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Definitions

• the present invention relates to a photoelectric conversion element, an imaging element, an optical sensor, a compound, and a method for manufacturing the compound.
• Non-Patent Document 1 discloses an ADA (acceptor-donor-acceptor) type dye that can be used as a p-type or n-type semiconductor.
• 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 imaging element, an optical sensor, a compound, and a method for producing the compound, which are related to the photoelectric conversion element.
• the substituent selected from the substituent group S described later represents a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aliphatic hydrocarbon group having 1 carbon atom and a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aromatic ring group which may have a substituent selected from the substituent group R Ar1 described later, a group represented by the formula (S-3) described later, or a group represented by the formula (S-4) described later.
• R N and R C1 to R C10 are respectively defined as R N and R C1 to R C10 in the above formula (1).
• R N and R C1 to R C4 are respectively defined as R N and R C1 to R C4 in the above formula (1).
• R 3 N has the same meaning as R 3 N in formula (1) above.
• 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 the compound represented by formula (1) and the n-type organic semiconductor.
• R N and R C1 to R C10 are respectively defined as R N and R C1 to R C10 in the above formula (1).
• X represents >NR N , >CR C1 R C2 , or >C ⁇ CR C3 R C4 .
• R N and R C1 to R C4 are respectively defined as R N and R C1 to R C4 in the above formula (1).
• X represents >NR 3 N.
• R 3 N has the same meaning as R 3 N in formula (1) above.
• a method for producing a compound represented by formula (2b) described later comprising a step of reacting a compound represented by formula (2a) described later with a compound represented by formula (X) described later.
• R Sn , R B1 and R B2 each independently represent a substituent, and multiple R Sn , R B1 and R B2 may be the same or different.
• R B1 and R B2 may be bonded to each other to form a ring structure.
• M + represents a monovalent metal cation.
• * represents a bonding position.
• the present invention it is possible to provide a photoelectric conversion element that has excellent quantum efficiency when receiving blue light. Furthermore, according to the present invention, it is possible to provide an imaging element, an optical sensor, a compound, and a method for producing the compound, which relate 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 hydrogen atom may be a protium atom (a normal hydrogen atom) or a deuterium atom (eg, a deuterium atom, etc.).
• substituent W in this specification will be described.
• substituent W include 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 heteroaryl 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 halogen atom (e
• each of the above groups may further have a substituent (e.g., one or more of the above groups) if possible.
• a substituent e.g., one or more of the above 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 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 i-propyl group, an n-butyl group, a t-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 that the alkoxy group may have include the same as the substituent in the alkyl group which may have a substituent.
• examples of the substituent that the alkylthio group may have include the same as the substituent 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 4 to 15 member atoms.
• 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, and a phenanthrene ring.
• aromatic heterocycle examples include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (for example, a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring), a tetrazine ring (for example, 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 naphthopyr
• the type of the substituent which the aromatic ring may have may be, for example, the groups 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 obtained by removing one or more (for example, 1 to 5, etc.) hydrogen atoms 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.).
• 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.
• 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, 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.
• the bonding direction of a divalent group (such as -CO-O-) described in this specification is not limited unless otherwise specified.
• a divalent group such as -CO-O-
• the compound when Y is -CO-O- in a compound represented by the formula "X-Y-Z", the compound may be either "X-O-CO-Z" or "X-CO-O-Z".
• the term "optionally having an etheric oxygen atom” means that the aliphatic hydrocarbon group may have a divalent linking group represented by -O- in the aliphatic hydrocarbon group (between carbon atoms) or at an end.
• the general formula or structural formula representing the compound may be described in only one of the cis and trans forms for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form.
• the photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) described later (hereinafter, also referred to as a "specific compound").
• the mechanism by which the photoelectric conversion element of the present invention having the above-mentioned configuration can solve the problems of the present invention is not necessarily clear, but the present inventors speculate as follows. It should be noted that the mechanism by which the effects are obtained is not limited by the following speculation, and in other words, even if the effects are obtained by a mechanism other than the following, it is included in the scope of the present invention.
• the compound disclosed in Literature 1 is an ADA dye having a structure in which a branched alkyl group is substituted on a fused ring structure such as fluorene as a donor site.
• a fused ring structure such as fluorene as a donor site.
• the dyes are likely to aggregate, which leads to a deterioration in the quantum efficiency of the photoelectric conversion element. Therefore, in Literature 1, the aggregation is suppressed by introducing a substituent such as an alkyl group.
• the substituent in Reference 1 the substituent is too large to efficiently transfer electrons and holes, and the quantum efficiency is still insufficient.
• the size of the substituent introduced into the fused ring structure of carbazole, fluorene, or the like is optimized, so that the above-mentioned aggregation of the dyes does not occur, and electrons and holes can be efficiently exchanged.
• the quantum efficiency of the photoelectric conversion element is improved compared to that of Literature 1.
• a better quantum efficiency when the photoelectric conversion element receives blue light is also referred to as a better effect of the present invention.
• the configuration of the photoelectric conversion element of the present invention will be described in detail below.
• 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 of the present invention has a photoelectric conversion film.
• the photoelectric conversion film contains a compound (specific compound) represented by formula (1).
• X represents >NR N , >CR C1 R C2 , >C ⁇ CR C3 R C4 , >SiR C5 R C6 , >GeR C7 R C8 , —OC(R C9 )(R C10 )—, a sulfur atom, an oxygen atom, or a selenium atom.
• R 1 N represents a substituent selected from the substituent group S described below.
• R C1 to R C10 each independently represent a hydrogen atom or a substituent selected from the substituent group S described below.
• R C1 and R C2 represents a substituent selected from the substituent group S
• at least one of R C3 and R C4 represents a substituent selected from the substituent group S
• at least one of R C5 and R C6 represents a substituent selected from the substituent group S
• at least one of R C7 and R C8 represents a substituent selected from the substituent group S
• at least one of R C9 and R C10 represents a substituent selected from the substituent group S.
• R and R , R and R , R and R , R and R , R and R , R and R may each independently bond directly or via a linking group to form a ring.
• R and R may both be benzene ring groups and bond directly (via a single bond) to form a fluorene ring.
• X preferably represents >NR N , >CR C1 R C2 , >C ⁇ CR C3 R C4 , >SiR C5 R C6 , >GeR C7 R C8 , or --OC(R C9 )(R C10 )-, more preferably represents >NR N , >CR C1 R C2 , or >C ⁇ CR C3 R C4 , even more preferably represents >NR N or >CR C1 R C2 , and most preferably represents >NR N. It is also preferred that both R C1 and R C2 represent a substituent selected from the substituent group S.
• both R C3 and R C4 represent a substituent selected from Substituent Group S.
• both R C5 and R C6 represent a substituent selected from Substituent Group S.
• both R C7 and R C8 represent a substituent selected from the substituent group S.
• both R C9 and R C10 represent a substituent selected from Substituent Group S.
• Substituent group S is a group consisting of the following substituents: Substituent group S: a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms (hereinafter also referred to as “substituent S A "), a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent (hereinafter also referred to as “substituent S B "), a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms and a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms (hereinafter also referred to as “substituent S AB “), a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms and an aromatic ring group which may have a substituent (hereinafter also referred to as "substituent S AAr "), a branched aliphatic hydrocarbon group having 3 carbon atoms and a cyclic aliphatic
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent, the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms and having a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms and having an aromatic ring group which may have a substituent, the branched aliphatic hydrocarbon group having 3 carbon atoms and having a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, and the branched aliphatic hydrocarbon group having 3 carbon atoms and having an aromatic ring group which may have a substituent may have an ethereal oxygen atom or may be substituted with a halogen atom.
• the number of carbon atoms in the substituent S A is not particularly limited as long as it is 1 to 3, but 1 or 2 is preferred.
• the substituent S A include a linear alkyl group having 1 to 3 carbon atoms, a linear alkenyl group having 2 or 3 carbon atoms, and a linear alkynyl group having 2 or 3 carbon atoms.
• Examples of the linear alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and an n-propyl group, and among these, a methyl group or an ethyl group is preferable.
• the linear alkenyl group having 2 or 3 carbon atoms include a vinyl group, an allyl group, and an isoallyl group.
• the linear alkynyl group having 2 or 3 carbon atoms include an ethynyl group, a 1-propynyl group, and a propargyl group.
• the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent S B may have either a monocyclic or polycyclic structure.
• the number of carbon atoms in the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent S B is not particularly limited as long as it is 3 to 8, but 3 to 6 carbon atoms is preferable, and 3 is more preferable.
• Examples of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent S B include a cyclic alkyl group having 3 to 8 carbon atoms and a cyclic alkenyl group having 3 to 8 carbon atoms.
• Examples of the cyclic alkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a cycloheptyl group, a 4-tetrahydropyranyl group, and a group formed by removing one hydrogen atom from bicyclo[1,1,1]pentane.
• Examples of cyclic alkenyl groups having 3 to 8 carbon atoms include groups obtained by removing one hydrogen atom from a cycloalkene having 3 to 8 carbon atoms.
• cycloalkenes examples include cyclobutene, cyclopentene, cyclohexene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene.
• the number of substituents that the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent S B may have is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2.
• the substituent that the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent S B may have, the groups exemplified in the substituent group R Ar1 described later are preferable, and a linear alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a halogen atom are more preferable.
• the substituent S AB is a straight-chain aliphatic hydrocarbon group having 1 to 3 carbon atoms which has a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, and corresponds to a group in which one or more hydrogen atoms in the above-mentioned substituent S A (straight-chain aliphatic hydrocarbon group having 1 to 3 carbon atoms) are substituted with a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms.
• the number of cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms is not particularly limited, but 1 to 3 is preferred, and 1 or 2 is more preferred.
• linear aliphatic hydrocarbon group having 1 to 3 carbon atoms in the substituent S AB are the same as the specific and preferred embodiments of the substituent S A described above.
• specific and preferred embodiments of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent S AB are the same as the specific and preferred embodiments of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent S B.
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms in the substituent S AB is preferably a linear alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
• the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent S AB is preferably a cyclic alkyl group having 3 to 8 carbon atoms, more preferably a cyclic alkyl group having 3 to 6 carbon atoms.
• substituent S AB examples include a methyl group having a cyclic alkyl group having 3 to 8 carbon atoms (hereinafter also referred to as “substituent S AB1 "; in other words, a group in which at least one hydrogen atom of a methyl group is substituted with a cyclic alkyl group having 3 to 8 carbon atoms), an ethyl group having a cyclic alkyl group having 3 to 8 carbon atoms (hereinafter also referred to as “substituent S AB2 "; in other words, a group in which a hydrogen atom of an ethyl group is substituted with a cyclic alkyl group having 3 to 8 carbon atoms), and an n-propyl group having a cyclic alkyl group having 3 to 8 carbon atoms (hereinafter also referred to as “substituent S AB3 "; in other words, a group in which a hydrogen atom of an n-propy
• Examples of the cyclic alkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a cycloheptyl group, a 4-tetrahydropyranyl group, and a group obtained by removing one hydrogen atom from bicyclo[1,1,1]pentane. Of these, a cyclopropyl group is preferable.
• the number of cyclic alkyl groups having 3 to 8 carbon atoms is not particularly limited, but is preferably 1 or 2.
• a group in which one or two hydrogen atoms of a methyl group are substituted with a cyclic alkyl group having 3 to 6 carbon atoms is preferable, and a group in which one or two hydrogen atoms of a methyl group are substituted with a cyclic alkyl group having 3 carbon atoms (cyclopropyl group) is more preferable.
• the number of cyclic alkyl groups having 3 to 8 carbon atoms is not particularly limited, but is preferably 1 or 2.
• the number of cyclic alkyl groups having 3 to 8 carbon atoms is not particularly limited, but is preferably 1 or 2.
• the substituent S AAr is a straight-chain aliphatic hydrocarbon group having 1 to 3 carbon atoms and having an aromatic ring group which may have a substituent, and corresponds to a group in which one or more hydrogen atoms in the above-mentioned substituent S A (straight-chain aliphatic hydrocarbon group having 1 to 3 carbon atoms) are substituted with a substituent S Ar (an aromatic ring group which may have a substituent) which will be described later.
• the number of aromatic ring groups which may have a substituent is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2.
• linear aliphatic hydrocarbon group having 1 to 3 carbon atoms and the aromatic ring group which may have a substituent in the substituent S AAr are the same as those of the above-mentioned substituent S A and the below-mentioned substituent S Ar .
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms in the substituent S AAr is preferably a linear alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
• aromatic ring group which may have a substituent in the substituent S AAr is preferably an aryl group, more preferably a phenyl group.
• the substituent S DB is a branched aliphatic hydrocarbon group having 3 carbon atoms which has a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, and corresponds to a group in which one or more hydrogen atoms in the branched aliphatic hydrocarbon group having 3 carbon atoms (hereinafter also referred to as "substituent S D ”) are substituted with a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms.
• the number of cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms is not particularly limited, but 1 to 3 is preferable, and 1 or 2 is more preferable.
• Examples of the branched aliphatic hydrocarbon group having 3 carbon atoms in the substituent S DB include an isopropyl group and an isopropenyl group. Of these, an isopropyl group is preferable.
• Specific and preferred embodiments of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the substituent S DB are as described above.
• the substituent S DAr is a branched aliphatic hydrocarbon group having 3 carbon atoms and having an aromatic ring group which may have a substituent, and corresponds to a group in which one or more hydrogen atoms in the above-mentioned substituent S D (branched aliphatic hydrocarbon group having 3 carbon atoms) are substituted with a substituent S Ar (an aromatic ring group which may have a substituent) described later.
• the number of aromatic ring groups which may have a substituent is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2.
• Specific and preferred embodiments of the substituent S D in the substituent S DAr are as described above.
• Specific and preferred embodiments of the substituent S 1 Ar in the substituent S 1 DAr are as described below.
• the aromatic ring constituting the aromatic ring group in the substituent S Ar may be either a monocyclic or polycyclic ring, and may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Specific embodiments of the monocyclic aromatic ring, polycyclic aromatic ring, aromatic hydrocarbon ring, and aromatic heterocyclic ring are as described above.
• the aromatic ring constituting the aromatic ring group in the substituent S Ar preferably has 4 to 15 member atoms, more preferably 4 to 10 member atoms, and even more preferably 4 to 6 member atoms.
• the aromatic hydrocarbon ring constituting the aromatic ring group in the substituent S Ar is preferably a benzene ring, a naphthalene ring, or an anthracene ring.
• the aromatic heterocycle constituting the aromatic ring group in the substituent S Ar is preferably a pyridine ring, a thiophene ring, a benzofuran ring (eg, a 2,3-benzofuran ring, etc.), or a benzothiophene ring (eg, a benzo[b]thiophene ring, etc.).
• the number of substituents which the aromatic ring group in Substituent S Ar may have is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2.
• Substituent S Examples of the substituent that the aromatic ring group in Ar may have include the groups exemplified as the substituent W above.
• the substituent that the aromatic ring group in the substituent S Ar may have, the groups exemplified in the substituent group R Ar1 described later are preferable, and a linear alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a halogen atom is more preferable.
• Substituent group R Ar1 The substituents selected from the above substituent group R Ar1 are as follows.
• Substituent group R Ar1 linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 5 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms, aromatic ring groups, halogen atoms, and *-Si(R Si ) 3 .
• R 3 Si represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, or an aromatic ring group.
• the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms may have an ethereal oxygen atom or be substituted with a halogen atom.
• substituent group R Ar1 specific and preferred embodiments of the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms are the same as the specific and preferred embodiments of the substituent S A and the substituent S B.
• examples of the branched aliphatic hydrocarbon group having 3 to 5 carbon atoms include a branched alkyl group having 3 to 5 carbon atoms (such as an isopropyl group), a branched alkenyl group having 3 to 5 carbon atoms, and a branched alkynyl group having 3 to 5 carbon atoms.
• the number of carbon atoms in the branched aliphatic hydrocarbon group having 3 to 5 carbon atoms is not particularly limited as long as it is 3 to 5, but is preferably 3 to 4.
• Specific and preferred embodiments of the aromatic ring group in the substituent group R Ar1 are the same as those of the aromatic ring group in the substituent S Ar , and among them, an aryl group is preferred, and a phenyl group is more preferred.
• L S1 represents a single bond or a linear alkylene group having 1 to 3 carbon atoms.
• R S1 independently represents a hydrogen atom, a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms, or a cyclic alkyl group having 3 carbon atoms.
• Multiple R S1 may be the same or different, provided that two or more of the three R S1 are other than a hydrogen atom.
• the alkylene group, the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, the branched aliphatic hydrocarbon group having 3 to 4 carbon atoms, and the cyclic alkyl group having 3 carbon atoms may have an ethereal oxygen atom or be substituted with a halogen atom.
• the group represented by formula (S-1) preferably has 3 to 9 carbon atoms, and more preferably 3 to 7 carbon atoms.
• the number of carbon atoms in the group represented by the above formula (S-1) means the total number of all carbon atoms contained in the group represented by the formula (S-1).
• L S1 is preferably a single bond or a methylene group, more preferably a single bond.
• the number of R S1 represented by a group other than a hydrogen atom is not particularly limited as long as it is two or more. It is preferable that one of R S1 is a hydrogen atom and the remaining two are groups other than a hydrogen atom. Of these, R S1 is preferably a methyl group, an isopropyl group, or a t-butyl group, and more preferably a methyl group or an isopropyl group.
• Q represents an oxygen atom or a sulfur atom
• Q is preferably an oxygen atom
• R Ac1 represents 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 definition of each group represented by R Ac1 is as described above.
• examples of the substituent that each group represented by R Ac1 may have include the groups exemplified by the above-mentioned substituent W.
• R Ac1 which may have a substituent
• a linear, branched or cyclic aliphatic hydrocarbon group which may have a halogen atom is particularly preferred.
• an aromatic ring group which may have a substituent represented by R Ac1 an aromatic ring group which may have a substituent selected from the above-mentioned group of substituents R Ar1 is particularly preferable.
• the substituent selected from the above-mentioned substituent group S represents a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aliphatic hydrocarbon group having 1 carbon atom and having a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aromatic ring group which may have a substituent selected from the substituent group R Ar1 , a group represented by formula (S-3), or a group represented by formula (S-4).
• substituent selected from the above-mentioned substituent group R Ar1 is as described above, but the substituent selected from the substituent group R Ar1 is preferably a substituent selected from the substituent group R Ar2 .
• Substituent group R Ar2 linear aliphatic hydrocarbon groups having 1 to 2 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, halogen atoms, and *-Si(R Si ) 3 .
• R 3 Si represents a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group.
• the linear aliphatic hydrocarbon group having 1 to 2 carbon atoms, the branched aliphatic hydrocarbon group having 3 to 4 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms may have an ethereal oxygen atom or be substituted with a halogen atom.
• each R S2 independently represents a hydrogen atom, a methyl group, an isopropyl group, or a t-butyl group.
• Multiple R S2 may be the same or different, provided that the group represented by formula (S-3) has 3 to 9 carbon atoms, and two or more of the three R S2 are other than a hydrogen atom.
• the group represented by formula (S-3) preferably has 3 to 9 carbon atoms, and more preferably 3 to 7 carbon atoms.
• the number of carbon atoms in the group represented by the above formula (S-3) means the total number of all carbon atoms contained in the group represented by the formula (S-3).
• the number of R S2 represented by a group other than a hydrogen atom is not particularly limited as long as it is two or more. It is preferable that one of R S2 is a hydrogen atom and the remaining two are groups other than a hydrogen atom. Of these, R S2 is preferably a methyl group or an isopropyl group.
• R Ac2 represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom, or an aromatic ring group which may have a substituent selected from the above substituent group R Ar1 .
• the aliphatic hydrocarbon group is preferably an alkyl group.
• the aromatic ring group which may have a substituent selected from the above substituent group R Ar1 is preferably an aromatic ring group having 4 to 10 ring atoms which may have a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, or a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, and more preferably a phenyl group which may have a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, or a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms.
• the two R X1 may be bonded to each other to form a ring.
• R X1 may be the same or different.
• Z 1 to Z 6 preferably two or less of Z 2 , Z 3 , Z 5 and Z 6
• R X1 examples include the groups exemplified as the above-mentioned substituent W, and more specifically, halogen atoms and alkyl groups are mentioned.
• the halogen atom is preferably a fluorine atom or a chlorine atom.
• the alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• substituents represented by R1 and R2 include the groups exemplified as the above-mentioned substituent W. Among them, in terms of the superior effect of the present invention, it is preferable that R1 and R2 are hydrogen atoms.
• a 1 and A 2 each independently represent a group represented by formula (A-1) above.
• each Y 1 independently represents a sulfur atom, an oxygen atom, ⁇ NR X2 , or ⁇ CR X3 R X4 .
• R X2 represents a hydrogen atom or a substituent.
• R X3 and R X4 independently represent a cyano group, —SO 2 R X5 , —COOR X6 , or —COR X7 .
• Y1 preferably represents an oxygen atom or a sulfur atom in that the effects of the present invention are more excellent.
• substituent represented by R 1 X2 include the substituents exemplified as the above-mentioned substituent W.
• R x5 to R x7 each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.
• the aliphatic hydrocarbon group is as defined above, and among them, an alkyl group is preferable, and a linear alkyl group is more preferable.
• the aliphatic hydrocarbon group preferably has 1 to 3 carbon atoms.
• the aromatic ring group is as defined above, and among them, an aryl group is preferable, and a phenyl group is more preferable.
• the aliphatic heterocyclic group is as defined above.
• C1 represents a ring containing 2 or more carbon atoms and which may have 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.
• the number of carbon atoms includes the two carbon atoms specified in the formula.
• the ring may be either aromatic or non-aromatic.
• the ring may be either a monocyclic or 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 fused ring is preferably 1 to 4, and more preferably 1 to 3.
• the ring may have a heteroatom, such as a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, or a boron atom, and is preferably a sulfur atom, a nitrogen atom, or an oxygen atom.
• the number of heteroatoms in the ring is preferably 0 to 10, and more preferably 0 to 5.
• substituents 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.
• the group represented by the above formula (A-1) is preferably a group represented by formula (A-2) in that the effects of the present invention are more excellent.
• X1 and X2 each independently represent an oxygen atom or a sulfur atom. It is preferable that both X1 and X2 represent an oxygen atom.
• C2 represents a ring containing 3 or more carbon atoms. 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 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 contained is preferably 2 to 6, and more preferably 2 or 3.
• 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.
• the group represented by the above formula (A-2) is preferably a group represented by the formula (C-1) or a group represented by the formula (C-2).
• Xc1 and Xc2 each independently represent a sulfur atom or an oxygen atom. At least one of Xc1 and Xc2 is preferably an oxygen atom, and it is more preferable that both Xc1 and Xc2 are oxygen atoms.
• C3 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.
• the number of carbon atoms includes 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.
• Examples of the aromatic ring represented by C3 include the rings exemplified above in the description of the aromatic ring.
• the aromatic ring represented by C3 is preferably a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring, and more preferably a benzene ring.
• the substituent that the aromatic ring may have include the groups exemplified for the substituent W above.
• X c3 to X c5 represent a sulfur atom or an oxygen atom. It is preferable that all of X c3 to X c5 are oxygen atoms.
• Rc1 and Rc2 each independently represent a hydrogen atom or a substituent. Examples of the substituent represented by Rc1 and Rc2 include the groups exemplified by the above-mentioned substituent W. Among them, an alkyl group or a phenyl group is preferable, and an alkyl group is more preferable. The phenyl group may further have a substituent, for example, the groups exemplified as the substituent W above.
• the molecular weight of the specific compound is preferably from 400 to 1,200, more preferably from 400 to 1,000, and even more preferably from 500 to 800.
• the molecular weight is within the above range, it is presumed that the sublimation temperature of the specific compound is low, and the quantum efficiency is excellent even when the photoelectric conversion film is formed at high speed.
• the specific compound has an ionization potential of -5.0 to -6.0 eV in a single film.
• the maximum absorption wavelength of the specific compound is preferably in the range of 400 to 600 nm, and more preferably in the range of 400 to 500 nm.
• the maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) by adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1.0.
• solvent chloroform
• the specific compound is evaporated and the value measured using the specific compound in a film state is regarded as the maximum absorption wavelength of the specific compound.
• the specific compounds are particularly useful as materials for photoelectric conversion films used in imaging devices, photosensors, or photovoltaic cells.
• the specific compounds often function as dyes within the photoelectric conversion films.
• the specific compounds can also be used as coloring materials, liquid crystal materials, organic semiconductor materials, charge transport materials, medicinal materials, and fluorescent diagnostic materials.
• a in the specific compounds exemplified above represents one of the following groups.
• the particular compound may be purified if necessary.
• Methods for purifying the specific compound include, for example, 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 n-type organic semiconductor may be an organic dye.
• organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, a
• the molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.
• the maximum absorption wavelength of the n-type organic semiconductor is preferably 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 the n-type organic semiconductor material 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 15 to 75 vol%, and more preferably 30 to 75 vol%. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, the n-type organic semiconductor, and 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 [0054] to [0065] 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
• Examples of p-type organic semiconductors include benzoxazole compounds (for example, compounds described in Figures 3 to 7 of JP-A-2022-123944), dicarbazole compounds (for example, compounds described in Figures 2 to 5 of JP-A-2022-122839), benzoquinazoline compounds (for example, compounds described in paragraphs [0053] to [0056] of JP-A-2022-120323), azine compounds (for example, compounds described in paragraphs [0041] to [0042] of JP-A-2022-120273), compounds described in Figures 2 to 10 of JP-A-2022-115832, indolotriphenylene compounds (for example, compounds described in Figures 2 to 5 of JP-A-2022-122839), and the like.
• benzoxazole compounds for example, compounds described in Figures 3 to 7 of JP-A-2022-123944
• dicarbazole compounds for example, compounds described in Figures 2 to 5 of JP-A-2022-122839
• 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 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,
• Cridinone dyes diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, WO2020/013246, WO2022/168856, JP2023-10305A, and JP2023-10299A described imidazoquinoxaline dyes, as well as acceptor-donor-acceptor type dyes in which two acidic nuclei are bound to a donor, and donor-acceptor-donor type dyes in which two donors are bound to an acceptor.
• organic dye among others, a cyanine dye, an imidazoquinoxaline dye, or an acceptor-donor-acceptor type dye is preferable, and an imidazoquinoxaline dye or an acceptor-donor-acceptor type dye is more preferable.
• the maximum absorption wavelength of the dye is preferably in the visible light region, more preferably 400 to 650 nm, and even more preferably 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 granphenes.
• conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO),
• 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 composed of an inorganic material.
• inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, 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 present invention also includes the invention of a compound.
• the compound of the present invention is the specific compound or an intermediate in the synthesis process of the specific compound, which is a compound represented by formula (2) (hereinafter also referred to as "intermediate A”), a compound represented by formula (3) (hereinafter also referred to as "intermediate B”), or a compound represented by formula (3c).
• Specific and preferred embodiments of Z 1 to Z 6 in formula (2) are the same as those of Z 1 to Z 6 in formula (1).
• R 3 represents a substituent selected from the substituent group T.
• Substituent group T a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and an aromatic ring group not containing a nitrogen atom which may have a substituent selected from the substituent group R Ar3 .
• the linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• the branched aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 3 to 5 carbon atoms.
• the cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 8 carbon atoms.
• the linear aliphatic hydrocarbon group, the branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group in the substituent group T may have an etheric oxygen atom.
• substituents selected from the substituent group R Ar3 are as follows.
• Substituent group R Ar3 a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, a halogen atom, and an aromatic ring group containing no nitrogen atom.
• Specific and preferred embodiments of each group exemplified in the substituent group R Ar3 are the same as the specific and preferred embodiments of each group exemplified in the substituent group T above.
• the linear aliphatic hydrocarbon group, the branched aliphatic hydrocarbon group and the cyclic aliphatic hydrocarbon group in the substituent group R Ar3 may have an ether oxygen atom or be substituted with a halogen atom.
• a linear alkyl group having 1 to 3 carbon atoms, a methoxy group, a branched alkyl group having 3 to 5 carbon atoms, or a cyclic alkyl group having 3 carbon atoms (cyclopropyl group) is preferable.
• R f represents a perfluoroalkyl group having 1 to 6 carbon atoms.
• R Sn , R B1 and R B2 each independently represent a substituent, and a plurality of R Sn , R B1 and R B2 may be the same or different.
• R B1 and R B2 may be bonded to each other to form a ring structure.
• M + represents a monovalent metal cation.
• the perfluoroalkyl group represented by Rf is preferably a trifluoromethyl group.
• the substituent represented by R Sn include an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, and an aliphatic heterocyclic group which may have a substituent.
• the substituent which each of the above groups may have include the groups exemplified by the above substituent W.
• R 3 Sn an aliphatic hydrocarbon group which may have an aromatic ring group is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group or a butyl group is even more preferable.
• the substituent represented by R B1 is not particularly limited as long as it is a substituent in an organoboron compound generally used in an aromatic coupling reaction, and examples thereof include a hydroxy group and an alkoxy group.
• the ring formed may be an aromatic ring (for example, a benzene ring) or a non-aromatic ring.
• Examples of the group represented by R B1 include groups represented by formula (B1) and formula (B2).
• the substituent represented by R B2 is not particularly limited as long as it is a substituent in an organoboron compound generally used in an aromatic coupling reaction, and examples thereof include a fluorine atom and an alkoxy group.
• Examples of the monovalent metal cation represented by M + include monovalent metal cations such as a lithium ion, a potassium ion, a sodium ion, a rubidium ion, and a cesium ion.
• the ring formed may be an aromatic ring (for example, a benzene ring) or a non-aromatic ring.
• R B2 Of the three R B2 , two R B2 may be bonded to each other to form a ring, or three R B2 may be bonded to each other to form a ring.
• R B2 examples include a group represented by formula (B3): In formula (B3), M + represents the above-mentioned monovalent metal cation.
• Ar represents an aromatic ring containing two or more carbon atoms as ring member atoms and no nitrogen atom as a ring member atom.
• the aromatic ring represented by Ar may be either a monocyclic or polycyclic ring, and may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring (aromatic heterocyclic ring not containing a nitrogen atom as a ring member atom). Specific embodiments of the monocyclic aromatic ring, polycyclic aromatic ring, aromatic hydrocarbon ring, and aromatic heterocyclic ring are as described above.
• the aromatic ring represented by Ar preferably has 4 to 15 member atoms, more preferably 4 to 10 member atoms, and even more preferably 4 to 6 member atoms.
• the aromatic hydrocarbon ring represented by Ar is preferably a benzene ring or a naphthalene ring.
• the aromatic heterocycle represented by Ar is preferably a thiophene ring, a benzofuran ring (eg, a 2,3-benzofuran ring), or a benzothiophene ring (eg, a benzo[b]thiophene ring).
• the aromatic ring represented by Ar may be substituted with a substituent selected from the above-mentioned substituent group T or a halogen atom. Specific and preferred embodiments of the substituent selected from the substituent group T are as described above.
• the number of the substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2.
• the aromatic ring represented by Ar has a substituent selected from the substituent group T
• the substituent selected from the substituent group T represented by R3 and the substituent selected from the substituent group T carried by the aromatic ring represented by Ar may be bonded to each other to form a non-aromatic ring.
• the aromatic ring represented by Ar is substituted with a plurality of substituents selected from the substituent group T
• the plurality of substituents may be bonded to each other to form a non-aromatic ring.
• the non-aromatic ring include an aliphatic ring
• examples of the non-aromatic ring include an aliphatic ring having 4 to 6 carbon atoms.
• Examples of the method for producing intermediate A include a method in which a compound having an aryl group on the nitrogen atom of carbazole (N-aryl-substituted carbazole) is subjected to a reaction such as halogenation or lithiation (lithiation) to introduce a group represented by R4 and a group represented by R5 .
• step P1 intermediate A (compound represented by formula (2)) can be efficiently produced by a compound production method including a step (hereinafter also referred to as step P1) of producing a compound represented by formula (2b) by reacting a compound represented by formula (2a) with a compound represented by formula (X), as shown below.
• the compound represented by formula (2b) is an embodiment in which R 4 and R 5 in formula (2) are each independently an iodine atom, *-O-S( ⁇ O) 2 R f , a bromine atom, a chlorine atom, or a fluorine atom.
• R X1 represents a hydrogen atom or a substituent.
• the two R X1 may be bonded to each other to form a ring.
• Z 1 to Z 6 have the same meanings as Z 1 to Z 6 in formula (2), and the preferred embodiments are also the same.
• R L4 and R L5 each independently represent *--O--S(.dbd.O) 2 R f , a bromine atom, a chlorine atom, or a fluorine atom.
• X1 and X2 each independently represent an iodine atom, *--O--S(.dbd.O) 2Rf , a bromine atom, or a chlorine atom, where Rf has the same meaning as Rf in formula (2).
• R L4 , R L5 , X1 and X2 satisfy the following requirements.
• both the ranking of the group represented by R L4 and the ranking of the group represented by R L5 are higher than the ranking of the group represented by X1 and are also higher than the ranking of the group represented by X2 .
• the order from 1st to 5th position indicates the difficulty of the leaving group to be eliminated, and the 5th position means that the leaving group is more difficult to eliminate.
• both the group represented by X1 and the group represented by X2 are more likely to be eliminated than the group represented by R L4 and are more likely to be eliminated than the group represented by R L5 , so that an intramolecular ring-forming reaction proceeds preferentially over an intermolecular reaction.
• X1 is a bromine atom at the third position
• X2 is a bromine atom at the third position
• R1 is an iodine atom at the first position
• R2 is an iodine atom at the first position
• the priorities of R1 and R2 are lower than the priorities of X1 and X2 (both of which are third), and therefore the above requirement is not satisfied.
• Examples of combinations of R L4 , R L5 , X1 and X2 that satisfy the above requirements include the following examples 1 to 4.
• the combination of Example 1 is particularly preferable.
• R 3 represents a substituent selected from the above-mentioned substituent group T.
• Ar represents an aromatic ring containing two or more carbon atoms as ring member atoms and not containing a nitrogen atom as a ring member atom.
• the aromatic ring represented by Ar may be substituted with a substituent selected from the above-mentioned substituent group T or a halogen atom.
• the aromatic ring represented by Ar has a substituent selected from the above-mentioned substituent group T
• the substituent selected from the above-mentioned substituent group T represented by R3 and the substituent selected from the above-mentioned substituent group T carried by the aromatic ring represented by Ar may be bonded to each other to form a non-aromatic ring.
• the aromatic ring represented by Ar is substituted with a plurality of substituents selected from the above-mentioned substituent group T, the plurality of substituents may be bonded to each other to form a non-aromatic ring.
• R3 and Ar in formula (X) have the same meanings as R3 and Ar in formula (2), and the preferred embodiments thereof are also the same.
• Z 1 to Z 6 , R L4 and R L5 have the same meanings as Z 1 to Z 6 , R L4 and R L5 in the above formula (2a).
• R3 and Ar have the same meanings as R3 and Ar in the above formula (X).
• the above step P1 is typically carried out under Buchwald-Hartwig cross-coupling conditions, and more specifically, the step P1 is preferably carried out in the presence of an organometallic catalyst and a base.
• organometallic catalyst include palladium catalysts, and more specifically, palladium salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate; complex compounds such as ⁇ -allylpalladium chloride dimer, palladium acetylacetonate, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, dichlorobis(acetonitrile)palladium, and dichlorobis(benzonitrile)palladium; and palladium complexes having a tertiary phosphine as a ligand, such as dichlorobis(triphenylphosphine)palladium, tetrakis(
• the above palladium catalyst may be prepared in situ by adding a tertiary phosphine to a palladium salt or complex compound.
• a palladium complex having a tertiary phosphine as a ligand is preferable, a palladium complex having a tertiary phosphine having at least one aryl group as a ligand is more preferable, and a palladium complex having a triarylphosphine as a ligand is even more preferable.
• the aryl group which the tertiary phosphine may have include a phenyl group which may have a group exemplified by the above-mentioned substituent W.
• the base examples include a base containing an alkali metal and a tertiary amine, and the base containing an alkali metal is preferred.
• the base containing an alkali metal is preferably an alkali metal alkoxide (e.g., sodium methoxide, sodium ethoxide, potassium t-butoxide, etc.), or an alkali metal carbonate, phosphate, hydroxide, or fluoride, more preferably an alkali metal alkoxide, and even more preferably an alkoxide consisting of a tert-butoxide anion and an alkali metal.
• the alkali metals include lithium, potassium, sodium, and cesium, with lithium, potassium, or sodium being preferred.
• reaction solvent in step P1 examples include toluene, tetrahydrofuran, 1,4-dioxane, 1,2-dichlorobenzene, benzene, xylene, mesitylene, anisole, chlorobenzene, dimethoxyethane, dimethylformamide (DMF), cyclopentyl methyl ether, 4-methyltetrahydropyran, acetonitrile, alcohols, and ionic liquids, and toluene is preferred.
• the reaction temperature is often a temperature at which the reaction mixture is refluxed depending on the reaction solvent used, and is preferably 50 to 200°C, more preferably 90 to 150°C.
• step P2 a step (hereinafter also referred to as "step P2") of converting the group represented by R L4 and the group represented by R L5 to a formyl group, *-Sn(R Sn ) 3 , *-B(R B1 ) 2 , or *-B - (R B2 ) 3 M + is further carried out, whereby a compound represented by formula (2) in which R 4 and R 5 are a formyl group, *-Sn(R Sn ) 3 , *-B(R B1 ) 2 , or *-B - (R B2 ) 3 M + is obtained.
• R Sn , R B1 and R B2 have the same meanings as R Sn , R B1 and R B2 in the intermediate A (compound represented by formula (2)), and the preferred embodiments thereof are also the same.
• an example of the step of converting the group represented by R L4 and the group represented by R L5 into a formyl group is a step of reacting the compound represented by formula (2b) with a formylating agent.
• a formylating agent known agents can be used, and examples thereof include N,N-disubstituted formamides, orthoformates, and compounds represented by formula (B′′).
• N,N-disubstituted formamide is a compound represented by the formula (B).
• R Y2 represents an organic group.
• a plurality of R Y2 may be the same or different.
• the organic group include an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, and an aliphatic heterocyclic group which may have a substituent. Of these, an aliphatic hydrocarbon group or an aromatic ring group is preferable.
• Examples of the compound represented by formula (B) include N,N-dimethylformamide (DMF), N-(diethylcarbamoyl)-N-methoxyformamide, 1-formylpiperidine, 4-formylmorpholine, N-methylformanilide, and N-formylsaccharin, and among these, DMF is preferred.
• DMF N,N-dimethylformamide
• diethylcarbamoyl)-N-methoxyformamide 1-formylpiperidine
• 4-formylmorpholine N-methylformanilide
• N-formylsaccharin examples include N,N-dimethylformamide (DMF), N-(diethylcarbamoyl)-N-methoxyformamide, 1-formylpiperidine, 4-formylmorpholine, N-methylformanilide, and N-formylsaccharin, and among these, DMF is preferred.
• R Y3 represents an alkyl group.
• a plurality of R Y3 may be the same or different.
• the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
• R represents an alkyl group having 1 to 6 carbon atoms.
• N-methoxyethyleneaniline is preferred.
• step P2A typically, the group represented by R4 and the group represented by R5 in the compound represented by formula (2b) are converted into metal active species using a metallation reagent, and then the formylating agent is reacted.
• the metallation reagent and reaction conditions used are not particularly limited, and known metallation reagents and reaction conditions can be applied.
• a lithium reagent or a magnesium reagent is particularly preferred.
• organolithium reagents are preferred, and examples thereof include alkyllithiums such as n-butyllithium, sec-butyllithium, and tert-butyllithium.
• the magnesium reagent may be an organomagnesium reagent (such as a Grignard reagent) or elemental magnesium.
• step P2B An example of the step of converting the group represented by R L4 and the group represented by R L5 in the compound represented by formula (2b) to *-Sn(R Sn ) 3 is a step of reacting the compound represented by formula (2b) with a compound represented by formula (Y) (hereinafter also referred to as "step P2B").
• step P2B a step of reacting the compound represented by formula (2b) with a compound represented by formula (Y) (hereinafter also referred to as "step P2B").
• step P2B (R Sn ) 3 Sn-Xa formula (Y)
• R 3 Sn has the same meaning as R 3 Sn in *-Sn(R 3 Sn ) 3 exemplified as R 4 and R 5 in formula (2) above.
• substituent represented by R Sn include an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, and an aliphatic heterocyclic group which may have a substituent.
• substituent which each of the above groups may have include the groups exemplified by the above substituent W.
• R 3 Sn an aliphatic hydrocarbon group which may have an aromatic ring group is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group or a butyl group is even more preferable.
• Rf has the same meaning as Rf in formula (2).
• step P2B typically, the group represented by R L4 and the group represented by R L5 in the compound represented by formula (2b) are converted to lithium using an organolithium reagent, and then the compound represented by formula (Y) is reacted.
• organolithium reagents include alkyllithiums such as n-butyllithium, sec-butyllithium, and tert-butyllithium.
• step P2B can also be carried out in the presence of a palladium catalyst.
• a palladium catalyst Specific reaction conditions can be referenced to the synthesis method described in the non-patent document "J. Org. Chem. 2016, 81, 8, 3356-3363.”
• the palladium catalyst those exemplified as the palladium catalyst in step P1 can be used.
• the step of converting the group represented by R L4 and the group represented by R L5 to *-B(R B1 ) 2 or *-B - (R B2 ) 3 M + can be, for example, a step of reacting the compound represented by formula (2b) above with a borylation agent.
• a borylation agent known agents can be used, and examples thereof include compounds represented by the formula (Z).
• Rf has the same meaning as Rf in the above formula (2).
• R B3 , R B4 and R B5 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.
• Plural R B3 and R B5 may be the same or different.
• R B3 and R B4 are preferably aliphatic hydrocarbon groups, more preferably alkyl groups, and even more preferably alkyl groups having 1 to 6 carbon atoms.
• R B3 may be bonded to each other to form a ring, and the compound represented by formula (Z) is preferably a compound represented by formula (Z').
• the group represented by *-B(OR B3 ) 2 is preferably a group represented by the above formula (B1) or (B2).
• R B5 is preferably an aliphatic hydrocarbon group or an aromatic ring group, more preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
• step P2C typically, the group represented by R L4 and the group represented by R L5 in the compound represented by formula (2b) are converted to lithium using an organolithium reagent, and then the compound represented by formula (Z) is reacted.
• the reaction conditions are not particularly limited as long as they are generally conditions for lithiation, and specific examples of the organolithium reagent are as described above.
• it is also effective to convert the group represented by R 4 and the group represented by R 5 to lithium or magnesium, and then react with a compound represented by formula (Z) to convert the group represented by R 4 and the group represented by R 5 to *-B(R B1 ) 2 or *-B - (R B2 ) 3 M + .
• Specific reaction conditions can be taken into consideration of the synthesis method described in the non-patent document "Org. Lett. 2006, 8, 18, 4071-4074".
• step P2C is often carried out in the presence of a palladium catalyst.
• a palladium catalyst Specific reaction conditions can be found in the synthesis method described in the non-patent document "European Polymer Journal (2019), 112, 283-290".
• the palladium catalyst and base that can be used in this synthesis method, those exemplified as the palladium catalyst and base in step P1 can be used.
• the step P2C can also be carried out without using a transition metal catalyst.
• reaction conditions include a case where a compound represented by the above formula (2b) is reacted with a compound represented by formula (Z) in which Xb is *-Si(R B5 ) 3.
• the synthesis method described in the non-patent document "J. Am. Chem. Soc. 2012, 134, 19997-20000" can be referred to.
• R4 and R5 each independently represent a fluorine atom, a chlorine atom , a bromine atom, an iodine atom, *-Sn(n-Bu) 3 , *-SnMe3, *-B(OH) 2 , * -BF3M + (M + represents a monovalent metal cation), a formyl group, or a group represented by any of the above formulas (B1) to (B3).
• intermediate B (a compound represented by formula (3)) will be described in detail.
• Intermediate B is represented by the following structural formula.
• Specific and preferred embodiments of Z 1 to Z 6 in formula (3) are the same as those of Z 1 to Z 6 in formula (1).
• Q represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
• R6 represents a substituent selected from the group U of substituents.
• Substituent group U an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, and an aliphatic heterocyclic group which may have a substituent.
• the aliphatic hydrocarbon group which may have a substituent is preferably a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms which may have a halogen atom, or a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a halogen atom.
• the aromatic ring group which may have a substituent is preferably an aromatic ring group which may have a substituent selected from the above substituent group R Ar1 , is preferably an aromatic ring group having 4 to 10 ring atoms which may have a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, or a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, and is more preferably a phenyl group which may have a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, or a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms.
• the method for producing intermediate B of the present invention includes a step 1 of reacting a compound represented by formula (3a) with a compound represented by formula (A) to obtain a compound represented by formula (3b) having a protecting group represented by SiR Y1 3 ; Step 2 of reacting the compound represented by formula (3b) with a metallation reagent, then reacting with a formylating agent, and further deprotecting the protecting group to obtain a compound represented by formula (3c); and step 3 of reacting a compound represented by formula (3c) with a compound represented by formula (C) to obtain a compound represented by formula (3).
• Z 1 to Z 6 have the same meanings as Z 1 to Z 6 in the above formula (3), and the preferred embodiments are also the same.
• X 3 and X 4 each independently represent an iodine atom, *—O—S( ⁇ O) 2 R f , a bromine atom, or a chlorine atom, preferably an iodine atom, a bromine atom, or a chlorine atom, more preferably a bromine atom.
• Step 1 is a step of reacting a compound represented by formula (3a) with a compound represented by formula (A) to obtain a compound represented by formula (3b) having a protecting group represented by SiR Y1 3 .
• R f has the same meaning as R f in formula (2). Among them, L 1 is preferably a bromine atom or a chlorine atom.
• R represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group.
• R Y1 is preferably a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, or an aromatic ring group.
• step 1 typically, the hydrogen atom on N in the compound represented by formula (3a) is converted to lithium using an organolithium reagent, and then the compound represented by formula (A) is reacted.
• organolithium reagents There are no particular limitations on the reaction conditions as long as they are generally conditions for lithiation, and specific examples of organolithium reagents are as described above.
• Step 2 is a step in which the compound represented by formula (3b) obtained in step 1 is reacted with a metallation reagent, then with a formylating agent, and the protecting group is deprotected to obtain a compound represented by formula (3c) described below.
• the metallization reagent may be a known one, for example, the reagent exemplified in step P2A.
• the reaction conditions are not particularly limited, and known reaction conditions may be applied.
• the formylating agent may be a known agent, such as the N,N-disubstituted formamide and orthoformate ester exemplified in the above step P2A.
• the reaction conditions may also be known, such as the conditions exemplified in the above step P2A.
• a method for deprotecting the protecting group represented by SiR Y1 3 for example, a method of reacting with an appropriate desilylation agent depending on the compound represented by formula (A) used can be mentioned.
• the desilylation agent is not particularly limited and any known desilylation agent can be used, and examples thereof include water, an acid, a base, and a fluoride ion.
• the silyl protecting group derived from the compound represented by formula (A) is easily deprotected, and deprotection may occur in a post-process (such as a separation process and a column purification process) after the completion of the reaction or due to moisture in the air. Even in such a case, it is within the scope of the present invention as long as a compound represented by formula (3c) can be obtained from a compound represented by formula (3b).
• steps 1 and 2 above may be carried out in one pot.
• Step 3 is a step of reacting the compound represented by formula (3c) obtained in step 2 with the compound represented by formula (C) to introduce a group derived from the compound represented by formula (C) onto N in formula (3c), thereby obtaining a compound represented by formula (3).
• Rf has the same meaning as Rf in formula (A).
• R6 has the same meaning as R6 in formula (3) above, and is preferably a methyl group or an ethyl group.
• Comparative Synthesis Example 1 (Comparative Synthesis Example of Intermediate (3)) As shown in the following scheme, 2,7-dibromocarbazole (100 mg), 2-fluoro-1,3-dimethylbenzene (76 mg), cesium carbonate (201 mg), and DMF (1.5 mL) were added to a recovery flask, heated to 100° C., and stirred for 1 hour, but the desired intermediate (3) was not obtained.
• intermediate (R1) was synthesized in the same manner as in the above ⁇ Synthesis of intermediate (12)>.
• intermediate (R1) 200 mg
• THF 5.5 mL
• normal butyl lithium 2.7 M, 0.5 mL
• DMF 0.4 mL
• Comparative Synthesis Example 3 (Comparative Synthesis Example of Intermediate (12)) As shown in the following scheme, an attempt was made to synthesize intermediate (12) using 2,7-dibromocarbazole as a starting material in the same manner as above, but a complex mixture was obtained and the desired intermediate (12) was not obtained.
• a photoelectric conversion element was produced using the above materials, and Tests X and Y were carried out.
• the photoelectric conversion element here comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B and an upper electrode 15.
• amorphous ITO was formed on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and a compound (EB-1) was further formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm).
• each specific compound or each comparative compound shown in Table 1 an n-type organic semiconductor (fullerene (C 60 )), and a p-type organic semiconductor (compound (P-1)) were co-evaporated by vacuum evaporation onto the electron blocking film 16A to a thickness of 80 nm in terms of a single layer.
• the film formation speed of the photoelectric conversion film 12 was set to 1.0 ⁇ /sec.
• a compound (EB-2) was deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm).
• Amorphous ITO was deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm).
• an aluminum oxide (Al 2 O 3 ) layer was formed thereon by atomic layer chemical vapor deposition (ALCVD).
• ACVD atomic layer chemical vapor deposition
• the dark current was measured by the following method. A voltage was applied to the lower and upper electrodes of each photoelectric conversion element to achieve an electric field strength of 2.5 ⁇ 10 5 V/cm, and the current value in a dark place (dark current) was measured. As a result, it was confirmed that the dark current in each photoelectric conversion element was 50 nA/cm 2 or less, which is a sufficiently low dark current.
• Quantum efficiency (relative ratio) (quantum efficiency at a wavelength of 460 nm of each example or each comparative example) / (quantum efficiency at a wavelength of 460 nm of the reference example)
• Quantum efficiency is 1.6 or more.
• Relative response speed is less than 0.5
• B Relative response speed is 0.5 or more and less than 1.0
• C Relative response speed is 1.0 or more and less than 1.5
• D Relative response speed is 1.5 or more and less than 2.0
• E Relative response speed is 2.0 or more
• ⁇ Response speed vs. electric field strength> For each of the obtained photoelectric conversion elements, the dependence of the response speed on the electric field strength was evaluated by the following method. In the evaluation of the above ⁇ Response speed>, the voltage applied to each photoelectric conversion element was changed to 7.5 ⁇ 10 4 V/cm, but the response speed at 7.5 ⁇ 10 4 V/cm was measured in the same manner as above. The electric field strength dependence of the response speed was evaluated based on the value obtained according to formula (S3) in accordance with the following criteria. In addition, the photoelectric conversion elements in the numerator and denominator of formula (S3) are the same.
• the rise time of the photoelectric conversion efficiency of Example 1-1 at a wavelength of 460 nm and a current density of 7.5 ⁇ 10 4 V/cm is compared with the rise time of the photoelectric conversion efficiency of Example 1-1 at a wavelength of 460 nm and a current density of 2.0 ⁇ 10 5 V/cm.
• Equation (S3): Dependence of response speed on electric field strength (rise time at 7.5 ⁇ 10 4 V/cm at a wavelength of 460 nm for each Example or Comparative Example)/(rise time at 2.0 ⁇ 10 5 V/cm at a wavelength of 460 nm for each Example or Comparative Example)
• ⁇ Manufacturing suitability> The manufacturability of each of the obtained photoelectric conversion elements was evaluated by the following method.
• Photoelectric conversion elements of each Example or Comparative Example were produced in the same manner as in the above ⁇ Production of Photoelectric Conversion Element>, except that the deposition rate of the photoelectric conversion film 12 was changed to 3.0 ⁇ /sec.
• the photoelectric conversion element obtained in the above ⁇ Preparation of photoelectric conversion element> was designated as photoelectric conversion element (A), and the photoelectric conversion element obtained by setting the film formation speed of the photoelectric conversion film 12 at 3.0 ⁇ /sec was designated as photoelectric conversion element (B).
• the quantum efficiency of each was determined in the same manner as in the evaluation of the above ⁇ Quantum efficiency>.
• the relative ratio B/A of the quantum efficiency of the photoelectric conversion element (B) to the quantum efficiency of the photoelectric conversion element (A) was calculated, and the manufacturing suitability of the obtained value was evaluated in accordance with the following criteria.
• Table 1 shows the evaluation results of the above test X.
• the symbols in Table 1 indicate the following:
• the substituent selected from the substituent group S represented by R N and R C1 to R C10 in formula (1) represents a straight-chain aliphatic hydrocarbon group having 1 to 2 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aliphatic hydrocarbon group having 1 carbon atom and having a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aromatic ring group which may have a substituent selected from the substituent group R Ar1 , a group represented by formula (S-3), or a group represented by formula (S-4), it is marked as "A", and when it is not the above, it is marked as "B”.
• the photoelectric conversion elements of the examples of the present invention have excellent quantum efficiency.
• the photoelectric conversion element of the comparative example using a comparative compound that does not fall under the specific compound had insufficient quantum efficiency.
• the quantum efficiency is more excellent in the specific compound when the substituent selected from the substituent group S represents a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aliphatic hydrocarbon group having 1 carbon atom and having a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aromatic ring group which may have a substituent selected from the substituent group R Ar1 , a group represented by the formula (S-3), or a group represented by the formula (S-4) (e.g., comparison between Example 1-1 and Example 1-27).
• the substituent selected from the substituent group S represents a linear aliphatic hydrocarbon group having 1 to 2 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aliphatic hydrocarbon group having 1 carbon atom and having a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aromatic ring
• the quantum efficiency of each of the obtained photoelectric conversion elements was measured by the following method. A voltage was applied to each photoelectric conversion element so as to achieve an electric field strength of 2.0 ⁇ 10 5 V/cm, and then light was irradiated from the upper electrode (transparent conductive film) side to evaluate the quantum efficiency at a wavelength of 460 nm or 600 nm. The quantum efficiency was evaluated based on the value obtained according to formula (S4) in accordance with the following criteria. In formula (S4), the quantum efficiency in the numerator and denominator is the quantum efficiency at the same wavelength. In addition, for the examples and comparative examples shown in Table 2, Example 2-15 was adopted as the reference example below.
• Quantum efficiency (relative ratio) (quantum efficiency at a wavelength of 460 nm or 600 nm of each example or comparative example) / (quantum efficiency at a wavelength of 460 nm or 600 nm of the reference example)
• Quantum efficiency is 1.6 or more.
• Quantum efficiency is 1.6 or more.
• B Quantum efficiency is 1.2 or more and less than 1.6.
• C Quantum efficiency is 0.8 or more and less than 1.2.
• D Quantum efficiency is 0.4 or more and less than 0.8.
• E Quantum efficiency is less than 0.4.
• the response speed of each of the obtained photoelectric conversion elements was evaluated by the following method. A voltage of 2.0 ⁇ 10 5 V/cm was applied to the photoelectric conversion element. Then, the LED was turned on momentarily to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 460 nm or 600 nm was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity. The response speed was evaluated based on the value obtained according to formula (S5) in accordance with the following criteria. In formula (S5), the rise times of the numerator and denominator are the rise times at the same wavelength.
• Equation (S5): Relative response speed (rise time at a wavelength of 460 nm or 600 nm for each example or comparative example) / (rise time at a wavelength of 460 nm or 600 nm for the reference example)
• 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 2.0
• E Relative response speed is 2.0 or more
• Table 2 shows the evaluation results of test Y.
• the notations in Table 2 are as described above for the notations in Table 1.

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