group of the above-mentioned preferred embodiments.
• Examples of the substituent that the alkoxy group may have include the groups exemplified for the substituent W.
• the definition of the aromatic ring constituting the above aromatic ring group is as described above, and examples of the aromatic ring group include an aryl group and a heteroaryl group.
• the number of ring members of the aromatic ring constituting the aromatic ring group is preferably 5 to 20, more preferably 5 to 10, and even more preferably 5 to 6.
• the number of carbon atoms in the aromatic ring group is not particularly limited, and is preferably from 4 to 20, more preferably from 4 to 10.
• the above aryl group is preferably a phenyl group which may have a substituent, and more preferably a phenyl group, tolyl group, xylyl group (2,6-xylyl group), and naphthyl group.
• the heteroaryl group is preferably a thiophene ring group which may have a substituent or a pyridine ring group which may have a substituent.
• substituents that the aromatic ring group may have include the groups exemplified for the substituent W, with an alkyl group, an alkoxy group, or a halogen atom being preferred.
• the number of substituents is not particularly limited, and may be one or more.
• Rs is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms that may have a halogen atom, or a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms that may have a halogen atom.
• the molecular weight of the specific compound is preferably 400 to 1,200, more preferably 400 to 1,000, even more preferably 400 to 800.
• the sublimation temperature of the specific compound is low, and it is presumed that the quantum efficiency is excellent even when a photoelectric conversion film is formed at high speed.
• the specific compound must have an ionization potential of -5.0 to -6.0 eV in a single film in terms of stability when used as a p-type organic semiconductor and energy level matching with an n-type organic semiconductor. is preferred.
• the maximum absorption wavelength of the specific compound is preferably in the range of 400 to 650 nm, more preferably in the range of 400 to 600 nm.
• the above-mentioned maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) by adjusting the absorption spectrum of a specific compound to a concentration such that the absorbance is 0.5 to 1.0.
• solvent chloroform
• the maximum absorption wavelength of the specific compound is determined by vapor-depositing the specific compound and using the specific compound in a film state.
• the specific compound is particularly useful as a material for a photoelectric conversion film used in an image sensor, an optical sensor, or a photovoltaic cell.
• the specific compound often functions as a dye within the photoelectric conversion film.
• the specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic material.
• R in the specific compound exemplified above represents any of the following groups. * represents the bonding position.
• a specific compound may be purified if necessary.
• purification methods for specific compounds include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, and purification using adsorbents such as activated carbon. Examples include recrystallization purification.
• One type of specific compound may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
• the photoelectric conversion film contains an n-type organic semiconductor in addition to the above-mentioned specific compound.
• the n-type organic semiconductor is a compound different from the above-mentioned specific compound.
• An n-type organic semiconductor is an acceptor organic semiconductor material (compound), and refers to an organic compound that has the property of easily accepting electrons. That is, an n-type organic semiconductor refers to an organic compound that has a larger electron affinity when two organic compounds are used in contact with each other. That is, any organic compound can be used as the acceptor organic semiconductor as long as it has electron-accepting properties.
• n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and derivatives thereof; fused aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives, etc.); 5- to 7-membered heterocyclic compounds having at least one member 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, pyrazole, imidazole and thiazole, etc.
• fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferred.
• the fullerene 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 fullerene.
• fullerene derivatives include compounds obtained by adding a substituent to the above-mentioned fullerene.
• the above substituent is preferably an alkyl group, an aryl group or a heterocyclic group.
• the fullerene derivative compounds described in JP-A No. 2007-123707 are preferred.
• the n-type organic semiconductor may be an organic dye.
• organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, Examples include acridine dyes,
• the molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.
• the maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less, or more than 400 nm and 600 nm or less.
• the photoelectric conversion film has a bulk heterostructure formed in a state in which a specific compound and an n-type organic semiconductor are mixed.
• the bulk heterostructure is a layer in which a specific compound and an n-type organic semiconductor are mixed and dispersed within the photoelectric conversion film.
• a photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. Note that the bulk heterostructure is explained in detail in paragraphs [0013] to [0014] of JP-A No. 2005-303266.
• 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 semiconductors 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 15 It is preferably 75% by volume, more preferably 20-60% by volume, even more preferably 20-50% by volume.
• the content of fullerenes relative to the total content of the n-type organic semiconductor material is preferably 50 to 100% by volume, more preferably 80 to 100% by volume.
• Fullerenes may be used alone or in combination of two or more.
• 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% by volume, more preferably 40 to 80% by volume.
• the content of the specific compound is preferably 15 to 75% by volume, more preferably 30 to 75% by volume.
• the photoelectric conversion film is substantially composed of a specific compound, an n-type organic semiconductor, and a p-type organic semiconductor included as desired. Substantially means that the total content of the specific compound, n-type organic semiconductor and p-type organic semiconductor is 90 to 100% by volume, preferably 95 to 100% by volume, with respect to the total mass of the photoelectric conversion film. More preferably 100% by volume.
• the photoelectric conversion film contains a p-type organic semiconductor in addition to the above-mentioned specific compound.
• the p-type organic semiconductor is a compound different from the above-mentioned specific compound.
• a p-type organic semiconductor is a donor organic semiconductor material (compound), and refers to an organic compound that has the property of easily donating electrons. That is, the p-type organic semiconductor refers to an organic compound that has a smaller ionization potential when two organic compounds are used in contact with each other.
• the p-type organic semiconductors may be used alone or in combination of two or more.
• Examples of p-type organic semiconductors include triarylamine compounds (for example, N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4, 4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl ( ⁇ -NPD), compound described in paragraphs [0128] to [0148] of JP 2011-228614, JP 2011-176259 Compounds described in paragraphs [0052] to [0063] of Japanese Patent Publication No. 2011-225544, compounds described in paragraphs [0119] to [0158] of Japanese Patent Application Publication No.
• TPD N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
• ⁇ -NPD 4, 4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl
• naphthalene derivatives anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives and fluoranthene derivatives, etc.
• porphyrin compounds phthalocyanine compounds
• triazole compounds oxa Examples include diazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having nitrogen-containing heterocyclic compounds as ligands.
• p-type organic semiconductors include JP 2022-123944, JP 2022-122839, JP 2022-120323, JP 2022-120273, and JP 2022-115832.
• Compounds described in JP-A No. 2022-108268, JP-A No. 2022-100258, JP-A No. 2022-181226, and JP-A No. 2023-005703 can also be used, and these compounds are included in the present specification. incorporated into the book.
• Examples of the p-type organic semiconductor include compounds having a smaller ionization potential than the n-type organic semiconductor, and if this condition is satisfied, the organic dyes exemplified as the n-type organic semiconductor can be used. Examples of compounds that can be used as p-type organic semiconductor compounds are shown 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 semiconductors 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 15 It is preferably 75% by volume, more preferably 20-60% by volume, even more preferably 25-50% by volume.
• a photoelectric conversion film containing a specific compound is a non-luminescent film and has characteristics different from organic light emitting diodes (OLEDs).
• a non-luminescent film means a film with a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, more preferably 0.1% or less. The lower limit is often 0% or more.
• the photoelectric conversion film contains a dye in addition to the above-mentioned specific compound.
• the dye is a compound different from the above specific compound.
• organic dyes are preferred. Examples of 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
• acceptor-donor-acceptor type dyes in which two acidic nuclei are bonded to a donor, and two donors bonded to an acceptor Examples include donor-acceptor-donor type dyes.
• donor-acceptor-donor type dyes include cyanine dyes, imidazoquinoxaline dyes, or acceptor-donor-acceptor type dyes are preferred.
• the above-mentioned imidazoquinoxaline dye is preferably a donor-acceptor type dye or an acceptor-donor-acceptor type dye, since it has a maximum absorption wavelength within a preferable range described below.
• the maximum absorption wavelength of the dye is preferably in the visible light region, more preferably from 400 to 650 nm, and even more preferably from 450 to 650 nm.
• the dyes may be used alone or in combination of two or more.
• the film thickness (layer equivalent) ⁇ 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 20 to 50% by volume.
• Dry film forming methods include, for example, physical vapor deposition methods such as evaporation methods (especially vacuum evaporation methods), sputtering methods, ion plating methods, and MBE (Molecular Beam Epitaxy) methods, as well as CVD (Chemical) methods such as plasma polymerization. Vapor Deposition) method is mentioned, and vacuum evaporation method is preferable.
• manufacturing conditions such as the degree of vacuum and the evaporation 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 has an electrode.
• the electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Electrically conductive materials include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected. Examples of the material constituting the upper electrode 15 include antimony tin oxide (ATO), fluorine doped tin oxide (FTO), tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO).
• ATO antimony tin oxide
• FTO fluorine doped tin oxide
• ITO indium tin oxide
• Conductive metal oxides such as Indium Tin Oxide (Indium Tin Oxide) and Indium Zinc Oxide (IZO); Metal thin films such as gold, silver, chromium, and nickel; Mixtures or laminations 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 conductive metal oxides are preferred in terms of high conductivity and transparency.
• the sheet resistance may be 100 to 10,000 ⁇ / ⁇ , and there is a large degree of freedom in the range of film thickness that can be made thin.
• An increase in light transmittance is preferable because it increases light absorption in the photoelectric conversion film and increases photoelectric conversion ability.
• the thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm.
• the lower electrode 11 may be transparent or may not be transparent and may reflect light.
• the material constituting the lower electrode 11 include tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO).
• conductive metal oxides metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN), etc.); mixtures or laminates of metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; carbon materials such as carbon nanotubes and granphene.
• the method for forming the electrode can be selected as appropriate depending on the electrode material. Specifically, wet methods such as printing methods and coating methods; physical methods such as vacuum evaporation methods, sputtering methods and ion plating methods; and chemical methods such as CVD and plasma CVD methods can be mentioned.
• wet methods such as printing methods and coating methods
• physical methods such as vacuum evaporation methods, sputtering methods and ion plating methods
• chemical methods such as CVD and plasma CVD methods
• CVD and plasma CVD methods can be mentioned.
• the material of the electrode is ITO, methods such as electron beam method, sputtering method, resistance heating vapor deposition method, chemical reaction method (sol-gel method, etc.), and coating of indium tin oxide dispersion can be used.
• the photoelectric conversion element preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.
• the intermediate layer include a charge blocking film.
• the charge blocking film include an electron blocking film and a hole blocking film.
• the electron blocking film is a donor organic semiconductor material (compound), and the above p-type organic semiconductor can be used. Additionally, polymeric materials can also be used as the electron blocking film. Examples of the polymeric material include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.
• the electron blocking film may be composed of a plurality of films.
• the electron blocking film may be composed of an inorganic material.
• inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for an electron blocking film, more voltage is applied to the photoelectric conversion film, resulting in higher quantum efficiency.
• Inorganic materials that can be used as electron blocking films include, for example, 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, and indium oxide. Copper, indium silver oxide and iridium oxide may be mentioned.
• the hole blocking film is an acceptor organic semiconductor material (compound), and the above n-type organic semiconductor can be used. Note that the hole blocking film may be composed of a plurality of films.
• Examples of the method for manufacturing the charge blocking film include a dry film forming method and a wet film forming method.
• Examples of the dry film forming method 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, and a physical vapor deposition method such as a vacuum vapor deposition method is preferable.
• Examples of wet film forming methods include inkjet method, spray method, nozzle printing method, spin coating method, dip coating method, casting method, die coating method, roll coating method, bar coating method, and gravure coating method. In terms of patterning, the inkjet method is preferred.
• each charge blocking film 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. Note that the position of the substrate is such that a conductive film, a photoelectric conversion film, and a 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 deteriorate significantly due to the presence of deterioration factors such as water molecules. Therefore, the entire photoelectric conversion film is covered with a sealing layer made of dense ceramics such as metal oxide, metal nitride, or metal nitride oxide, or diamond-like carbon (DLC), which does not allow water molecules to penetrate. The above deterioration can be prevented by sealing.
• the sealing layer include the descriptions in paragraphs [0210] to [0215] of JP-A No. 2011-082508, the contents of which are incorporated herein.
• An image sensor is an element that converts optical information of an image into an electrical signal.
• multiple photoelectric conversion elements are arranged on the same plane in a matrix, and each photoelectric conversion element (pixel) converts an optical signal into an electrical signal.
• pixel is a device that can convert the image into an electrical signal and sequentially output the electrical signal to the outside of the image sensor for each pixel.
• each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
• the photoelectric conversion element of the present invention is preferably used as an optical sensor.
• the above photoelectric conversion element may be used alone, or may be used as a line sensor in which the above photoelectric conversion elements are arranged in a straight line, or as a two-dimensional sensor in which the above photoelectric conversion elements are arranged on a plane.
• the present invention also includes inventions of compounds.
• the compound of the present invention is the above-mentioned specific compound.
• the photoelectric conversion element includes 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 is formed into a film by sputtering on a glass substrate to form a lower electrode 11 (thickness: 30 nm), and a compound (EB-1) is further vacuum-heated and vapor-deposited on the lower electrode 11.
• An electron blocking film 16A was formed by a method.
• each material shown in Tables 1 and 2 was codeposited in a predetermined ratio on the electron blocking film 16A using a vacuum evaporation method to form a film on the glass substrate at room temperature.
• a photoelectric conversion film 12 having a bulk heterostructure of 240 nm was formed.
• 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 the upper electrode 15 (transparent conductive film) (thickness: 10 nm).
• an aluminum oxide (Al 2 O 3 ) layer was formed thereon by an ALCVD (Atomic Layer Chemical Vapor Deposition) method.
• the laminate was heated at 150° C. for 30 minutes in a glove box to obtain a photoelectric conversion element.
• the dark current of each of the obtained photoelectric conversion elements was measured by the following method. A voltage was applied to the lower electrode and the upper electrode of each photoelectric conversion element so that the electric field strength was 2.5 ⁇ 10 5 V/cm, and the current value in the dark (dark current) was measured. As a result, it was confirmed that the dark current of each photoelectric conversion element was 50 nA/cm 2 or less, indicating a sufficiently low dark current.
• the quantum efficiency of each of the obtained photoelectric conversion elements was measured by the following method. After applying a voltage to each photoelectric conversion element to have an electric field strength of 2.0 ⁇ 10 5 V/cm, light is irradiated from the upper electrode (transparent conductive film) side to determine the quantum efficiency (photoelectric conversion) at a wavelength of 460 nm. efficiency) was evaluated, and the quantum efficiency was determined according to formula (S1).
• Quantum efficiency (relative ratio) (Quantum efficiency at wavelength 460 nm of each example or each comparative example) / (Quantum efficiency at wavelength 460 nm of standard example)
• the response speed of each of the obtained photoelectric conversion elements was evaluated by the following method.
• a voltage was applied to the photoelectric conversion element at an intensity of 2.0 ⁇ 10 5 V/cm.
• an LED light emitting diode
• the photocurrent at a wavelength of 460 nm at that time is measured with an oscilloscope, and the signal intensity is 97% from 0% signal intensity.
• the rise time until the signal intensity rose to % was measured, and the relative response speed was evaluated according to equation (S2).
• Relative response speed (rise time at wavelength 460 nm of each example or each comparative example)/(rise time at wavelength 460 nm of reference example)
• Examples 1-1 to 1-36 and Comparative Examples 1-1 to 1-2 listed in Table 1 in formula (S2), Example 1-1 is adopted as the above standard example, and regarding Examples 2-1 to 2-3 and Comparative Example 2-1 listed in Table 2, Example 1-1 is adopted as the above standard example in formula (S2). 2-1 was adopted.
• Example 1-1 the rise time at 7.5 ⁇ 10 4 V/cm at a wavelength of 460 nm for the photoelectric conversion efficiency of Example 1-1 and the rise time at a wavelength of 460 nm for the photoelectric conversion efficiency of Example 1-1
• the rise time at 2.0 ⁇ 10 5 V/cm is compared with that at 2.0 ⁇ 10 5 V/cm.
• C The electric field strength dependence of the response speed is 3.0 or more. 4. Less than 0
• D The dependence of response speed on electric field strength is 4.0 or more and less than 5.0
• E The dependence of response speed on electric field strength is 5.0 or more
• Tables 1 and 2 show the evaluation results of Test X above. Each notation in Tables 1 and 2 indicates the following.
• the “Formula (2)” column cases where the specific compound was a compound represented by Formula (2) were marked as "A”, and cases other than the above were marked as "B".
• the "(Ar-1), (Ar-2)” column indicates "A” when Ar is a compound represented by the above formula (Ar-1) or the above formula (Ar-2) in the specific compound.
• the quantum efficiency of each of the obtained photoelectric conversion elements was measured by the following method. After applying a voltage to each photoelectric conversion element to have an electric field strength of 2.0 ⁇ 10 5 V/cm, light is irradiated from the upper electrode (transparent conductive film) side to determine the quantum efficiency at a wavelength of 460 nm or 600 nm. was evaluated, and the quantum efficiency was determined according to equation (S4).
• Quantum efficiency (relative ratio) (Quantum efficiency at wavelength 460 nm or wavelength 600 nm of each example or each comparative example) / (Quantum efficiency at wavelength 460 nm or wavelength 600 nm of standard example)
• Quantum efficiency is less than 0.4 Regarding Examples 3-1 to 3-43 and Comparative Examples 3-1 to 3-2 listed in Table 3, as the above reference example in formula (S4) Example 3-1 was adopted, and for Examples 4-1 to 4-3 and Comparative Example 4-1 listed in Table 4, Example 4-1 was adopted as the above reference example in formula (S4). did.
• Relative response speed (rise time at wavelength 460 nm or wavelength 600 nm of each example or each comparative example)/(rise time at wavelength 460 nm or wavelength 600 nm of reference example)
• Relative response speed is 2.0 or more
• Example 3-1 to 3-43 and Comparative Examples 3-1 to 3-2 listed in Table 3 in formula (S5) Example 3-1 is adopted as the above standard example, and regarding Examples 4-1 to 4-3 and Comparative Example 4-1 listed in Table 4, Example 3-1 is adopted as the above standard example in formula (S5). 4-1 was adopted.
• Tables 3 and 4 show the evaluation results of Test Y.
• the "ratio" column represents the mass ratio of the specific compound or comparative compound, the dye, the p-type organic semiconductor, and the n-type organic semiconductor in order from the left.
• the specific compound: dye: p-type organic semiconductor: n-type organic semiconductor 0.5:0.5:1:1.
• Other notations in Tables 3 and 4 are as described above for each notation in Tables 1 and 2.

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