Photoelectric conversion element, imaging element, light sensor, compound, and compound production method

Abstract

The present invention provides a photoelectric conversion element that exhibits excellent quantum efficiency when having received blue light. Also provided are an imaging element, a light sensor, a compound, and a compound production method relating to the photoelectric conversion element. A photoelectric conversion element according to the present invention includes an electrically conductive film, a photoelectric conversion film, and a transparent electrically conductive film in the stated order. The photoelectric conversion film contains a compound represented by formula (1).

Description

Photoelectric conversion element, imaging element, optical sensor, compound, and method for manufacturing compound

[0001] The present invention relates to a photoelectric conversion element, an imaging element, an optical sensor, a compound, and a method for producing the compound.

[0002] In recent years, development of devices having photoelectric conversion films (e.g., image sensors) has progressed. For example, Non-Patent Document 1 discloses an ADA (acceptor-donor-acceptor) dye that can be used as a p-type semiconductor or an n-type semiconductor.

[0003] Wurthner et al., org. chem. front. 2016, 3, 545-555.

[0004] In recent years, with the demand for improved performance of image sensors, optical sensors, and the like, further improvements are being sought in the properties required of the photoelectric conversion elements used therein. For example, there is an even greater demand for high quantum efficiency when the photoelectric conversion element receives blue light (particularly a wavelength of 460 nm). Here, the above-mentioned blue light refers to light with a wavelength in the range of 400 to 500 nm. The present inventors have studied a photoelectric conversion element containing the ADA-type dye described in Non-Patent Document 1 as a p-type semiconductor and have found that there is room for further improvement in the quantum efficiency when the above-mentioned blue light is received.

[0005] Therefore, 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.

[0006] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, they have found that the above problems can be solved by the following configuration.

[0007] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1) described later. [2] A photoelectric conversion element wherein the substituent selected from the substituent group S described later is 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, or a substituent selected from the substituent group R described later. Ａｒ１

[0023] The photoelectric conversion element according to [1], wherein X represents an aromatic ring group optionally having a substituent selected from the following, a group represented by formula (S-3) described later, or a group represented by formula (S-4) described later. [3] The photoelectric conversion element according to [1] or [2], wherein the group represented by formula (A-1) is a group represented by formula (A-2) described later. [4] The photoelectric conversion element according to [3], wherein the group represented by formula (A-2) is a group represented by formula (C-1) described later or a group represented by formula (C-2) described later. [5] The photoelectric conversion element according to [1], wherein X is >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 The photoelectric conversion element according to any one of [1] to [4], wherein R Ｎ and R Ｃ１ ~R Ｃ１０ are R in the above formula (1), Ｎ , and R Ｃ１ ~R Ｃ１０ [6] X is >NR Ｎ , >CR Ｃ１ R Ｃ２ , or >C=CR Ｃ３ R Ｃ４ The photoelectric conversion element according to any one of [1] to [5], wherein R Ｎ and R Ｃ１ ~R Ｃ４ are R in the above formula (1), Ｎ , and R Ｃ１ ~R Ｃ４ [7] X is >NRＮ The photoelectric conversion element according to any one of [1] to [6], wherein R Ｎ is R in the above formula (1). Ｎ [8] The photoelectric conversion element according to any one of [1] to [7], wherein the photoelectric conversion film further comprises an n-type organic semiconductor, and wherein the photoelectric conversion film has a bulk heterostructure formed by mixing the compound represented by formula (1) with the n-type organic semiconductor. [9] The photoelectric conversion element according to [8], wherein the n-type organic semiconductor comprises a fullerene selected from the group consisting of fullerenes and derivatives thereof.

[10] The photoelectric conversion element according to any one of [1] to [9], wherein the photoelectric conversion film further comprises a dye.

[11] The photoelectric conversion element according to any one of [1] to

[10] , wherein the photoelectric conversion film further comprises a p-type organic semiconductor.

[12] The photoelectric conversion element according to any one of [1] to

[11] , wherein one or more intermediate layers are provided between the conductive film and the transparent conductive film in addition to the photoelectric conversion film.

[13] An imaging element having the photoelectric conversion element according to any one of [1] to

[12] .

[14] An optical sensor having the photoelectric conversion element according to any one of [1] to

[12] .

[15] A compound represented by formula (1) described later.

[16] A compound selected from the substituent group S described later, which is selected from the substituent group S described later, which is selected from the substituent group R described later, which is selected from the substituent group R described later, which is selected from the substituent group S described later, which is selected from the substituent group R described later, Ａｒ１ The compound according to

[15] , wherein X represents an aromatic ring group optionally having a substituent selected from the group consisting of: a group represented by formula (S-3) described later, or a group represented by formula (S-4) described later.

[17] The compound according to

[15] or

[16] , wherein the group represented by formula (A-1) described later is a group represented by formula (A-2) described later.

[18] The compound according to

[17] , wherein the group represented by formula (A-2) is a group represented by formula (C-1) described later or a group represented by formula (C-2) described later.

[19] The compound according to

[18] , wherein X represents >NR Ｎ , >CR Ｃ１ R Ｃ２ , >C=CR Ｃ３ R Ｃ４ , >SiR Ｃ５ RＣ６ , >GeR Ｃ７ R Ｃ８ , or -OC(R Ｃ９ ) (R Ｃ１０ The compound according to any one of

[15] to

[18] , wherein R Ｎ and R Ｃ１ ~R Ｃ１０ are R in the above formula (1), Ｎ , and R Ｃ１ ~R Ｃ１０

[20] X is >NR Ｎ , >CR Ｃ１ R Ｃ２ , or >C=CR Ｃ３ R Ｃ４ The compound according to any one of

[15] to

[19] , wherein R Ｎ and R Ｃ１ ~R Ｃ４ are R in the above formula (1), Ｎ , and R Ｃ１ ~R Ｃ４

[21] X is >NR Ｎ The compound according to any one of

[15] to

[20] , wherein R Ｎ is R in the above formula (1). Ｎ

[22] A compound represented by formula (2) described later.

[23] A method for producing a compound, comprising a step of reacting a compound represented by formula (2a) described later with a compound represented by formula (X) described later to produce a compound represented by formula (2b) described later.

[24] A step of reacting a compound represented by formula (2a) described later with a compound represented by formula (X) described later to produce a compound represented by formula (2b) described later; and Ｌ４ and groups represented by R Ｌ５ The group represented by the formula (I) is a formyl group, *-Sn(R Ｓｎ ) ３ , *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋ and converting R Ｓｎ , R Ｂ１ and RＢ２ each independently represents a substituent, and a plurality of R Ｓｎ , R Ｂ１ and R Ｂ２ may be the same or different from each other. Ｂ１ Peers and R Ｂ２ may be bonded to each other to form a ring structure. ＋ represents a monovalent metal cation. * represents a bonding position.

[25] A compound represented by formula (3) described later.

[26] A compound represented by formula (3a) described later is reacted with a compound represented by formula (A) described later to obtain SiR Ｙ１ ３ A method for producing a compound, comprising: Step 1 obtaining a compound represented by formula (3b) described below having a protecting group represented by the formula: Step 2 reacting the compound represented by formula (3b) with a metallation reagent, followed by reaction with a formylating agent and further deprotecting the protecting group to obtain a compound represented by formula (3c) described below; and Step 3 reacting the compound represented by formula (3c) with a compound represented by formula (C) described below to obtain a compound represented by formula (3) described below.

[27] A compound represented by formula (3c) described below.

[0008] According to the present invention, a photoelectric conversion element having excellent quantum efficiency when receiving blue light can be provided. Furthermore, according to the present invention, an imaging element, an optical sensor, a compound, and a method for producing the compound, which are related to the photoelectric conversion element, can be provided.

[0009] 1 is a schematic cross-sectional view showing an example of the configuration of a photoelectric conversion element.

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] The meaning of each description in this specification is as follows. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In this specification, a hydrogen atom may be a protist atom (a normal hydrogen atom) or a deuterium atom (for example, a deuterium atom, etc.).

[0012] The symbol "*" shown in a chemical formula represents a bonding position unless otherwise specified. In this specification, when there are multiple substituents and linking groups, etc. (hereinafter also referred to as "substituents, etc.") represented by a specific symbol, or when multiple substituents, etc. are specified at the same time, it means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc. In this specification, unless otherwise specified, "substituents" include groups exemplified as the substituent W described below.

[0013] (Substituent W) The substituent W in this specification will be described. Examples of the substituent W include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (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, Examples of the substituent W include secondary or tertiary amino groups (including anilino groups), alkylthio groups, arylthio groups, heterocyclic thio groups, alkyl or arylsulfinyl groups, alkyl or arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, aryl or heterocyclic azo groups, imido groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, carboxy groups, phosphate groups, sulfonic acid groups, hydroxy groups, thiol groups, acylamino groups, carbamoyl groups, ureido groups, boronic acid groups, and primary amino groups. Furthermore, each of the above groups may further have a substituent (e.g., one or more of the above groups, etc.) if possible. For example, an alkyl group which may have a substituent is also included as one form of the substituent W. Furthermore, when 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 compounds described below may have, as substituents, 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 does not have a primary amino group.

[0014] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0015] In this specification, the aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. In addition, unless otherwise specified in this specification, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include 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. In addition, the alkyl group may be a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group, and may have these ring structures as partial structures. In the alkyl group that may have a substituent, examples of the substituent that the alkyl group may have include the groups exemplified for the substituent W. Of these, 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), or a halogen atom (preferably a fluorine atom or a chlorine atom) is preferred.

[0016] In this specification, unless otherwise specified, 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. In the alkoxy group which may have a substituent, 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. In the alkylthio 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.

[0017] In this specification, unless otherwise specified, the alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group is preferably 2 to 20. In the alkenyl group which may have a substituent, examples of the substituent that the alkenyl group may have include the same as the substituents in the alkyl group which may have a substituent. In this specification, unless otherwise specified, the alkynyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20. In the alkynyl group which may have a substituent, examples of the substituent that the alkynyl group may have include the same as the substituents in the alkyl group which may have a substituent.

[0018] In this specification, unless otherwise specified, 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, etc.). 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, etc.) aromatic ring is an aromatic ring having multiple (e.g., 2 to 6) condensed aromatic ring structures as a ring structure. The number of ring member atoms of the aromatic ring is preferably 4 to 15. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. When the aromatic ring is an aromatic heterocycle, the number of heteroatoms contained as ring member atoms is, for example, 1 to 10. Examples of 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. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.Examples of the aromatic heterocycle 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 naphthopyrrole ring, a naphthofuran ring, a naphthothiophene ring, a naphthoimidazole ring, a naphthoxazole ring, a 3H-pyrrolidine ring, a pyrroloimidazole ring (for example, a 5H-pyrrolo[1,2-a]imidazole ring), an imidazooxazole ring (for example, an imidazo[2,1-b]oxazo a thienothiazole ring (for example, a thieno[2,3-d]thiazole ring), a benzothiadiazole ring, a benzodithiophene ring (for example, a benzo[1,2-b:4,5-b']dithiophene ring), a thienothiophene ring (for example, a thieno[3,2-b]thiophene ring), a thiazolothiazole ring (for example, a thiazolo[5,4-d]thiazole ring), a naphthodithiophene ring (for example, a naphtho[ Examples of the aromatic ring that may have a substituent include a benzothienobenzothiophene ring, a dithieno[3,2-b:2',3'-d]thiophene ring, and a 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring. In the aromatic ring that may have a substituent, examples of the substituent that the aromatic ring may have include the groups exemplified by the substituent W. When the aromatic ring has a substituent, the number of the substituents may be one or more (e.g., 1 to 4). In this specification, the term "aromatic ring group" includes, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from the aromatic ring. In this specification, the term "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.In the present specification, the term "heteroaryl group" refers to, for example, a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic heterocycle among the above aromatic rings. In the present specification, the term "arylene group" refers to, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic hydrocarbon ring among the above aromatic rings. In the present specification, the term "heteroarylene group" refers to, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the above aromatic rings. In the optionally substituted aromatic ring group, optionally substituted aryl group, optionally substituted heteroaryl group, optionally substituted arylene group, and optionally substituted heteroarylene group, the types of substituents that these groups may have include, for example, the groups exemplified for the substituent W. When these optionally substituted groups have substituents, the number of substituents may be 1 or more (e.g., 1 to 4).

[0019] In this specification, the number of ring members of the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and still more preferably 6 to 8. Examples of heteroatoms 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 aliphatic heterocycles 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 γ-butyrolactone.

[0020] The bonding direction of divalent groups (such as -CO-O-) shown in this specification is not limited unless otherwise specified. For example, 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." In this specification, "optionally containing an ethereal 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 the terminal.

[0021] In this specification, with respect to compounds that may have geometric isomers (cis-trans isomers), 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.

[0022] [Photoelectric Conversion Element] The photoelectric conversion element of the present invention has a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) (hereinafter also referred to as a "specific compound") described below. The mechanism by which the photoelectric conversion element of the present invention can solve the problems of the present invention by adopting the above-described configuration is not necessarily clear, but the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The compound disclosed in Literature 1 is an ADA-type dye having a structure in which a branched alkyl group is substituted on a fused ring structure such as fluorene as a donor moiety. When aromatic rings have a fused ring structure, the dyes are likely to aggregate, leading to a deterioration in the quantum efficiency of the photoelectric conversion element. Therefore, Literature 1 suppresses aggregation by introducing a substituent such as an alkyl group. However, the substituent in Literature 1 is too large to efficiently exchange electrons and holes, resulting in insufficient quantum efficiency. On the other hand, in the case of the specific compound of the present invention, the size of the substituent introduced into the fused ring structure of carbazole, fluorene, etc. is optimized, so that the above-mentioned aggregation of dyes does not occur, and electrons and holes can be efficiently exchanged, which is presumably why the quantum efficiency of the photoelectric conversion element is improved compared to that of Literature 1. Hereinafter, superior quantum efficiency when the photoelectric conversion element receives blue light (light with a wavelength in the range of 400 to 500 nm) is also referred to as superior effects of the present invention. The configuration of the photoelectric conversion element of the present invention is described in detail below.

[0023] FIG. 1 shows a cross-sectional schematic diagram of one embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in FIG. 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 an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in FIG. 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 and 2 may be changed as appropriate depending on the application and characteristics.

[0024] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 through the upper electrode 15. 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 a voltage of 1×10 is applied between the pair of electrodes. －５ ~1 x 10 ７ In terms of performance and power consumption, it is preferable to apply a voltage of 1×10 V / cm. －４ ~1 x 10 ７ V / cm is more preferable, and 1×10 －３ ~5 x 10 ６ V / cm is more preferable. Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode in FIGS. 1 and 2. When the photoelectric conversion element 10a (or 10b) is used as a photosensor or incorporated into an imaging element, a voltage can be applied in a similar manner. As will be described in detail later, 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.

[0025] [Photoelectric Conversion Film] The photoelectric conversion element of the present invention has a photoelectric conversion film.

[0026] <Specific Compound> The photoelectric conversion film contains a compound (specific compound) represented by formula (1).

[0027]

[0028] In formula (1), X is >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. Ｎ represents a substituent selected from the substituent group S described below. Ｃ１ ~R Ｃ１０ each independently represents a hydrogen atom or a substituent selected from the substituent group S described below. Ｃ１ and R Ｃ２ represents a substituent selected from the substituent group S, and R Ｃ３ and R Ｃ４ represents a substituent selected from the substituent group S, and R Ｃ５ and R Ｃ６ represents a substituent selected from the substituent group S, and R Ｃ７ and R Ｃ８ represents a substituent selected from the substituent group S, and R Ｃ９ and R Ｃ１０ At least one of R represents a substituent selected from the substituent group S. Ｃ１ and R Ｃ２ , R Ｃ３ and R Ｃ４ , R Ｃ５ and R Ｃ６ , R Ｃ７ and R Ｃ８ , and R Ｃ９ and R Ｃ１０ may each independently bond directly or via a linking group to form a ring. For example, R Ｃ１ and R Ｃ２and may both be benzene ring groups and may be directly bonded (bonded via a single bond) to form a fluorene ring. Ｎ , >CR Ｃ１ R Ｃ２ , >C=CR Ｃ３ R Ｃ４ , >SiR Ｃ５ R Ｃ６ , >GeR Ｃ７ R Ｃ８ , or -OC(R Ｃ９ ) (R Ｃ１０ )-, and >NR Ｎ , >CR Ｃ１ R Ｃ２ , or >C=CR Ｃ３ R Ｃ４ More preferably, it represents >NR Ｎ Or >CR Ｃ１ R Ｃ２ More preferably, it represents >NR Ｎ It is most preferred that R Ｃ１ and R Ｃ２ Preferably, both of R represent a substituent selected from the substituent group S. Ｃ３ and R Ｃ４ Preferably, both of R represent a substituent selected from the substituent group S. Ｃ５ and R Ｃ６ Preferably, both of R represent a substituent selected from the substituent group S. Ｃ７ and R Ｃ８ Preferably, both of R represent a substituent selected from the substituent group S. Ｃ９ and R Ｃ１０ and preferably represent a substituent selected from the substituent group S.

[0029] Substituent Group S Substituent Group S is a group consisting of the following substituents. Substituent Group S: linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms (hereinafter referred to as "substituent S"). Ａ "), a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent (hereinafter 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 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 referred to as "substituent S ＡＡｒ "), a branched aliphatic hydrocarbon group having 3 carbon atoms and a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms (hereinafter referred to as "substituent S ＤＢ "), a branched aliphatic hydrocarbon group having 3 carbon atoms and an aromatic ring group which may have a substituent (hereinafter referred to as "substituent S ＤＡｒ "), an aromatic ring group which may have a substituent (hereinafter referred to as "substituent S Ａｒ "), a group represented by formula (S-1), and a group represented by formula (S-2). In the substituent group S, 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 which has a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which has an aromatic ring group which may have a substituent, the branched aliphatic hydrocarbon group having 3 carbon atoms which has a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, and the branched aliphatic hydrocarbon group having 3 carbon atoms which has an aromatic ring group which may have a substituent may have an etheric oxygen atom or may be substituted with a halogen atom.

[0030] Substituent S Ａ The number of carbon atoms of is not particularly limited as long as it is 1 to 3, but is preferably 1 or 2. Ａ Examples of the linear alkyl group 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 preferred. Examples of the linear alkenyl group having 2 or 3 carbon atoms include a vinyl group, an allyl group, or an isoallyl group. Examples of the linear alkynyl group having 2 or 3 carbon atoms include an ethynyl group, a 1-propynyl group, or a propargyl group.

[0031] Substituent S Ｂ The cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms may have either a monocyclic or polycyclic structure.Ｂ The number of carbon atoms in the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms is not particularly limited as long as it is 3 to 8, but 3 to 6 carbon atoms is preferred, and 3 is more preferred. Ｂ Examples of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms 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 obtained by removing one hydrogen atom from bicyclo[1,1,1]pentane. Examples of the cyclic alkenyl group having 3 to 8 carbon atoms include a group obtained by removing one hydrogen atom from a cycloalkene having 3 to 8 carbon atoms. Examples of cycloalkenes include cyclobutene, cyclopentene, cyclohexene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene. Substituent S Ｂ The number of substituents that the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms may have is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2. Ｂ Examples of the substituent that the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms may have include the groups exemplified above for the substituent W. Among these, the substituent S Ｂ The substituents that the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms may have include those in the substituent group R Ａｒ１ 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 preferred.

[0032] Substituent S ＡＢ As described above, is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which has a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms. Ａ This corresponds to a group in which one or more hydrogen atoms in 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. ＡＢ Among them, the number of cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2. ＡＢSpecific and preferred embodiments of the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms in Ａ The specific and preferred embodiments are the same as those of the substituent S ＡＢ Specific and preferred embodiments of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the above formula are the substituents S Ｂ The specific embodiments and preferred embodiments of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms are the same as those of the substituent S ＡＢ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferably a linear alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. ＡＢ Of these, the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms is preferably a cyclic alkyl group having 3 to 8 carbon atoms, more preferably a cyclic alkyl group having 3 to 6 carbon atoms.

[0033] Substituent S ＡＢ Examples of the substituent include a methyl group having a cyclic alkyl group having 3 to 8 carbon atoms (hereinafter 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 referred to as "substituent S ＡＢ２ In other words, a group in which the 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 referred to as "substituent S ＡＢ３ In other words, a group obtained by substituting a hydrogen atom of an n-propyl group with a cyclic alkyl 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 obtained by removing one hydrogen atom from bicyclo[1,1,1]pentane. Of these, a cyclopropyl group is preferred.

[0034] Substituent S ＡＢ１ Among them, the number of cyclic alkyl groups having 3 to 8 carbon atoms is not particularly limited, but is preferably 1 or 2. ＡＢ１Among these, 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 preferred, 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 preferred.

[0035] Substituent S ＡＢ２ Among them, the number of cyclic alkyl groups having 3 to 8 carbon atoms is not particularly limited, but is preferably 1 or 2. ＡＢ３ Among them, the number of cyclic alkyl groups having 3 to 8 carbon atoms is not particularly limited, but is preferably 1 or 2.

[0036] Substituent S ＡＡｒ As described above, is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms and an aromatic ring group which may have a substituent, and the above-mentioned substituent S Ａ (a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms) Ａｒ (an aromatic ring group which may have a substituent) ＡＡｒ Among them, 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.

[0037] Substituent S ＡＡｒ Specific and preferred embodiments of the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms and the aromatic ring group which may have a substituent are the above-mentioned substituents S Ａ and the substituent S Ａｒ The specific and preferred embodiments are the same as those of the substituent S ＡＡｒ The linear aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferably a linear alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. ＡＡｒ The aromatic ring group which may have a substituent is preferably an aryl group, more preferably a phenyl group.

[0038] Substituent S ＤＢ As described above, is a branched aliphatic hydrocarbon group having 3 carbon atoms and having a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms. Ｄ") by substituting one or more hydrogen atoms with a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms. ＤＢ Among them, the number of cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2. ＤＢ In the formula (I), examples of the branched aliphatic hydrocarbon group having 3 carbon atoms include an isopropyl group and an isopropenyl group. Of these, an isopropyl group is preferred. ＤＢ Specific and preferred embodiments of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the formula (I) are the substituents S Ｂ Specific and preferred embodiments of the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms are as described above.

[0039] Substituent S ＤＡｒ As described above, is a branched aliphatic hydrocarbon group having 3 carbon atoms and an aromatic ring group which may have a substituent, and the above-mentioned substituent S Ｄ (a branched aliphatic hydrocarbon group having 3 carbon atoms) Ａｒ (an aromatic ring group which may have a substituent) ＤＡｒ 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. ＤＡｒ In the formula, the substituent S Ｄ Specific and preferred embodiments of the substituent S are as described above. ＤＡｒ In the formula, the substituent S Ａｒ Specific and preferred embodiments of the above will be described later.

[0040] Substituent S Ａｒ The aromatic ring constituting the aromatic ring group in 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, the polycyclic aromatic ring, the aromatic hydrocarbon ring, and the aromatic heterocyclic ring are as described above. Ａｒ The number of ring atoms in the aromatic ring constituting the aromatic ring group is preferably 4 to 15, more preferably 4 to 10, and even more preferably 4 to 6. ＡｒThe aromatic hydrocarbon ring constituting the aromatic ring group in the formula (I) is preferably a benzene ring, a naphthalene ring, or an anthracene ring. Ａｒ The aromatic heterocycle constituting the aromatic ring group is preferably a pyridine ring, a thiophene ring, a benzofuran ring (for example, a 2,3-benzofuran ring), or a benzothiophene ring (for example, a benzo[b]thiophene ring).

[0041] Substituent S Ａｒ The number of substituents that the aromatic ring group in the formula (I) may have is not particularly limited, but is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2. Ａｒ Examples of the substituent that the aromatic ring group in the formula (I) may have include the groups exemplified above as the substituent W. Ａｒ When the aromatic ring group in the formula (I) has a plurality of substituents, the substituents may be bonded to each other to form a non-aromatic ring. Ａｒ The substituents that the aromatic ring group in Ａｒ１ 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 preferred.

[0042] ・Substituent group R Ａｒ１ The above-mentioned substituent group R Ａｒ１ The substituents selected from the substituent group R are as follows: Ａｒ１ : 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, an aromatic ring group, a halogen atom, and *—Si(R Ｓｉ ) ３ .R 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. Ａｒ１ Among these, 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 etheric oxygen atom or may be substituted with a halogen atom.

[0043] Substituent group R Ａｒ１ Among these, 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 described in the section on the substituent S Ａ and substituent S Ｂ The specific embodiments and preferred embodiments are the same as those of the substituent group R. Ａｒ１ Among these, 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 3 to 4 is preferred. Substituent group R Ａｒ１ Among these, specific and preferred embodiments of the aromatic ring group include the substituent S Ａｒ Among them, an aryl group is preferred, and a phenyl group is more preferred.

[0044] R Ｓｉ Specific and preferred embodiments of 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, which are represented by the following formula, are described in the substituent group R Ａｒ１ The embodiments and preferred embodiments of each group are the same as those described above. Ｓｉ Specific and preferred embodiments of the aromatic ring group represented by the formula (I) are as described above, but among these, an aryl group is preferred, and a phenyl group is more preferred.

[0045] The group represented by formula (S-1) is as follows: *-L Ｓ１ -C(R Ｓ１ ) ３ Formula (S-1) In formula (S-1), L Ｓ１ represents a single bond or a linear alkylene group having 1 to 3 carbon atoms. Ｓ１ each 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. Ｓ１ may be the same or different from each other. Ｓ１Among these, two or more are other than hydrogen atoms. 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 etheric oxygen atom or may be substituted with a halogen atom.

[0046] The number of carbon atoms in the group represented by formula (S-1) is preferably 3 to 9, and more preferably 3 to 7. The number of carbon atoms in the group represented by formula (S-1) means the total number of all carbon atoms contained in the group represented by formula (S-1). Ｓ１ is preferably a single bond or a methylene group, more preferably a single bond. Ｓ１ The number of R is not particularly limited as long as it is two or more. Ｓ１ It is preferred that one of R is a hydrogen atom and the remaining two are other than hydrogen atoms. Ｓ１ Among these, a methyl group, an isopropyl group, or a t-butyl group is preferred, and a methyl group or an isopropyl group is more preferred.

[0047] The group represented by formula (S-2) is as follows: *-C(=Q)R Ａｃ１ Formula (S-2): In formula (S-2), Q represents an oxygen atom or a sulfur atom. Q is preferably an oxygen atom. 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. Ａｃ１ The definitions of the groups represented by R are as described above. Ａｃ１ Examples of the substituent that each group represented by the following formula may have include the groups exemplified as the substituent W above.

[0048] R Ａｃ１ Among these, the aliphatic hydrocarbon group represented by the formula (I) which may have a substituent is preferably a linear, branched or cyclic aliphatic hydrocarbon group which may have a halogen atom. Ａｃ１ The aromatic ring group which may have a substituent represented by the following formula (I) is particularly preferably the aromatic ring group represented by the following formula (I): Ａｒ１An aromatic ring group optionally having a substituent selected from the following is preferred.

[0049] In terms of the effects of the present invention being more excellent, the substituents selected from the above-mentioned substituent group S are selected from 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, a substituent group R Ａｒ１ It is preferable that the aromatic ring group optionally having a substituent selected from the above, a group represented by formula (S-3), or a group represented by formula (S-4).

[0050] In addition, the above-mentioned substituent group R Ａｒ１ Specific and preferred embodiments of the substituents selected from the group R Ａｒ１ The substituents selected from the group R Ａｒ２ The substituent group R is preferably a substituent selected from the following: Ａｒ２ : 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, a halogen atom, and *-Si(R Ｓｉ ) ３ .R 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. Ａｒ２ Among these, 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 etheric oxygen atom or may be substituted with a halogen atom.

[0051] The group represented by formula (S-3) is as follows: *—C(R Ｓ２ ) ３ Formula (S-3) In formula (S-3), R Ｓ２ Each of R independently represents a hydrogen atom, a methyl group, an isopropyl group, or a t-butyl group. Ｓ２ may be the same or different from each other, provided that the number of carbon atoms in the group represented by formula (S-3) is 3 to 9, and the three R Ｓ２ Among these, two or more are other than hydrogen atoms.

[0052] The number of carbon atoms in the group represented by formula (S-3) is preferably 3 to 9, and more preferably 3 to 7. The number of carbon atoms in the group represented by formula (S-3) means the total number of all carbon atoms contained in the group represented by formula (S-3). Ｓ２ The number of R is not particularly limited as long as it is two or more. Ｓ２ It is preferred that one of R is a hydrogen atom and the remaining two are other than hydrogen atoms. Ｓ２ Among these, a methyl group or an isopropyl group is preferable.

[0053] The group represented by formula (S-4) is as follows: *—C(═O)R Ａｃ２ Formula (S-4) R Ａｃ２ is 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 the above-mentioned substituent group R Ａｒ１ The aliphatic hydrocarbon group is preferably an alkyl group. Ａｒ１ The aromatic ring group which may have a substituent selected from the above 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.

[0054] In formula (1), Z １ ~Z ６ are each independently -CR Ｘ１ = or a nitrogen atom. １ ~Z ６ Two adjacent ones are -CR Ｘ１ If =, then two R Ｘ１ may be bonded to each other to form a ring. Ｘ１represents a hydrogen atom or a substituent. １ ~Z ６ Four or more of the above are -CR Ｘ１ It is preferred that all of them represent -CR Ｘ１ It is more preferable that Z represents ≡ ... １ ~Z ６ Two or more of the above are -CR Ｘ１ =, R Ｘ１ may be the same or different. １ ~Z ６ Two or less of (preferably, Z ２ , Z ３ , Z ５ and Z ６ Two or less of these) are R Ｘ１ is a substituent -CR Ｘ１ = and Z １ ~Z ６ The remainder of the groups is preferably -CH=, and Z １ ~Z ６ It is more preferable that all of the groups are —CH═.

[0055] R Ｘ１ Examples of the substituent represented by the formula (I) include the groups exemplified for the substituent W above, and more specifically, include a halogen atom and an alkyl group. 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 even more preferably a methyl group.

[0056] In formula (1), R １ and R ２ R each independently represents a hydrogen atom or a substituent. １ and R ２ Examples of the substituent represented by the formula (I) include the groups exemplified as the substituent W. Among them, in terms of the effects of the present invention being more excellent, R １ and R ２ is preferably a hydrogen atom.

[0057] In formula (1), A １ and A ２each independently represents a group represented by the above formula (A-1). １ each independently represents a sulfur atom, an oxygen atom, or ═NR Ｘ２ , or =CR Ｘ３ R Ｘ４ Represents R Ｘ２ represents a hydrogen atom or a substituent. Ｘ３ and R Ｘ４ each independently represents a cyano group, —SO ２ R Ｘ５ , -COOR Ｘ６ , or -COR Ｘ７ Represents.

[0058] Y １ R preferably represents an oxygen atom or a sulfur atom, as this provides better effects of the present invention. Ｘ２ Examples of the substituent represented by the formula (I) include the substituents exemplified above for the substituent W. Ｘ５ ~R Ｘ７ R each independently 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. Ｘ５ ~R Ｘ７ Examples of the substituent that these groups represented by the formula (I) may have include the substituents exemplified for the substituent W above. The aliphatic hydrocarbon group is defined as above, and among them, an alkyl group is preferred, and a linear alkyl group is more preferred. The aliphatic hydrocarbon group preferably has 1 to 3 carbon atoms. The aromatic ring group is defined as above, and among them, an aryl group is preferred, and a phenyl group is more preferred. The aliphatic heterocyclic group is defined as above.

[0059] In formula (A-1), C １represents a ring containing two or more carbon atoms and optionally having a substituent. The number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms is the number including the two carbon atoms specified in the formula. The ring may be either aromatic or non-aromatic. The ring may be either monocyclic or polycyclic, 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, more preferably 1 to 3. The ring may have a heteroatom. Examples of 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, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms in the ring is preferably 0 to 10, more preferably 0 to 5.

[0060] Above C １ Among the carbon atoms constituting the ring represented by the formula (A-1), the carbon atom at the bonding position marked with * and Y １ Carbon atoms other than the carbon atom bonded to may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S). Examples of the substituent that the ring may have include the groups exemplified for the substituent W above, and a halogen atom, an alkyl group, an aromatic ring group, or a silyl group is preferred, and a halogen atom or an alkyl group is more preferred. The alkyl group may be linear, branched, or cyclic, and a linear group is preferred. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0061] Above C １The ring represented by the formula (I) is preferably a ring used as an acidic nucleus (for example, the acidic nucleus in a merocyanine dye), and examples thereof include the following nuclei: (a) 1,3-dicarbonyl nucleus: for example, a 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-4,6-dione; (b) pyrazolinone nucleus: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, and 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one; (c) isoxazolinone nucleus: for example, 3-phenyl-2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one; (d) oxindole nucleus: for example, 1-alkyl-2,3-dihydro-2-oxindole; (e) 2,4,6-trioxohexahydropyrimidine nucleus: for example, barbituric acid, 2-thiobarbituric acid, and derivatives thereof. Examples of 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). (f) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and derivatives thereof. Examples of the derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-allylrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and 3-heteroarylrhodanines such as 3-(2-pyridyl)rhodanine. (g) 2-thio-2,4-oxazolidinedione nucleus (2-thio-2,4-(3H,5H)-oxazoledione nucleus): for example, 3-ethyl-2-thio-2,4-oxazolidinedione. (h) thianaphthenone nucleus: for example, 3(2H)-thianaphthenone-1,1-dioxide. (i) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione.(j) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, and 3-phenyl-2,4-thiazolidinedione. (k) thiazolin-4-one nucleus: for example, 4-thiazolinone and 2-ethyl-4-thiazolinone. (l) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione. (m) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione. (n) Imidazolin-5-one nucleus: for example, 2-propylmercapto-2-imidazolin-5-one. (o) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione. (p) Benzothiophen-3(2H)-one nucleus: for example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one and dioxobenzothiophen-3(2H)-one. (q) Indanone nucleus: for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone and 3,3-dimethyl-1-indanone. (r) Benzofuran-3-(2H)-one nucleus: for example, benzofuran-3-(2H)-one. (s) 2,2-dihydrophenalene-1,3-dione nucleus, etc.

[0062] The group represented by the formula (A-1) is preferably a group represented by the formula (A-2) in that the effects of the present invention are more excellent.

[0063]

[0064] In formula (A-2), X １ and X ２ Each of X independently represents an oxygen atom or a sulfur atom. １ and X ２ Preferably, both of C represent an oxygen atom. ２ represents a ring containing 3 or more carbon atoms. ２The three carbon atoms contained in are the three carbon atoms specified 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 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. When the ring is a polycyclic ring, the number of rings contained is preferably 2 to 6, more preferably 2 or 3. The ring may have a heteroatom. Examples of 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, and a sulfur atom, a nitrogen atom, or an oxygen atom is preferred. The number of heteroatoms contained in the ring is preferably 0 to 10, more preferably 0 to 5. ２ Among the carbon atoms constituting the ring represented by the formula (A-2), the carbon atom at the bonding position marked with * and X １ and X ２ A carbon atom other than the carbon atom bonded to the ring C may be substituted with a carbonyl carbon (>C=O) or a thiocarbonyl carbon (>C=S). １ The substituents are the same as those that may be possessed by the group.

[0065] The group represented by the formula (A-2) is preferably a group represented by the formula (C-1) or a group represented by the formula (C-2).

[0066]

[0067] In formula (C-1), X ｃ１ and X ｃ２ Each of the X independently represents a sulfur atom or an oxygen atom. ｃ１ and X ｃ２ At least one of X is preferably an oxygen atom, ｃ１ and X ｃ２ It is more preferable that both of the groups are oxygen atoms.

[0068] In formula (C-1), C ３represents 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 is the number including the two carbon atoms specified in the formula. The aromatic ring may be either a monocyclic or polycyclic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but an aromatic hydrocarbon ring is preferred. The C ３ Examples of the aromatic ring represented by the formula (I) include the rings exemplified in the description of the aromatic ring above. ３ The aromatic ring represented by the formula (I) is preferably a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring, and more preferably a benzene ring. Examples of the substituent that the aromatic ring may have include the groups exemplified for the substituent W.

[0069] In the above formula (C-2), X ｃ３ ~X ｃ５ represents a sulfur atom or an oxygen atom. ｃ３ ~X ｃ５ are preferably all oxygen atoms. ｃ１ and R ｃ２ R each independently represents a hydrogen atom or a substituent. ｃ１ and R ｃ２ Examples of the substituent represented by the formula (I) include the groups exemplified by the above-mentioned substituent W, among which an alkyl group or a phenyl group is preferred, and an alkyl group is more preferred. The above-mentioned phenyl group may further have a substituent, and examples thereof include the groups exemplified by the above-mentioned substituent W.

[0070] In the above formula (1), A １ and A ２ is a group represented by formula (A-1), the specific compound is represented by formula (1A-1), １ and A ２ is a group represented by formula (A-2), the specific compound is represented by formula (1A-2). When the group represented by formula (A-2) is a group represented by formula (C-1), the specific compound is represented by formula (1C-1), and when the group represented by formula (A-2) is a group represented by formula (C-2), the specific compound is represented by formula (1C-2).

[0071]

[0072] The molecular weight of the specific compound is preferably 400 to 1,200, more preferably 400 to 1,000, and even more preferably 500 to 800. When the molecular weight is within the above range, the sublimation temperature of the specific compound is lowered, and it is presumed that the quantum efficiency is excellent even when a photoelectric conversion film is formed at high speed.

[0073] The specific compound preferably has an ionization potential of −5.0 to −6.0 eV in a single film from the viewpoints of stability when used as a p-type organic semiconductor and matching of the energy level with an n-type organic semiconductor.

[0074] The maximum absorption wavelength of the specific compound is preferably in the wavelength range of 400 to 600 nm, more preferably in the wavelength range of 400 to 500 nm. The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1.0. However, if the specific compound is insoluble in chloroform, the maximum absorption wavelength of the specific compound is determined by evaporating the specific compound and measuring the value using the specific compound in a film state.

[0075] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging device, a photosensor, or a photovoltaic cell. The specific compound often functions as a dye in the photoelectric conversion film. The specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic material.

[0076] Specific examples of the specific compound are shown below, but the present invention is not limited to these.

[0077]

[0078]

[0079]

[0080]

[0081]

[0082] In the specific compounds exemplified above, A represents any of the following groups.

[0083]

[0084]

[0085]

[0086]

[0087] The specific compound may be purified as necessary. Examples of methods for purifying the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, and purification using an adsorbent such as activated carbon and recrystallization purification.

[0088] The content of the specific compound in the photoelectric conversion film (=film thickness of the specific compound in terms of a single layer / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 20 to 50% by volume. Only one type of specific compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is in the above range.

[0089] <n-Type Organic Semiconductor> 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 specific compound. The n-type organic semiconductor is an acceptor organic semiconductor material (compound) and refers to an organic compound that has the property of easily accepting electrons. In other words, the n-type organic semiconductor refers to the 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 can be used as the acceptor organic semiconductor as long as it is an organic compound with electron-accepting properties. Examples of 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 a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyridine ... 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 JP 2006-100767 A.

[0090] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferred. Examples of 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. Examples of fullerene derivatives include compounds in which a substituent is added to the above-mentioned fullerenes. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. As the fullerene derivative, the compounds described in JP 2007-123707 A are preferred.

[0091] The n-type organic semiconductor may be an organic dye. Examples of the organic dye 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, acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, and metal complex dyes.

[0092] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0093] 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.

[0094] The photoelectric conversion film preferably has a bulk heterostructure formed in a state in which a specific compound and an n-type organic semiconductor are mixed. The bulk heterostructure is a layer in the photoelectric conversion film in which a specific compound and an n-type organic semiconductor are mixed and dispersed. The 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.

[0095] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.

[0096] When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (thickness of the n-type organic semiconductor in terms of a single layer / thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 20 to 50 vol%.

[0097] When the n-type organic semiconductor material contains fullerenes, the content of the fullerenes relative to the total content of the n-type organic semiconductor material (film thickness in monolayer equivalent of fullerenes / total film thickness in monolayer equivalent of each n-type organic semiconductor material×100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume. Fullerenes may be used singly or in combination of two or more types.

[0098] In terms of the response speed of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor) x 100) is preferably 20 to 80% by volume, more preferably 40 to 80% by volume. When the photoelectric conversion film contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the specific compound (film thickness in monolayer equivalent of the specific compound / (film thickness in monolayer equivalent of the specific compound + film thickness in monolayer equivalent of the n-type organic semiconductor + film thickness in monolayer equivalent of the p-type organic semiconductor) x 100) is preferably 15 to 75% by volume, more preferably 30 to 75% by volume. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, the n-type organic semiconductor, and a p-type organic semiconductor that is included as desired. "Substantially" means that the total content of the specific compound, n-type organic semiconductor, and p-type organic semiconductor is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume, relative to the total mass of the photoelectric conversion film.

[0099] <p-Type Organic Semiconductor> 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 specific compound. The p-type organic semiconductor is a donor organic semiconductor material (compound) and refers to an organic compound that has the property of easily donating electrons. In other words, the p-type organic semiconductor refers to the 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 types.

[0100] 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 (α-NPD), compounds described in paragraphs

[0128] to

[0148] of JP-A No. 2011-228614, compounds described in paragraphs

[0052] to

[0063] of JP-A No. 2011-176259, compounds described in paragraphs

[0119] to

[0158] of JP-A No. 2011-225544, compounds described in paragraphs

[0119] to

[0158] of JP-A No. 2015-1 compounds described in paragraphs

[0044] to

[0051] of JP-A No. 53910 and paragraphs

[0086] to

[0090] of JP-A No. 2012-094660, etc.), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (for example, thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b]thiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivatives, JP-A No. 2012-094660, etc. Compounds described in paragraphs

[0031] to

[0036] of WO 2018-014474, compounds described in paragraphs

[0043] to

[0045] of WO 2016 / 194630, compounds described in paragraphs

[0025] to

[0037] and

[0099] to

[0109] of WO 2017 / 159684, compounds described in paragraphs

[0029] to

[0034] of JP 2017-076766 A, compounds described in paragraphs

[0015] to

[0025] of WO 2018 / 207722, compounds described in paragraphs

[0045] to

[0053] of JP 2019-058 995, the compounds described in paragraphs

[0045] to

[0055] of WO2019 / 081416, the compounds described in paragraphs

[0063] to

[0089] of JP2019-80052, the compounds described in paragraphs

[0033] to

[0036] of JP2019-80052, the compounds described in paragraphs

[0044] to

[0054] of WO2019 / 054125, the compounds described in paragraphs

[0041] to

[0046] of W2019 / 093188, etc.), the compounds described in paragraphs

[0034] to

[0037] of JP2019-050398, the compounds described in paragraphs

[0033] to

[0036] of JP2018-206878,The compound of paragraph

[0038] of JP 2018-190755 A, the compound of paragraphs

[0019] to

[0021] of JP 2018-026559 A, the compound of paragraphs

[0031] to

[0056] of JP 2018-170487 A, the compound of paragraphs

[0036] to

[0041] of JP 2018-078270 A, the compound of paragraphs

[0055] to

[0082] of JP 2018-11 the compounds of paragraphs

[0041] to

[0050] of JP-A-3425, the compounds of paragraphs

[0044] to

[0048] of JP-A-2018-085430, the compounds of paragraphs

[0041] to

[0045] of JP-A-2018-056546, the compounds of paragraphs

[0042] to

[0049] of JP-A-2018-046267, the compounds of paragraphs

[0031] to

[0036] of JP-A-2018-014474, and WO2018 / 01646 Compounds described in paragraphs

[0036] to

[0046] of Japanese Patent Application Laid-Open No. 2020-010024, paragraphs

[0045] to

[0048] , etc.), cyanine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand. 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), and compounds described in Figures 2 to 10 of JP-A-2022-115832.Indolotriphenylene compounds (for example, compounds described in paragraphs

[0065] to

[0072] of JP 2022-108268 A), indolocarbazole compounds (for example, compounds described in paragraphs

[0052] to

[0073] of JP 2023-005703 A and paragraph

[0028] of JP 2022-100258 A), triscarbazolylphenyl compounds (for example, compounds described in paragraphs

[0038] to

[0040] of JP 2022-181226 A), JP 2022-027575 A, paragraphs

[0070] to

[0082] of the compounds described, and JP 2021-163968 A, paragraphs

[0051] to

[0064] of the compounds described, and the like. Examples of p-type organic semiconductors include compounds that have a smaller ionization potential than n-type organic semiconductors, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductor compounds are listed below.

[0101]

[0102]

[0103]

[0104]

[0105] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.

[0106] When the photoelectric conversion film contains a p-type organic semiconductor, the content of the p-type organic semiconductor in the photoelectric conversion film (thickness of the p-type organic semiconductor in terms of a single layer / thickness of the photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 25 to 50 vol%.

[0107] The photoelectric conversion film containing the 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 having a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, more preferably 0.1% or less. The lower limit is often 0% or more.

[0108] <Dye> The photoelectric conversion film preferably contains a dye in addition to the specific compound. The dye is a compound different from the specific compound. The dye is preferably an organic dye. Examples of the organic dye 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, and benzophenone dyes. Examples of the dye include clidinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, imidazoquinoxaline dyes described in WO2020 / 013246, WO2022 / 168856, JP2023-10305A, and JP2023-10299A, as well as acceptor-donor-acceptor type dyes in which two acidic nuclei are bonded to a donor, and donor-acceptor-donor type dyes in which two donors are bonded to an acceptor. Among the organic dyes, cyanine dyes, imidazoquinoxaline dyes, and acceptor-donor-acceptor type dyes are preferred, and imidazoquinoxaline dyes and acceptor-donor-acceptor type dyes are more preferred.

[0109] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably from 400 to 650 nm, and even more preferably from 450 to 650 nm.

[0110] The content of the dye in the photoelectric conversion film relative to the total content of the specific compound and the dye (=(film thickness of the dye in terms of a single layer / (film thickness of the specific compound in terms of a single layer+film thickness of the dye in terms of a single layer)×100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and still more preferably 20 to 50 vol%.

[0111] <Film formation method> Examples of the film formation method for the photoelectric conversion film include dry film formation methods. Examples of dry film formation methods include physical vapor deposition methods such as vapor deposition (particularly vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization, and vacuum deposition methods are preferred. When forming the photoelectric conversion film by vacuum deposition, manufacturing conditions such as the degree of vacuum and deposition temperature can be set according to conventional methods.

[0112] The thickness of the photoelectric conversion film is preferably from 10 to 1,000 nm, more preferably from 50 to 800 nm, and even more preferably from 50 to 500 nm.

[0113] [Electrodes] The photoelectric conversion element preferably has electrodes. The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of conductive materials include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident through the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as tin oxide doped with antimony or fluorine (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); thin metal films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and nanocarbon materials such as carbon nanotubes and graphene. Of these, conductive metal oxides are preferred in terms of high conductivity and transparency.

[0114] Typically, when the conductive film is made thinner than a certain range, the resistance value often increases rapidly. In a solid-state imaging device incorporating a photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10,000 Ω / □, and there is a wide degree of freedom in the range of film thickness that can be reduced. Furthermore, the thinner the film thickness of the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the higher the light transmittance. An increase in light transmittance is desirable because it increases light absorption in the photoelectric conversion film and enhances photoelectric conversion performance. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance that accompany a reduction in film thickness, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0115] Depending on the application, the lower electrode 11 may be made transparent or may be made non-transparent and reflect light. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, etc., 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 (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and granphenes.

[0116] 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. When the electrode material is ITO, examples include electron beam methods, sputtering, resistance heating deposition, chemical reaction methods (such as the sol-gel method), and coating of a dispersion of indium tin oxide.

[0117] [Charge-blocking film: electron-blocking film, hole-blocking film] The photoelectric conversion element preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. Examples of the intermediate layer include a charge-blocking film. When the photoelectric conversion element has this film, the properties (quantum efficiency, response speed, etc.) of the resulting photoelectric conversion element are more excellent. Examples of the charge-blocking film include an electron-blocking film and a hole-blocking film.

[0118] [Electron Blocking Film] The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. Polymer materials can also be used as the electron blocking film. Examples of polymer materials include polymers of phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and the like, and derivatives thereof.

[0119] The electron blocking film may be composed of multiple films. The electron blocking film may be composed of an inorganic material. In general, inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher quantum efficiency. Examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

[0120] [Hole-Blocking Film] The hole-blocking film is an acceptor organic semiconductor material (compound), and the n-type organic semiconductors described above can be used. The hole-blocking film may be composed of multiple films.

[0121] Examples of methods for producing a charge blocking film include dry film formation and wet film formation. Examples of dry film formation include vapor deposition and sputtering. Vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition such as vacuum deposition being preferred. Examples of wet film formation include inkjet printing, spray printing, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with the inkjet method being preferred in terms of high-precision patterning.

[0122] The thickness of each of the charge blocking films (electron blocking film and hole blocking film) is preferably from 3 to 200 nm, more preferably from 5 to 100 nm, and even more preferably from 5 to 30 nm.

[0123] [Substrate] The photoelectric conversion element may further include a substrate. Examples of the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate. The substrate is usually positioned such that a conductive film, a photoelectric conversion film, and a transparent conductive film are stacked in this order on the substrate.

[0124] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. The performance of photoelectric conversion materials may be significantly degraded in the presence of degrading factors such as water molecules. Therefore, the degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer made of ceramics such as dense metal oxides, metal nitrides, or metal nitride oxides, or diamond-like carbon (DLC), which do not allow water molecules to penetrate. Examples of sealing layers include those described in paragraphs

[0210] to

[0215] of JP 2011-082508 A, the contents of which are incorporated herein by reference.

[0125] [Image capture element] An example of an application of a photoelectric conversion element is an image capture element. An image capture element is an element that converts the optical information of an image into an electrical signal, and typically has multiple photoelectric conversion elements arranged in a matrix on the same plane, with each photoelectric conversion element (pixel) converting the optical signal into an electrical signal and outputting the electrical signal pixel by pixel from the image capture element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.

[0126] [Optical Sensor] Other applications of 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. As an optical sensor, the photoelectric conversion element may be used alone, or may be used as a line sensor in which the photoelectric conversion elements are arranged linearly or as a two-dimensional sensor in which the photoelectric conversion elements are arranged on a plane.

[0127] [Compound] The present invention also includes a compound invention. The compound of the present invention is the specific compound described above, or an intermediate in the synthesis process of the specific compound, that 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).

[0128] <Specific Compound> Specific and preferred embodiments of the specific compound are as described above.

[0129] <Intermediate A> Intermediate A (a compound represented by formula (2)) is represented by the following structural formula.

[0130]

[0131] In the above formula (2), Z １ ~Z ６ are each independently -CR Ｘ１ = or represents a nitrogen atom. Ｘ１ represents a hydrogen atom or a substituent. １ ~Z ６ Two adjacent ones are -CR Ｘ１ If =, then two R Ｘ１ may be bonded to each other to form a ring. １ ~Z ６ Specific and preferred embodiments of the formula (1) are １ ~Z ６ The specific and preferred embodiments are the same as those of the above.

[0132] In the above formula (2), R ３ represents a substituent selected from the substituent group T. The substituent group T includes a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and the substituent group R Ａｒ３An aromatic ring group containing no nitrogen atom which may have a substituent selected from the following. The number of carbon atoms in the linear aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3. The number of carbon atoms in the branched aliphatic hydrocarbon group is preferably 3 to 10, more preferably 3 to 6, and still more preferably 3 to 5. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 10, and more preferably 3 to 8. In addition, 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.

[0133] The substituent group R in the above-mentioned substituent group T Ａｒ３ The substituents selected from the substituent group R are as follows: Ａｒ３ : a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, a halogen atom, and an aromatic ring group containing no nitrogen atom. Ａｒ３ Specific and preferred embodiments of each group exemplified in the substituent group R are the same as those of each group exemplified in the substituent group T. Ａｒ３ Among these, the linear aliphatic hydrocarbon group, the branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group may have an etheric oxygen atom or may be substituted with a halogen atom.

[0134] Among them, the substituent selected from the substituent group T is preferably 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).

[0135] In the above formula (2), R ４ and R ５ are each independently an iodine atom, *—O—S(═O) ２ R ｆ , bromine atom, chlorine atom, fluorine atom, formyl group, *-Sn(R Ｓｎ ) ３ , *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋Represents R ｆ represents a perfluoroalkyl group having 1 to 6 carbon atoms. Ｓｎ , R Ｂ１ and R Ｂ２ each independently represents a substituent, and a plurality of R Ｓｎ , R Ｂ１ and R Ｂ２ may be the same or different from each other. Ｂ１ Peers and R Ｂ２ may be bonded to each other to form a ring structure. ＋ represents a monovalent metal cation.

[0136] R ｆ A trifluoromethyl group is preferred as the perfluoroalkyl group represented by R Ｓｎ Examples of the substituent represented by the formula (I) 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. Examples of the substituent which each of the above groups may have include the groups exemplified above as the substituent W. Ｓｎ Among these, the substituent represented by R is preferably an aliphatic hydrocarbon group which may have an aromatic ring group, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably a methyl group or a butyl group. Ｂ１ The substituent represented by R 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. Ｂ１ When R are bonded to each other to form a ring, the ring formed may be an aromatic ring (for example, a benzene ring) or a non-aromatic ring. Ｂ１ Examples of the group represented by the formula (B1) and the group represented by the formula (B2) include:

[0137]

[0138] R Ｂ２ The substituent represented by M 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 R include a lithium ion, a potassium ion, a sodium ion, a rubidium ion, and a cesium ion. Ｂ２ When they are bonded to each other to form a ring, the ring formed may be an aromatic ring (for example, a benzene ring) or a non-aromatic ring. Ｂ２ Of these, 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. Ｂ２ Examples of the group represented by formula (B3) include a group represented by formula (B3). ＋ represents the monovalent metal cation.

[0139]

[0140] R ４ and R ５ The manufacturing suitability of a specific compound and R ４ and R ５ From the viewpoint of ease of functional group transformation starting from *-O-S(=O) ２ R ｆ A bromine atom, a chlorine atom, or a fluorine atom is preferred, and a bromine atom or a formyl group is more preferred.

[0141] In the above formula (2), 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.

[0142] 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 (an 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 number of ring member atoms of the aromatic ring represented by Ar is preferably 4 to 15, more preferably 4 to 10, and even more preferably 4 to 6. Of these, the aromatic hydrocarbon ring represented by Ar is preferably a benzene ring or a naphthalene ring. Furthermore, the aromatic heterocyclic ring represented by Ar is preferably a thiophene ring, a benzofuran ring (e.g., a 2,3-benzofuran ring), or a benzothiophene ring (e.g., a benzo[b]thiophene ring).

[0143] 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. When the aromatic ring represented by Ar is substituted with a substituent selected from the substituent group T or a halogen atom, the number of substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 or 2.

[0144] When the aromatic ring represented by Ar has a substituent selected from the substituent group T, R ３ and a substituent selected from the substituent group T carried on the aromatic ring represented by Ar may be bonded to each other to form a non-aromatic ring. Furthermore, when 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. Examples of the non-aromatic ring include an aliphatic ring, and examples of such a non-aromatic ring include an aliphatic ring having 4 to 6 carbon atoms.

[0145] <Method for Producing Intermediate A> As a method for producing intermediate A, for example, a compound in which an aryl group is present on the nitrogen atom of carbazole (N-aryl-substituted carbazole) is subjected to a reaction such as halogenation or lithiation (lithiation) to form an R ４ and R ５However, as described in the non-patent document "Helvetica Chimica Acta (2006), 89(6), 1123-1139" and the like, when an N-aryl-substituted carbazole is halogenated or lithiated, reactions generally proceed at the 3- and 6-positions, making it difficult to obtain intermediate A, which is a compound substituted at the 2- and 7-positions.

[0146] Step P1 In view of the above, the present inventors have conducted various studies and have found that intermediate A (compound represented by formula (2)) can be efficiently produced by a compound production method including the step 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 (hereinafter also referred to as step P1). The compound represented by formula (2b) can be produced by a method comprising the steps of: ４ and R ５ are each independently an iodine atom, *—O—S(═O) ２ R ｆ , a bromine atom, a chlorine atom, or a fluorine atom, and as will be described in detail later, in the compound represented by formula (2b), R Ｌ４ and groups represented by R Ｌ５ The group represented by the formula (I) is a formyl group, *-Sn(R Ｓｎ ) ３ , *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋ By converting the compound represented by formula (2) into ４ and R ５ each independently represents a formyl group, *-Sn(R Ｓｎ ) ３ , *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋ A compound is obtained which is

[0147]

[0148] In formula (2a), Z１ ~Z ６ are each independently -CR Ｘ１ = or represents a nitrogen atom. Ｘ１ represents a hydrogen atom or a substituent. １ ~Z ６ Two adjacent ones are -CR Ｘ１ If =, then two R Ｘ１ may be bonded to each other to form a ring. １ ~Z ６ is Z in formula (2) １ ~Z ６ The same definition and preferred embodiments are also the same.

[0149] In formula (2a), R Ｌ４ and R Ｌ５ are each independently *-O-S(=O) ２ R ｆ , a bromine atom, a chlorine atom, or a fluorine atom. １ and X ２ are each independently an iodine atom, *—O—S(═O) ２ R ｆ , a bromine atom, or a chlorine atom. ｆ is R in formula (2) ｆ However, R Ｌ４ , R Ｌ５ , X １ and X ２ meets the following requirements:

[0150] Requirements: Iodine atom at the first position, *-O-S(=O) ２ R ｆ is ranked as the second, the bromine atom as the third, the chlorine atom as the fourth, and the fluorine atom as the fifth, and the ranking increases from the first to the fifth position. Ｌ４ and the order of the groups represented by R Ｌ５ Both of the priorities of the groups represented by X １ and the order of the group represented by X ２ In the above requirement, the order from the 1st position to the 5th position indicates the difficulty of the leaving group to be removed, and the 5th position means that the leaving group is more difficult to be removed. In other words, the higher the order (the closer to the 5th position), the more difficult it is to be removed. Therefore, R Ｌ４, R Ｌ５ , X １ and X ２ By satisfying the requirements, X １ and X ２ Both of the groups represented by R Ｌ４ and is more likely to be eliminated than a group represented by R Ｌ５ Since the group is more likely to leave than the group represented by the formula:

[0151] For example, X １ is the iodine atom in the first position, X ２ is the first iodine atom, R Ｌ４ a bromine atom in which R is the third position; and Ｌ５ is a bromine atom at the third position, R Ｌ４ and R Ｌ５ The rankings of (both 3rd place) are X １ and X ２ Since the rankings of X and X are higher than the rankings of X and X (both ranked first), the above requirement is met. １ is a bromine atom in the third position, X ２ is a bromine atom in the third position, R Ｌ４ an iodine atom in which R is in the first position; Ｌ５ is an iodine atom at the first position, R Ｌ４ and R Ｌ５ The rankings of (both first place) are X １ and X ２ (both ranked 3rd) and therefore do not meet the above requirements. Ｌ４ , R Ｌ５ , X １ and X ２ Examples of the combination of X include the following examples 1 to 4. Example 1: X １ = I, X ２ = I, R Ｌ４ =Br, R Ｌ５ =Br Example 2: X １ = I, X ２ =*-OS(=O) ２ R ｆ , R Ｌ４ =Br, R Ｌ５ =Br Example 3: X １ = I, X ２= I, R Ｌ４ =Br, R Ｌ５ =Cl Example 4:X １ =Br, X ２ =Br, R Ｌ４ = Cl, R Ｌ５ As a combination that satisfies the requirement of =Cl, the combination of Example 1 is particularly preferable.

[0152] In formula (X), 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. When the aromatic ring represented by Ar has a substituent selected from the above-mentioned substituent group T, R ３ and a substituent selected from the substituent group T possessed by the aromatic ring represented by Ar may be bonded to each other to form a non-aromatic ring. When 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. ３ and Ar is R in formula (2). ３ and Ar, and the preferred embodiments thereof are also the same.

[0153] In formula (2b), Z １ ~Z ６ , R Ｌ４ and R Ｌ５ represents Z in the above formula (2a). １ ~Z ６ , R Ｌ４ and R Ｌ５ It is synonymous with R ３ and Ar is R in the above formula (X). ３ and Ar.

[0154] The above step P1 is typically carried out under Buchwald-Hartwig cross-coupling conditions, and more specifically, step P1 is preferably carried out in the presence of an organometallic catalyst and a base. Examples of organometallic catalysts include palladium catalysts, and more specifically, palladium salts such as palladium chloride, palladium acetate, palladium trifluoroacetate, and palladium nitrate; complex compounds such as π-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(triphenylphosphine)palladium, dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, and dichlorobis(tricyclohexylphosphine)palladium. The palladium catalyst may be prepared in the reaction system by adding a tertiary phosphine to a palladium salt or complex compound. As the organometallic catalyst, a palladium complex having a tertiary phosphine as a ligand is preferred, a palladium complex having a tertiary phosphine having at least one aryl group as a ligand is more preferred, and a palladium complex having a triarylphosphine as a ligand is even more preferred. Examples of the aryl group that the tertiary phosphine may have include a phenyl group that may have a group exemplified by the above-mentioned substituent W.

[0155] Examples of the base include a base containing an alkali metal and a tertiary amine, with the base containing an alkali metal being preferred. Examples of the base containing an alkali metal include alkali metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium t-butoxide, etc.), or alkali metal carbonates, phosphates, hydroxides, and fluorides, with alkali metal alkoxides being more preferred, and alkoxides comprising a tert-butoxide anion and an alkali metal being even more preferred. Examples of the alkali metal include lithium, potassium, sodium, and cesium, with lithium, potassium, or sodium being preferred.

[0156] Examples of the reaction solvent in step P1 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, with toluene being preferred. The reaction temperature is often a reflux temperature depending on the reaction solvent used, and is preferably 50 to 200°C, more preferably 90 to 150°C.

[0157] Step P2: In the compound represented by the above formula (2b), R Ｌ４ and groups represented by R Ｌ５ The group represented by the formula (I) is a formyl group, *-Sn(R Ｓｎ ) ３ , *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋ (hereinafter also referred to as "step P2") is further carried out to convert R ４ and R ５ is a formyl group, *-Sn(R Ｓｎ ) ３ , *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋A compound having the formula: R Ｓｎ , R Ｂ１ and R Ｂ２ represents R in intermediate A (compound represented by formula (2)). Ｓｎ , R Ｂ１ and R Ｂ２ The same applies to the preferred embodiments thereof.

[0158] Step P2A: In the compound represented by the above formula (2b), R Ｌ４ and groups represented by R Ｌ５ An example of the step of converting the group represented by formula (2b) into a formyl group is a step of reacting the compound represented by formula (2b) with a formylating agent. Known formylating agents can be used, and examples of the formylating agent include N,N-disubstituted formamides, orthoformates, and compounds represented by formula (B″).

[0159] An example of the N,N-disubstituted formamide is a compound represented by formula (B): OHC-NR Ｙ２ ２ Formula (B) In formula (B), R Ｙ２ represents an organic group. Ｙ２ may be the same or different. Examples of 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, and among these, an aliphatic hydrocarbon group or an aromatic ring group is preferred. 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.

[0160] Examples of orthoformic acid esters include compounds represented by formula (B'): HC(OR Ｙ３ ) ３ Formula (B') In formula (B'), R Ｙ３ represents an alkyl group. Ｙ３may be the same or different. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

[0161] The compound represented by the above formula (B″) is as follows. In formula (B″), R represents an alkyl group having 1 to 6 carbon atoms. Of the compounds represented by the above formula (B″), N-methoxyethyleneaniline is particularly preferred.

[0162]

[0163] Step P2A is typically carried out by reacting R ４ and groups represented by R ５ In many cases, a group represented by the formula (I) is converted into a 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. Among these, the metallation reagent used in step P2A is preferably a lithium reagent or a magnesium reagent. Among these, the lithium reagent is preferably an organolithium reagent, and examples of the lithium reagent include alkyllithiums such as n-butyllithium, sec-butyllithium, and tert-butyllithium. Examples of the magnesium reagent include organomagnesium reagents (such as Grignard reagents). Note that the magnesium reagent also includes magnesium itself.

[0164] Step P2B: In the compound represented by the above formula (2b), R Ｌ４ and groups represented by R Ｌ５ The group represented by *-Sn(R Ｓｎ ) ３ An example of the step of converting the compound represented by formula (2b) into the compound represented by formula (Y) (hereinafter also referred to as "step P2B") is a step of reacting the compound represented by formula (2b) with the compound represented by formula (Y). Ｓｎ ) ３ Sn-X ａ Formula (Y)

[0165] In formula (Y), R Ｓｎ is R in the above formula (2). ４ and R ５*-Sn(R Ｓｎ ) ３ R in Ｓｎ It is synonymous with R Ｓｎ Examples of the substituent represented by the formula (I) 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. Examples of the substituent which each of the above groups may have include the groups exemplified above as the substituent W. Ｓｎ Among these, the substituent represented by formula (Y) is preferably an aliphatic hydrocarbon group which may have an aromatic ring group, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably a methyl group or a butyl group. ａ is an iodine atom, *-O-S(=O) ２ R ｆ , a bromine atom, a chlorine atom, or *-Sn(R Ｓｎ ) ３ Represents R ｆ is R in the above formula (2). ｆ It is synonymous with X. ａ Among them, iodine atom, *-O-S(=O) ２ R ｆ , a bromine atom, or a chlorine atom is preferred, and a chlorine atom is more preferred.

[0166] Step P2B is typically carried out by reacting R Ｌ４ and groups represented by R Ｌ５ In many cases, a group represented by the formula (Y) is converted to lithium using an organolithium reagent, and then the compound represented by the formula (Y) is reacted. The reaction conditions are not particularly limited as long as they are generally suitable for lithiation. Examples of organolithium reagents include alkyllithiums such as n-butyllithium, sec-butyllithium, and tert-butyllithium.

[0167] Step P2B can also be carried out in the presence of a palladium catalyst. Specific reaction conditions can be found in the synthesis method described in the non-patent document "J. Org. Chem. 2016, 81, 8, 3356-3363." The palladium catalysts exemplified in Step P1 can be used.

[0168] Step P2C: In the compound represented by the above formula (2b), R Ｌ４ and groups represented by R Ｌ５ The group represented by *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋ An example of the step of converting the compound represented by formula (2b) to the compound represented by formula (2b) is a step of reacting the compound represented by formula (2b) with a borylation agent. As the borylation agent, known borylation agents can be used, and examples thereof include compounds represented by formula (Z). ｂ -B(OR Ｂ３ ) ２ Formula (Z) In formula (Z), X ｂ is an iodine atom, *-O-S(=O) ２ R ｆ , bromine atom, chlorine atom, *-B(OR Ｂ３ ) ２ , *-OR Ｂ４ , or *-Si(R Ｂ５ ) ３ Represents.

[0169] R ｆ is R in the above formula (2). ｆ It is synonymous with R Ｂ３ , R Ｂ４ and R Ｂ５ each independently 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. Ｂ３ and R Ｂ５ may be the same or different. Ｂ３ and R Ｂ４ Among these, R is preferably an aliphatic hydrocarbon group, more preferably an alkyl group, and even more preferably an alkyl group having 1 to 6 carbon atoms. Ｂ３ R 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'). Ｂ３ When they are bonded to each other to form a ring, *-B(OR Ｂ３ ) ２The group represented by the formula (B1) or (B2) is preferred.

[0170]

[0171] The above *-Si(R Ｂ５ ) ３ In this case, R Ｂ５ Among these, an aliphatic hydrocarbon group or an aromatic ring group is preferable, and an alkyl group having 1 to 6 carbon atoms or a phenyl group is more preferable.

[0172] Step P2C is typically carried out by reacting R Ｌ４ and groups represented by R Ｌ５ In many cases, a group represented by the formula (Z) is converted to lithium using an organolithium reagent, and then reacted with the compound represented by the formula (Z). The reaction conditions are not particularly limited as long as they are generally lithiation conditions, and specific examples of the organolithium reagent are as described above. ４ and groups represented by R ５ After converting the group represented by formula (Z) into magnesium, the group represented by formula (Z) is reacted to form R ４ and groups represented by R ５ The group represented by *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋ It is also effective to convert it into the following: Specific reaction conditions can be referred to the synthesis method described in the non-patent document "Org. Lett. 2006, 8, 18, 4071-4074."

[0173] In addition, step P2C is often carried out in the presence of 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 are the same as those exemplified as the palladium catalyst and base in step P1.

[0174] In addition to the above-mentioned reaction conditions, step P2C can also be carried out without using a transition metal catalyst. Such reaction conditions include, for example, a reaction of a compound represented by the above formula (2b) with X ｂ *-Si(R Ｂ５ ) ３ and a compound represented by formula (Z):

[0175] Specific examples of the compound represented by formula (2) are shown below, but the present invention is not limited to these. ４ and R ５ are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, *-Sn(n-Bu) ３ , *-SnMe ３ , *-B(OH) ２ , *-BF ３ M ＋ (M ＋ represents a monovalent metal cation, a formyl group, or a group represented by any one of the above formulae (B1) to (B3).

[0176]

[0177]

[0178] <Intermediate B> Next, intermediate B (a compound represented by formula (3)) will be described in detail. Intermediate B is represented by the following structural formula.

[0179]

[0180] In formula (3), Z １ ~Z ６ are each independently -CR Ｘ１ = or represents a nitrogen atom. Ｘ１ represents a hydrogen atom or a substituent. １ ~Z ６ Two adjacent ones are -CR Ｘ１ If =, then two R Ｘ１ may be bonded to each other to form a ring. １ ~Z ６Specific and preferred embodiments of the formula (1) are １ ~Z ６ The specific and preferred embodiments are the same as those of the above.

[0181] In formula (3), Q represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. ６ represents a substituent selected from the substituent group U. 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. In the substituent group U, 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. In the substituent group U, the aromatic ring group which may have a substituent is preferably a group selected from the substituent group R Ａｒ１ 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 is preferred, and 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 is more preferred.

[0182] <Method for Producing Intermediate B> The method for producing intermediate B of the present invention comprises reacting a compound represented by formula (3a) with a compound represented by formula (A) to obtain SiR Ｙ１ ３ The method for producing a compound includes: Step 1 of obtaining a compound represented by formula (3b) having a protecting group represented by the following formula: Step 2 of reacting the compound represented by formula (3b) with a metallation reagent, followed by reaction with a formylating agent, and then deprotecting the protecting group to obtain a compound represented by formula (3c); and Step 3 of reacting the compound represented by formula (3c) with a compound represented by formula (C) to obtain a compound represented by formula (3).

[0183]

[0184] In formulas (3a) to (3c), Z １ ~Z ６ is Z in the above formula (3). １ ~Z ６ The same definitions and preferred embodiments are also the same. ３ and X ４ are each independently 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.

[0185] Step 1 Step 1 will be described in detail below. Step 1 is a process for reacting a compound represented by formula (3a) with a compound represented by formula (A) to obtain SiR Ｙ１ ３ In formula (A), L is a protecting group represented by formula (3b). １ represents a leaving group. Examples of the leaving group include a halogen atom or *-O-S(=O) ２ R ｆ Examples include: R ｆ is R in formula (2) ｆ It is synonymous with L. １ Among them, a bromine atom or a chlorine atom is preferable as R. Ｙ１ 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. Ｙ１ R may be the same or different. Ｙ１ Among these, 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 is preferred.

[0186] In the above 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. 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.

[0187] Step 2 Next, step 2 will be described in detail. Step 2 is a step in which the compound represented by formula (3b) obtained in step 1 is reacted with a metallation reagent, followed by reaction with a formylating agent, and then the protecting group is deprotected to obtain a compound represented by formula (3c) described below. In step 2, a known metallation reagent can be used, and for example, the reagents exemplified in step P2A can be used. The reaction conditions are not particularly limited, and known reaction conditions can be applied. As the formylation agent, a known agent can be used, and for example, the N,N-disubstituted formamide and orthoformate ester exemplified in step P2A can be used. Known reaction conditions can also be adopted, and for example, the conditions exemplified in step P2A can be used.

[0188] SiR Ｙ１ ３ Examples of methods for deprotecting the protecting group represented by formula (3c) include a method of reacting an appropriate desilylating agent depending on the compound represented by formula (A) used. The desilylating agent is not particularly limited and any known desilylating agent can be used, and examples include water, an acid, a base, and a fluoride ion. Depending on the structure of the compound represented by formula (A), the silyl protecting group derived from the compound represented by formula (A) may be easily deprotected, and deprotection may occur in a post-reaction step (such as a separation step or a column purification step) or due to moisture in the air. Even in such cases, the present invention is within the scope of the present invention as long as a compound represented by formula (3c) is obtained from a compound represented by formula (3b).

[0189] Depending on the reaction conditions, the above steps 1 and 2 may be carried out in one pot.

[0190] Step 3 Next, step 3 will be described in detail. Step 3 is a step in which the compound represented by formula (3c) obtained in step 2 is reacted 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). In formula (C), L ２ represents a leaving group. Examples of the leaving group include *—O—(C═O)R６ , a halogen atom, and *—O—S(═O) ２ R ｆ Examples include: ｆ is R in formula (A). ｆ It is synonymous with R ６ is R in the above formula (3). ６ and a methyl group or an ethyl group is preferred. ２ As the group, *-O-(C=O)R ６ or a halogen atom is preferred, *—O—(C═O)R ６ , a chlorine atom, or a bromine atom is more preferred, and *—O—(C═O)R ６ or a chlorine atom is more preferred.

[0191] Specific examples of the compound represented by formula (3) are shown below, but the present invention is not limited to these.

[0192]

[0193] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0194] [Materials Used in Photoelectric Conversion Film] The various components contained in the photoelectric conversion film are shown below.

[0195] [Synthesis of Compound 1 (Synthesis Example 1 of Specific Compound)] Compound 1 was synthesized according to the following scheme.

[0196]

[0197] <Synthesis of Intermediate (1)> Intermediate (1) was synthesized using 2,7-dibromocarbazole and 2-bromopropane as starting materials according to the method described in Marciniec et al., Org. Biomol. Chem., 2016, 14, 9406.

[0198] <Synthesis of Intermediate (2)> Intermediate (1) (7.0 g) and tetrahydrofuran (THF, 180 mL) were placed in a 300 mL three-neck flask and cooled to -78°C under a nitrogen atmosphere. A hexane solution of n-butyllithium (2.8 M, Fujifilm Wako Pure Chemical Industries, Ltd., 27 mL) was added and stirred for 1 hour, after which N,N-dimethylformamide (DMF, 15 mL) was added and stirred at room temperature for 1 hour. The resulting reaction solution was washed sequentially with a saturated aqueous ammonium chloride solution and saturated saline, and the organic phase was recovered. The resulting organic phase was dried over sodium sulfate, and the solvent was removed. The resulting crude product was purified by silica gel column chromatography (eluent: hexane / dichloromethane = 1 / 1), yielding 2.4 g of Intermediate (2) (yield 40%).

[0199] <Synthesis of Compound 1> Intermediate (2) (500 mg), 1,3-dimethylbarbituric acid (Tokyo Chemical Industry Co., Ltd., 765 mg), acetic acid (20 mL), and piperidine (Fujifilm Wako Pure Chemical Industries, Ltd., 37 μL) were placed in a 100 mL recovery flask and reacted at 100°C for 17 hours under a nitrogen atmosphere. After completion of the reaction, the precipitated solid was filtered off, and the crude product was recrystallized from dichloromethane and methanol. The obtained solid was purified by sublimation to obtain 767 mg of Compound 1 (yield 75%). １ The H-NMR (Nuclear Magnetic Resonance) data is shown below. １ H-NMR (CDCl ３ ): δ (ppm) = 8.94 (2H, s), 8.79 (2H, s), 8.18 (2H, d), 7.86 (2H, dd), 5.15 (1H, sep), 3.47 (6H, s), 3.45 (6H, s), 1.84 (6H, d)

[0200] [Synthesis of Compound 3 (Synthesis Example 2 of Specific Compound)] Compound 3 was synthesized according to the following scheme.

[0201]

[0202] <Synthesis of Intermediate (3)> 4,4'-Dibromo-2,2'-diiodobiphenyl (Combi-Blocks, 18 g), 2,6-dimethylaniline (Fujifilm Wako Pure Chemical Industries, Ltd., 5.8 g), potassium t-butoxide (Fujifilm Wako Pure Chemical Industries, Ltd., 11 g), toluene (750 mL), and tetrakis(triphenylphosphine)palladium(0) (Tokyo Chemical Industry Co., Ltd., 3.7 g) were placed in a 2 L three-neck flask and stirred at 100°C under a nitrogen atmosphere for 39 hours. After cooling the reaction solution to room temperature, insoluble components were removed by filtration through Celite, and the solvent was removed from the obtained filtrate. The obtained crude product was purified by silica gel column chromatography (eluent: hexane / toluene = 99 / 1) to obtain 3.7 g of Intermediate (3) (yield 25%). The obtained Intermediate (3) １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ = 7.97 (d, 2H), 7.39 (dd, 2H), 7.38 (d, 1H), 7.29 (d, 2H), 7.07 (d, 2H) 1.86 (s, 6H)

[0203] <Synthesis of Intermediate (4)> Intermediate (4) was synthesized in the same manner as in the above <Synthesis of Intermediate (2)>. １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ = 10.1 (s, 2H), 8.37 (d, 2H), 7.87 (dd, 2H), 7.54 (s, 2H), 7.43 (d, 1H), 7.32 (d, 2H), 1.85 (s, 6H)

[0204] <Synthesis of Compound 3> Intermediate (4) (250 mg), 1,3-dimethylbarbituric acid (310 mg), acetic acid (25 mL), and piperidine (15 μL) were placed in a 100 mL recovery flask and reacted at 100°C for 2 hours under a nitrogen atmosphere. The precipitated solid was filtered off, and the crude product was recrystallized from dichloromethane and methanol. The obtained solid was purified by sublimation to obtain 250 mg (yield 54%) of Compound 3. １ The H-NMR data is shown below. １ H-NMR (CDCl３ ): δ = 8.65 (2H, s), 8.26 (2H, d), 8.17 (2H, dd), 7.70 (2H, s), 7.42 (1H, dd), 2.11 (2H, d), 3.41 (6H, s), 3.36 (6H, s), 1.92 (6H, s)

[0205] 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.

[0206]

[0207] [Synthesis of Compound 24 (Synthesis Example 3 of Specific Compound)] Compound 24 was synthesized according to the following scheme.

[0208]

[0209] <Synthesis of Intermediate (5)> Intermediate (5) was synthesized in the same manner as in the synthesis of the above <Synthesis of Intermediate (3)>, except that 2,6-dimethylaniline was replaced with 2,4,6-trimethylaniline. １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ = 7.96 (d, 2H), 7.38 (dd, 2H), 7.09 (d, 2H), 7.08 (d, 2H), 2.43 (s, 3H), 1.81 (s, 6H)

[0210] <Synthesis of Intermediate (6)> Intermediate (6) was synthesized in the same manner as in <Synthesis of Intermediate (2)> above, except that intermediate (5) was used instead of intermediate (3). １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ = 10.1 (s, 2H), 8.36 (d, 2H), 7.86 (dd, 2H), 7.55 (d, 2H), 7.13 (d, 2H), 2.45 (s, 3H), 1.80 (s, 6H)

[0211] <Synthesis of Compound 24> Compound 24 was synthesized in the same manner as in the synthesis of Compound 3 above, except that 1,3-dimethylbarbituric acid was replaced with 1,3-indandione, using intermediate (6) instead of intermediate (4). １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ = 8.63 (dd, 2H), 8.34 (d, 2H), 8.02 (m, 8H), 7.80 (m, 4H), 7.21 (s, 2H), 2.51 (s, 3H), 1.91 (s, 6H)

[0212] [Synthesis of Compound 34 (Synthesis Example 4 of Specific Compound)] Compound 34 was synthesized according to the following scheme.

[0213]

[0214] <Synthesis of Intermediate (7)> ​​Intermediate (7) was synthesized in the same manner as in the synthesis of Intermediate (3) above, except that 2,6-dimethylaniline was replaced with 2,6-diisopropylaniline. １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ = 7.97 (d, 2H), 7.57 (t, 1H), 7.39 (d, 2H), 7.39 (dd, 2H), 7.07 (d, 2H), 2.14 (sept, 2H), 0.99 (d, 12H)

[0215] <Synthesis of Intermediate (8)> Intermediate (8) was synthesized in the same manner as in <Synthesis of Intermediate (2)> above, except that intermediate (7) was used instead of intermediate (1). １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ = 10.1 (s, 2H), 8.37 (d, 2H), 7.87 (dd, 2H), 7.62 (t, 1H), 7.55 (d, 2H), 7.43 (d, 2H), 2.12 (sept, 2H), 0.97 (d, 12H)

[0216] <Synthesis of Compound 34> Compound 34 was synthesized in the same manner as in the synthesis of Compound 3 above, except that 1,3-dimethylbarbituric acid was replaced with 1,3-indandione, using intermediate (8) instead of intermediate (4). １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ = 8.70 (dd, 2H), 8.36 (d, 2H), 8.02-7.96 (m, 6H), 7.82-7.78 (m, 4H), 7.69 (t, 1H), 7.50 (d, 2H), 2.22 (sept, 2H), 1.02 (d, 12H).

[0217] In the above Synthesis Examples 1 to 4, R ４ and groups represented by R ５ A specific compound is synthesized from intermediate A (hereinafter also referred to as "formyl intermediate") in which the group represented by R ４ and groups represented by R ５ The group represented by *-Sn(R Ｓｎ ) ３ , *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋ It is also possible to use intermediate A (hereinafter also referred to as "other intermediate"), which is a compound represented by the formula (I), as a starting material, and convert it into the above-mentioned formyl intermediate, and then synthesize a specific compound by referring to Synthesis Examples 1 to 4. Synthesis examples of other intermediates are shown below.

[0218] <Synthesis of Sn-body> R ４ and groups represented by R ５ The group represented by *-Sn(R Ｓｎ ) ３ Intermediate A (hereinafter also referred to as "Sn body") was synthesized according to the following scheme.

[0219]

[0220] The above intermediate (3) (3.0 g) and THF (77 mL) were placed in a three-necked flask and cooled to -78°C under a nitrogen atmosphere. A hexane solution of n-butyllithium (2.8 M, 12 mL) was added and stirred for 1 hour, after which tributyltin chloride (Tokyo Chemical Industry Co., Ltd., 9.5 mL) was added and stirred at room temperature for 1 hour. The resulting reaction solution was washed successively with a saturated aqueous ammonium chloride solution and saturated saline, and the organic phase was recovered. The resulting organic phase was dried over sodium sulfate, and the solvent was further removed. The resulting crude product was purified by silica gel column chromatography (NH ２ The Sn-form was purified using a column (eluent: hexane) to obtain 5.0 g of the Sn-form (yield: 85%). The structure of the Sn-form was confirmed by LC-MS (Liquid Chromatography-Mass Spectrometry). LC-MS (Sn-form): 851.3 (M ＋ )

[0221] <Synthesis of B-form> R ４ and groups represented by R ５ The group represented by *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋ Intermediate A (hereinafter also referred to as "B"), which is represented by the following formula, was synthesized according to the following scheme.

[0222]

[0223] The above intermediate (3) (1.0 g) and THF (100 mL) were placed in a three-neck flask and cooled to -100°C under a nitrogen atmosphere. A hexane solution of n-butyllithium (2.8 M, 1.8 mL) was added and stirred for 1.5 hours, after which trimethoxyborane (Tokyo Chemical Industry Co., Ltd., 0.58 g) was added and the reaction was carried out at room temperature for 18 hours. 100 mL of ethyl acetate and 100 mL of hydrochloric acid (3 M, 100 mL) were added to the resulting reaction solution and stirred, after which the aqueous phase was removed. The resulting organic phase was washed with water and then dried over sodium sulfate, and the solvent was removed. The resulting crude product was purified by silica gel column chromatography (eluent: toluene) to obtain 0.38 g (yield 45%) of Form B. The structure of Form B was confirmed by LC-MS. LC-MS (Form B): 359.0 (M ＋ )

[0224] [Synthesis of Compound 36 (Synthesis Example 5 of Specific Compound)] Compound 36 was synthesized according to the following scheme.

[0225]

[0226] <Synthesis of Intermediate (11)> 2,7-Dibromocarbazole (5.0 g) and THF (280 mL) were placed in a three-neck flask and cooled to 0°C under a nitrogen atmosphere. A hexane solution of n-butyllithium (2.7 M, Fujifilm Wako Pure Chemical Industries, Ltd., 5.8 mL) was added and stirred for 5 minutes, followed by the addition of trimethylchlorosilane (2.0 mL). After stirring at room temperature for 30 minutes, the disappearance of 2,7-dibromocarbazole and the formation of intermediate (10) were confirmed by LC-MS. A hexane solution of n-butyllithium (2.7 M, 23 mL) was added dropwise to the reaction solution at −78°C, followed by the dropwise addition of DMF (12 mL), and the mixture was stirred at room temperature for 10 minutes. Ethyl acetate (280 mL) was added to the resulting reaction solution, which was then washed sequentially with water and brine, and the organic phase was recovered. The resulting organic phase was dried over sodium sulfate, and the solvent was then removed. The obtained crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 1 / 1) to obtain 1.4 g of intermediate (11) (yield: 40%). １ The H-NMR data is shown below. １H-NMR (DMSO-d ６ ): δ=12.1 (s, 1H), 10.2 (s, 2H), 8.44 (d, 2H), 8.15 (d, 2H), 7.78 (dd, 2H).

[0227] <Synthesis of Intermediate (12)> Intermediate (11) (1.3 g), 4-dimethylaminopyridine (Fujifilm Wako Pure Chemical Industries, Ltd., 0.29 g), THF (45 mL), triethylamine (2.5 mL), and acetic anhydride (Fujifilm Wako Pure Chemical Industries, Ltd., 2.2 mL) were added to a three-necked flask and stirred at room temperature for 1 hour. 300 mL of chloroform was added to the reaction solution, and the mixture was washed successively with a saturated aqueous ammonium chloride solution and brine, and then the organic phase was recovered. The obtained organic phase was dried over sodium sulfate, and the solvent was further removed. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform / ethyl acetate = 7 / 3) to obtain 0.74 g (yield 48%) of intermediate (12). １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ=10.2 (s, 2H), 8.81 (s, 2H), 8.24 (d, 2H), 8.01 (d, 2H), 3,04 (s, 3H).

[0228] Comparative Synthesis Example 2 (Comparative Synthesis Example of Intermediate (12)) Synthesis of intermediate (12) was attempted according to the following scheme.

[0229]

[0230] Intermediate (R1) was synthesized using 2,7-dibromocarbazole as a starting material in the same procedure as in the above <Synthesis of Intermediate (12)>. Next, intermediate (R1) (200 mg), THF (5.5 mL), and n-butyllithium (2.7 M, 0.5 mL) were placed in a three-necked flask and stirred at -90°C under a nitrogen atmosphere for 1 hour. DMF (0.4 mL) was added to the reaction solution, and the mixture was warmed to room temperature. The product was confirmed by LC-MS, but decomposition of the acetyl group and other factors had progressed, and the desired intermediate (12) was not obtained.

[0231] 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 procedure as above, but a complex mixture was obtained, and the desired intermediate (12) was not obtained.

[0232]

[0233] <Synthesis of Compound 36> Compound 36 was synthesized in the same manner as in the synthesis of Compound 3 above, except that intermediate (12) was used instead of intermediate (4), and 1,3-dimethylbarbituric acid was replaced with 1,3-indandione. Because compound 36 has low solubility, its structure was confirmed by LDI-MS (laser desorption ionization mass spectrometry). LDI-MS (Compound 36): 521.1 (M ＋ )

[0234] The specific compounds and comparative compounds used in the photoelectric conversion film other than Compound 1, Compound 3, Compound 24, Compound 34, and Compound 36 were synthesized with reference to the above Synthesis Examples 1 to 5. The materials used in the photoelectric conversion film are shown below. Compounds 1 to 38 correspond to the specific compounds, and Compounds C-1 to C-6 correspond to the comparative compounds.

[0235] [Specific compounds and comparative compounds]

[0236]

[0237]

[0238]

[0239]

[0240] [n-type organic semiconductor] C60: fullerene (C ６０ )

[0241] [p-type organic semiconductor]

[0242]

[0243] [Pigment]

[0244]

[0245] [Evaluation] Photoelectric conversion elements were fabricated using the above materials, and tests X and Y were carried out.

[0246] [Test X] <Preparation of Photoelectric Conversion Element> A photoelectric conversion element having the configuration shown in FIG. 2 was prepared using the various components shown above. Here, the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15. Specifically, amorphous ITO was formed on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and compound (EB-1) was further formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm). Subsequently, with the temperature of the glass substrate controlled at 25°C, each specific compound or each comparative compound shown in Table 1 and an n-type organic semiconductor (fullerene (C ６０ )) and a p-type organic semiconductor (compound (P-1)) were co-deposited by vacuum deposition to form a film having a thickness of 80 nm in terms of a single layer. This formed a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. At this time, the film formation rate of the photoelectric conversion film 12 was 1.0 Å / sec. Furthermore, 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). After a SiO film was formed as a sealing layer on the upper electrode 15 by vacuum deposition, aluminum oxide (Al ２ O ３ The resulting laminate was heated at 150° C. for 30 minutes in a glove box to prepare a photoelectric conversion element of each example and comparative example.

[0247]

[0248] <Dark Current> The dark current of each of the obtained photoelectric conversion elements was measured by the following method. ５A voltage was applied to the photoelectric conversion element so as to obtain an electric field strength of 50 nA / cm. The current value in a dark place (dark current) was measured. As a result, the dark current was 50 nA / cm for all the photoelectric conversion elements. ２ It was confirmed that the dark current was sufficiently low.

[0249] <Quantum Efficiency> The quantum efficiency of each of the obtained photoelectric conversion elements was measured by the following method. ５ After applying a voltage to achieve an electric field strength of 100 volts / cm, light was irradiated from the upper electrode (transparent conductive film) side to evaluate the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 460 nm, and the value obtained according to formula (S1) was evaluated in accordance with the following criteria. In formula (S1), for the Examples and Comparative Examples listed in Table 1, Examples 1 to 18 were adopted as the reference Examples below. Formula (S1): Quantum efficiency (relative ratio) = (quantum efficiency at a wavelength of 460 nm of each Example or Comparative Example) / (quantum efficiency at a wavelength of 460 nm of the reference Example)

[0250] (Evaluation criteria) AA: Quantum efficiency is 1.6 or more A: Quantum efficiency is 1.4 or more and less than 1.6 B: Quantum efficiency is 1.2 or more and less than 1.4 C: Quantum efficiency is 0.9 or more and less than 1.2 D: Quantum efficiency is 0.5 or more and less than 0.9 E: Quantum efficiency is less than 0.5

[0251] <Response Speed ​​(Responsivity)> The response speed of each of the obtained photoelectric conversion elements was evaluated by the following method. ５ A voltage was applied to the sample so that the intensity was 1000 V / cm. Thereafter, an LED (light emitting diode) was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 460 nm at that time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity. The value obtained according to formula (S2) was used to evaluate the response speed in accordance with the following criteria. In formula (S2), for the Examples and Comparative Examples listed in Table 1, Examples 1-18 were adopted as the reference Examples below. Formula (S2): Relative response speed = (rise time at a wavelength of 460 nm for each Example or Comparative Example) / (rise time at a wavelength of 460 nm for the reference Example)

[0252] (Evaluation Criteria) A: 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

[0253] <Dependence of response speed on electric field strength> The dependence of response speed on electric field strength of each of the obtained photoelectric conversion elements was evaluated by the following method. In the evaluation of the above <Response speed>, a voltage of 7.5×10 ４ The same procedure was followed except that the pressure was changed to 7.5 × 10 ４ The response speed at 1000 V / cm was measured, and the value obtained according to formula (S3) was used to evaluate the electric field strength dependency of the response speed in light of the following criteria. Note that the photoelectric conversion elements in the numerator and denominator of formula (S3) are the same. For example, with regard to Example 1-1, the photoelectric conversion efficiency of Example 1-1 at a wavelength of 460 nm was 7.5 × 10 ４ V / cm and the photoelectric conversion efficiency of Example 1-1 at a wavelength of 460 nm of 2.0 × 10 ５ The rise time at a wavelength of 460 nm for each example or comparative example is compared with that at a wavelength of 460 nm for each example or comparative example. ４ V / cm) / (2.0×10 at a wavelength of 460 nm for each Example or Comparative Example ５ V / cm rise time)

[0254] (Evaluation Criteria) A: The electric field strength dependency of the response speed is less than 2.0 B: The electric field strength dependency of the response speed is 2.0 or more and less than 3.0 C: The electric field strength dependency of the response speed is 3.0 or more and less than 4.0 D: The electric field strength dependency of the response speed is 4.0 or more and less than 5.0 E: The electric field strength dependency of the response speed is 5.0 or more

[0255] <Manufacturing Suitability> The manufacturability of each obtained photoelectric conversion element was evaluated by the following method. Photoelectric conversion elements of each Example or Comparative Example were manufactured using the same procedure as in the above <Fabrication of Photoelectric Conversion Element>, except that the deposition rate of the photoelectric conversion film 12 was changed to 3.0 Å / sec. The photoelectric conversion element obtained in the above <Fabrication of Photoelectric Conversion Element> was designated as photoelectric conversion element (A), and the photoelectric conversion element obtained with the deposition rate of the photoelectric conversion film 12 set to 3.0 Å / sec was designated as photoelectric conversion element (B). The quantum efficiency of each element was determined using the same procedure as in the evaluation of <Quantum Efficiency> above. For photoelectric conversion elements having the same configuration as in the Example or Comparative Example, 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) (quantum efficiency of photoelectric conversion element (B) / quantum efficiency of photoelectric conversion element (A)) was calculated, and the manufacturability of the obtained value was evaluated based on the following criteria.

[0256] (Evaluation Criteria) A: The relative ratio B / A is 0.90 or more. B: The relative ratio B / A is 0.85 or more and less than 0.90. C: The relative ratio B / A is 0.80 or more and less than 0.85. D: The relative ratio B / A is 0.75 or more and less than 0.80. E: The relative ratio B / A is less than 0.75.

[0257] The evaluation results of the above test X are shown in Table 1. The symbols in Table 1 indicate the following: The column "Substituent S Rule 1" indicates the group R Ｎ and R Ｃ１ ~R Ｃ１０ The substituent selected from the group S of substituents represented by the formula (I) is 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, or a group R Ａｒ１When X represents an aromatic ring group which may have a substituent selected from the group consisting of 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 case above, it is marked as "B". When X is a sulfur atom, an oxygen atom, or a selenium atom, it is marked as "-". In the column "Formula (A-1) = Formula (A-2)", it is marked as "A" when the group represented by formula (A-1) is a group represented by formula (A-2) above, and when it is not the case above, it is marked as "B". In the column "Formula (A-1) = Formula (C-1) or Formula (C-2)", it is marked as "A" when the group represented by formula (A-1) in formula (1) is a group represented by formula (C-1) or formula (C-2) above, and when it is not the case above, it is marked as "B". In the column "X = has a substituent S", it is marked as "A" when X in formula (1) is >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 )- is designated as "A", and other cases are designated as "B". Ｎ , C.R. ２ " column indicates whether X is >NR in formula (1). Ｎ , >CR Ｃ１ R Ｃ２ , or >C=CR Ｃ３ R Ｃ４ The case where X=NR is defined as "A", and the case other than the above is defined as "B". Ｎ " column indicates that in formula (1), X is NR Ｎ The case where the above expression is expressed is designated as "A", and the case other than the above is designated as "B".

[0258]

[0259]

[0260] As is clear from the results in the table, the photoelectric conversion elements of the examples of the present invention were confirmed to have excellent quantum efficiency. On the other hand, the photoelectric conversion elements of the comparative examples using comparative compounds that do not fall under the specific compounds had insufficient quantum efficiency.

[0261] Furthermore, from the results in Table 1, when the specific compound has a substituent S (in formula (1), X is >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 )-)), it was confirmed that the quantum efficiency and responsiveness were better (e.g., comparison with Examples 1-15 to 1-20). In the specific compound, when the substituent selected from the substituent group S is 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, a substituent group R Ａｒ１ It was confirmed that when the compound represented by the formula (A-1) is a group represented by formula (A-2), the quantum efficiency is superior (e.g., comparison between Example 1-1 and Example 1-27). In a specific compound, when the group represented by formula (A-1) is a group represented by formula (A-2), the quantum efficiency is superior (e.g., comparison between Example 1-25 and Example 1-26). It was confirmed that when the group represented by formula (A-2) is a group represented by formula (C-1) or a group represented by formula (C-2), the quantum efficiency is superior (e.g., comparison between Example 1-10 to Example 1-14 and Example 1-26). It was also confirmed that when the group represented by formula (A-2) is a group represented by formula (C-1), the response speed (responsiveness) is superior (e.g., comparison between Example 1-3 and Example 1-4). In formula (1), when X is >NR Ｎ , >CR Ｃ１ R Ｃ２ , or >C=CR Ｃ３ R Ｃ４ It was confirmed that the quantum efficiency was better when X represented >NR Ｎ It was confirmed that the quantum efficiency was even better when A was expressed (comparison between Examples 1-1 to 1-9 and Examples 1-10 or 1-12, etc.).１ and A ２ It was confirmed that when and are groups represented by formula (C-1), the response speed is superior.

[0262] [Test Y] <Preparation of photoelectric conversion element> Each specific compound or each comparative compound shown in Table 2, an n-type organic semiconductor (fullerene (C ６０ )), a p-type organic semiconductor (compound (P-1)), and a dye were co-deposited by a vacuum deposition method in a ratio of compound:dye:p-type organic semiconductor:n-type organic semiconductor=1:1:2:2 in terms of a single film, to form a photoelectric conversion film, and the other procedures were the same as in Test X, to prepare photoelectric conversion elements in each of the Examples and Comparative Examples.

[0263] <Dark Current> The dark current was measured in the same manner as in Test X. As a result, the dark current was 50 nA / cm in all the photoelectric conversion elements. ２ It was confirmed that the dark current was sufficiently low.

[0264] <Quantum Efficiency> The quantum efficiency of each of the obtained photoelectric conversion elements was measured by the following method. ５ After applying a voltage to achieve an electric field strength of 1000 V / cm, 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, and the value obtained according to formula (S4) was evaluated in accordance with the following criteria. In formula (S4), the quantum efficiencies in the numerator and denominator are quantum efficiencies at the same wavelength. Furthermore, for the Examples and Comparative Examples listed in Table 2, Examples 2-15 were used as the reference Examples below. Formula (S4): 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)

[0265] (Evaluation Criteria) The evaluation criteria for quantum efficiency at a wavelength of 460 nm are as follows: AA: quantum efficiency of 1.6 or more A: quantum efficiency of 1.4 or more and less than 1.6 B: quantum efficiency of 1.2 or more and less than 1.4 C: quantum efficiency of 0.9 or more and less than 1.2 D: quantum efficiency of 0.5 or more and less than 0.9 E: quantum efficiency less than 0.5

[0266] (Evaluation Criteria) The evaluation criteria for quantum efficiency at a wavelength of 600 nm are as follows: A: Quantum efficiency of 1.6 or more B: Quantum efficiency of 1.2 or more and less than 1.6 C: Quantum efficiency of 0.8 or more and less than 1.2 D: Quantum efficiency of 0.4 or more and less than 0.8 E: Quantum efficiency less than 0.4

[0267] <Response Speed> The response speed of each of the obtained photoelectric conversion elements was evaluated by the following method. ５ A voltage was applied to the sample so that the intensity was 100 V / cm. Thereafter, the LED was momentarily turned on to irradiate the sample with light from the upper electrode (transparent conductive film) side. The photocurrent at a wavelength of 460 nm or 600 nm at this time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity. The value obtained according to formula (S5) was used to evaluate the response speed in accordance with the following criteria. In formula (S5), the rise times in the numerator and denominator are rise times at the same wavelength. Furthermore, for the Examples and Comparative Examples listed in Table 2, Example 2-15 was used as the reference Example below. Formula (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)

[0268] (Evaluation Criteria) A: 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

[0269] <Dependence of Response Speed ​​on Electric Field Strength> The dependence of response speed on electric field strength of each of the obtained photoelectric conversion elements was evaluated by the following method. In the evaluation of the response speed of Test Y, a voltage of 7.5×10 ４ The same procedure was followed except that the pressure was changed to 7.5 × 10 ４The response speed at 460 nm or 600 nm V / cm was measured, and the value obtained according to formula (S6) was used to evaluate the electric field strength dependency of the response speed in accordance with the following criteria. In formula (S6), the photoelectric conversion elements in the numerator and denominator are the same. Formula (S6): Electric field strength dependency of response speed = 7.5 × 10 ４ V / cm) / (2.0×10 at a wavelength of 460 nm or 600 nm in each Example or Comparative Example) ５ V / cm rise time)

[0270] (Evaluation Criteria) A: The electric field strength dependency of the response speed is less than 2.0 B: The electric field strength dependency of the response speed is 2.0 or more and less than 3.0 C: The electric field strength dependency of the response speed is 3.0 or more and less than 4.0 D: The electric field strength dependency of the response speed is 4.0 or more and less than 5.0 E: The electric field strength dependency of the response speed is 5.0 or more

[0271] Table 2 shows the evaluation results of Test Y. The symbols in Table 2 are as described above for the symbols in Table 1.

[0272]

[0273] From the results shown in the above table, it was confirmed that the photoelectric conversion element of the present invention can obtain the desired effects.

[0274] 10a, 10b Photoelectric conversion element 11 Conductive film (lower electrode) 12 Photoelectric conversion film 15 Transparent conductive film (upper electrode) 16A Electron blocking film 16B Hole blocking film

Claims

1. A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1). 【Chemical Formula 1】 In formula (1), X is >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 Ｎ represents a substituent selected from the substituent group S. R Ｃ１ ~R Ｃ１０ each independently represents a hydrogen atom or a substituent selected from the group of substituents S. However, at least one of R Ｃ１ and R Ｃ２ represents a substituent selected from the group of substituents S, and at least one of R Ｃ３ and R Ｃ４ represents a substituent selected from the group of substituents S, and at least one of R Ｃ５ and R Ｃ６ represents a substituent selected from the group of substituents S, and at least one of R Ｃ７ and R Ｃ８ represents a substituent selected from the group of substituents S, and at least one of R Ｃ９ and R Ｃ１０ represents a substituent selected from the group of substituents S. At least one of R Ｃ１ and R Ｃ２ , R Ｃ３ and R Ｃ４ , R Ｃ５ and R Ｃ６ , R Ｃ７ and R Ｃ８ , and R Ｃ９ and R Ｃ１０ may each independently be bonded directly or via a linking group to form a ring. Z １ to Z ６ each independently represents -CR Ｘ１ = or a nitrogen atom. Z １ to Z ６ When two adjacent ones of them are -CR Ｘ１ =, the two Rs Ｘ１ may be bonded to each other to form a ring. R Ｘ１ represents a hydrogen atom or a substituent. R １ and R ２ each independently represents a hydrogen atom or a substituent. A １ and A ２ each independently represents a group represented by formula (A-1). In formula (A-1), * represents a bonding position. C １ represents a ring containing 2 or more carbon atoms and may have a substituent. Y １ 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 each independently represents a cyano group, -SO ２ R Ｘ５ , -COOR Ｘ６ , or -COR Ｘ７ . R Ｘ５ to R Ｘ７ each independently 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. Substituent group S: a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent, a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms having a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms having an aromatic ring group which may have a substituent, a branched aliphatic hydrocarbon group having 3 carbon atoms having a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a branched aliphatic hydrocarbon group having 3 carbon atoms having an aromatic ring group which may have a substituent, an aromatic ring group which may have a substituent, a group represented by formula (S-1), and a group represented by formula (S-2). Among the substituent group S, 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 having a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms having an aromatic ring group which may have a substituent, the branched aliphatic hydrocarbon group having 3 carbon atoms having a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, and the branched aliphatic hydrocarbon group having 3 carbon atoms having an aromatic ring group which may have a substituent may have an etheric oxygen atom and may be substituted with a halogen atom. * - L Ｓ１ -C(R Ｓ１ ) ３ Formula (S-1) *-C(=Q)R Ａｃ１ Formula (S-2) In formula (S-1), * represents a bonding position. L Ｓ１ represents a single bond or a linear alkylene group having 1 to 3 carbon atoms. R Ｓ１ each 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. A plurality of Rs Ｓ１ may be the same as or different from each other. However, among the three Rs Ｓ１ two or more 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 etheric oxygen atom and may be substituted with a halogen atom. In formula (S-2), * represents a bonding position. Q represents an oxygen atom or a sulfur 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.

2. The substituent selected from the substituent group S is 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 having a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or a substituent group R Ａｒ１ The photoelectric conversion element according to claim 1, which may have a substituent selected from an aromatic ring group which may have a substituent, a group represented by formula (S-3), or a group represented by formula (S-4). Substituent group R Ａｒ１ : 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, an aromatic ring group, a halogen atom, and *-Si(R Ｓｉ ). * represents the bonding position. ３ ​ R 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. A plurality of R Ｓｉ may be the same as or different from each other. The substituent group R Ａｒ１ Among them, 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 etheric oxygen atom and may be substituted with a halogen atom. *-C(R Ｓ２ ) ３ Formula (S-3) *-C(=O)R Ａｃ２ Formula (S-4) In formula (S-3), * represents a bonding position. R Ｓ２ each independently represents a hydrogen atom, a methyl group, an isopropyl group, or a t-butyl group. A plurality of Rs Ｓ２ may be the same as or different from each other. However, the number of carbon atoms in the group represented by the formula (S-3) is 3 to 9, and among the three Rs Ｓ２ two or more are other than hydrogen atoms. In formula (S-4), * represents a bonding position. 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 group of the substituents R Ａｒ１ above.

3. The photoelectric conversion element according to claim 1, wherein the group represented by formula (A-1) is a group represented by formula (A-2). [Chemical 2] In formula (A-2), * represents a bonding position. C ２ represents a ring containing 3 or more carbon atoms. X １ and X ２ each independently represents an oxygen atom or a sulfur atom.

4. The photoelectric conversion element according to claim 3, wherein the group represented by formula (A-2) is a group represented by formula (C-1) or a group represented by formula (C-2). 【Chemical Formula 3】 In Formula (C-1) and Formula (C-2), * represents a bonding position. In Formula (C-1), X ｃ１ and X ｃ２ each independently represents a sulfur atom or an oxygen atom. C ３ represents an aromatic ring which may have a substituent. In Formula (C-2), X ｃ３ to X ｃ５ each independently represents a sulfur atom or an oxygen atom. R ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent.

5. X is >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 ), the photoelectric conversion element according to any one of claims 1 to 4. R Ｎ and R Ｃ１ ~R Ｃ１０ are respectively R in the formula (1) above Ｎ , and R Ｃ１ ~R Ｃ１０ and have the same meaning as

6. X is >NR Ｎ , >CR Ｃ１ R Ｃ２ , or >C=CR Ｃ３ R Ｃ４ The photoelectric conversion element according to any one of claims 1 to 4, wherein X represents... R Ｎ and R Ｃ１ ~R Ｃ４ are respectively the R Ｎ , and R Ｃ１ ~R Ｃ４ in the formula (1) above and are synonymous with R

7. X is > NR Ｎ The photoelectric conversion element according to any one of claims 1 to 4, wherein X represents Ｎ . R Ｎ is synonymous with R in the formula (1). Ｎ ​

8. The photoelectric conversion film further contains an n-type organic semiconductor, The photoelectric conversion element according to any one of claims 1 to 4, wherein the photoelectric conversion film has a bulk heterojunction structure formed in a state where the compound represented by the formula (1) and the n-type organic semiconductor are mixed.

9. The photoelectric conversion element according to claim 8, wherein the n-type organic semiconductor contains fullerenes selected from the group consisting of fullerene and its derivatives.

10. The photoelectric conversion element according to any one of claims 1 to 4, wherein the photoelectric conversion film further contains a dye.

11. The photoelectric conversion element according to any one of claims 1 to 4, wherein the photoelectric conversion film further contains a p-type organic semiconductor.

12. The photoelectric conversion element according to any one of claims 1 to 4, which has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.

13. An imaging device having the photoelectric conversion element according to any one of claims 1 to 4.

14. An optical sensor having the photoelectric conversion element according to any one of claims 1 to 4.

15. A compound represented by formula (1). [Chemical Formula 4] In formula (1), X is >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 Ｎ represents a substituent selected from the substituent group S. R Ｃ１ ~R Ｃ１０ each independently represents a hydrogen atom or a substituent selected from the group of substituents S. However, at least one of R Ｃ１ and R Ｃ２ represents a substituent selected from the group of substituents S, and at least one of R Ｃ３ and R Ｃ４ represents a substituent selected from the group of substituents S, and at least one of R Ｃ５ and R Ｃ６ represents a substituent selected from the group of substituents S, and at least one of R Ｃ７ and R Ｃ８ represents a substituent selected from the group of substituents S, and at least one of R Ｃ９ and R Ｃ１０ represents a substituent selected from the group of substituents S. At least one of R Ｃ１ and R Ｃ２ , R Ｃ３ and R Ｃ４ , R Ｃ５ and R Ｃ６ , R Ｃ７ and R Ｃ８ , and R Ｃ９ and R Ｃ１０ may each independently be bonded directly or via a linking group to form a ring. Z １ to Z ６ each independently represents -CR Ｘ１ = or a nitrogen atom. Z １ to Z ６ When two adjacent ones of them are -CR Ｘ１ =, the two Rs Ｘ１ may be bonded to each other to form a ring. R Ｘ１ represents a hydrogen atom or a substituent. R １ and R ２ each independently represents a hydrogen atom or a substituent. A １ and A ２ each independently represents a group represented by formula (A-1). In formula (A-1), * represents a bonding position. C １ represents a ring containing 2 or more carbon atoms and may have a substituent. Y １ 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 each independently represents a cyano group, -SO ２ R Ｘ５ , -COOR Ｘ６ , or -COR Ｘ７ . R Ｘ５ to R Ｘ７ each independently 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. Substituent group S: a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms which may have a substituent, a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms having a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms having an aromatic ring group which may have a substituent, a branched aliphatic hydrocarbon group having 3 carbon atoms having a cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms, a branched aliphatic hydrocarbon group having 3 carbon atoms having an aromatic ring group which may have a substituent, an aromatic ring group which may have a substituent, a group represented by formula (S-1), and a group represented by formula (S-2). Among the substituent groups S, 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 the substituent, the linear aliphatic hydrocarbon group having 1 to 3 carbon atoms and having the 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 the substituent, the branched aliphatic hydrocarbon group having 3 carbon atoms and having the 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 the substituent may have an etheric oxygen atom and may be substituted with a halogen atom. * - L Ｓ１ -C(R Ｓ１ ) ３ Formula (S-1) *-C(=Q)R Ａｃ１ Formula (S-2) In formula (S-1), * represents the bonding position. L Ｓ１ represents a single bond or a linear alkylene group having 1 to 3 carbon atoms. R Ｓ１ each 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. A plurality of Rs Ｓ１ may be the same as or different from each other. However, among the three Rs Ｓ１ two or more are other than hydrogen atoms. 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 etheric oxygen atom and may be substituted with a halogen atom. In formula (S-2), * represents the bonding position. Q represents an oxygen atom or a sulfur 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.

16. The substituent selected from the substituent group S is 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 having a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or a substituent group R Ａｒ１ The compound according to claim 15, which may have a substituent selected from an aromatic ring group, a group represented by formula (S-3), or a group represented by formula (S-4). Substituent group R Ａｒ１ : 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, an aromatic ring group, a halogen atom, and *-Si(R Ｓｉ ). * represents the bonding position. ３ ​ R 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. A plurality of R Ｓｉ may be the same as or different from each other. The substituent group R Ａｒ１ Among them, 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 etheric oxygen atom and may be substituted with a halogen atom. *-C(R Ｓ２ ) ３ Formula (S-3) *-C(=O)R Ａｃ２ Formula (S-4) In formula (S-3), * represents the bonding position. R Ｓ２ each independently represents a hydrogen atom, a methyl group, an isopropyl group, or a t-butyl group. A plurality of Rs Ｓ２ may be the same as or different from each other. However, the number of carbon atoms in the group represented by the formula (S-3) is 3 to 9, and two or more of the three Rs Ｓ２ are other than hydrogen atoms. In formula (S-4), * represents the bonding position. 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 group of the substituents R Ａｒ１ above.

17. The compound according to claim 15, wherein the group represented by the formula (A-1) is a group represented by the formula (A-2). [Chemical Formula 5] In formula (A-2), * represents the bonding position. C ２ represents a ring containing 3 or more carbon atoms. X １ and X ２ each independently represents an oxygen atom or a sulfur atom.

18. The compound according to claim 17, wherein the group represented by the formula (A-2) is a group represented by the formula (C-1) or a group represented by the formula (C-2). [Chemical Formula 6] In formula (C-1) and formula (C-2), * represents the bonding position. In formula (C-1), X ｃ１ and X ｃ２ each independently represents a sulfur atom or an oxygen atom. C ３ represents an aromatic ring which may have a substituent. In formula (C-2), X ｃ３ to X ｃ５ each independently represents a sulfur atom or an oxygen atom. R ｃ１ and R ｃ２ each independently represents a hydrogen atom or a substituent.

19. X is >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 ), the compound according to any one of claims 15 to 18. R Ｎ and R Ｃ１ ~R Ｃ１０ are respectively R in the formula (1) above Ｎ and R Ｃ１ ~R Ｃ１０ and have the same meaning.

20. X is >NR Ｎ , >CR Ｃ１ R Ｃ２ , or >C=CR Ｃ３ R Ｃ４ A compound according to any one of claims 15 to 18, wherein X represents >NR, >CR, or >C=CR R Ｎ and R Ｃ１ ~R Ｃ４ are respectively the R Ｎ in the formula (1) above, and R Ｃ１ ~R Ｃ４ and have the same meaning as

21. X is >NR Ｎ The compound according to any one of claims 15 to 18, wherein X represents >NR R Ｎ is synonymous with R in the formula (1). Ｎ ​

22. The compound represented by formula (2). 【Chemical Formula 7】 In formula (2), Z １ to Z ６ each independently represents -CR Ｘ１ = or a nitrogen atom. R Ｘ１ represents a hydrogen atom or a substituent. Z １ ~Z ６ Of these, when two adjacent ones are -CR Ｘ１ =, the two Rs Ｘ１ may be bonded to each other to form a ring. R ３ represents a substituent selected from the substituent group T. Substituent group T: a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and substituent group R Ａｒ３ An aromatic ring group containing no nitrogen atom which may have a substituent selected from Among the substituent groups T, the linear aliphatic hydrocarbon group, the branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group may have an etheric oxygen atom. Substituent group R Ａｒ３ A straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, a halogen atom, or an aromatic ring group that does not contain a nitrogen atom. The substituent group R Ａｒ３ Among them, the linear aliphatic hydrocarbon group, the branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group may have an etheric oxygen atom and may be substituted with a halogen atom. R ４ and R ５ each independently represents an iodine atom, *-O-S(=O) ２ R ｆ , a bromine atom, a chlorine atom, a fluorine atom, a formyl group, *-Sn(R Ｓｎ ) ３ , *-B(R Ｂ１ ) ２ , or *-B － (R Ｂ２ ) ３ M ＋ wherein M is as defined above 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 as or different from each other. R Ｂ１ 's, and R Ｂ２ 's may be bonded to each other to form a ring structure. M ＋ represents a monovalent metal cation. * represents a bonding position. Ar represents an aromatic ring containing 2 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 substituent group T or a halogen atom. When the aromatic ring represented by Ar has a substituent selected from the substituent group T, R ３ The substituent selected from the substituent group T represented by and the substituent selected from the substituent group T that the aromatic ring represented by Ar has may be bonded to each other to form a non-aromatic ring. When a plurality of substituents selected from the substituent group T are substituted on the aromatic ring represented by Ar, the plurality of substituents may be bonded to each other to form a non-aromatic ring.

23. A process for producing a compound, comprising reacting a compound represented by formula (2a) with a compound represented by formula (X) to produce a compound represented by formula (2b). 【Chemical 8】 In formula (2a), Z １ to Z ６ each independently represents -CR Ｘ１ = or a nitrogen atom. R Ｘ１ represents a hydrogen atom or a substituent. Z １ ~Z ６ Of these, when two adjacent ones are -CR Ｘ１ =, the two Rs Ｘ１ may be bonded to each other to form a ring. R Ｌ４ and R Ｌ５ each independently represents *-O-S(=O) ２ R ｆ , a bromine atom, a chlorine atom, or a fluorine atom. X １ and X ２ each independently represents an iodine atom, *-O-S(=O) ２ R ｆ , a bromine atom, or a chlorine atom. R ｆ represents a perfluoroalkyl group having 1 to 6 carbon atoms. However, R Ｌ４ , R Ｌ５ , X １ and X ２ shall satisfy the following requirements. Requirement: An iodine atom is in the 1st position, *-O-S(=O) ２ R ｆ is in the 2nd position, a bromine atom is in the 3rd position, a chlorine atom is in the 4th position, and a fluorine atom is in the 5th position. When the ranking becomes higher from the 1st position to the 5th position, R Ｌ４ the ranking of the group represented by, and the ranking of the group represented by R Ｌ５ are both higher than the ranking of the group represented by X １ and higher than the ranking of the group represented by X ２ . In formula (X), R ３ represents a substituent selected from the substituent group T. Substituent group T: a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and substituent group R Ａｒ３ An aromatic ring group containing no nitrogen atom which may have a substituent selected from In the substituent group T, the linear aliphatic hydrocarbon group, the branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group may have an etheric oxygen atom. Substituent group R Ａｒ３ : A linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, a halogen atom, and an aromatic ring group not containing a nitrogen atom. The substituent group R Ａｒ３ Among them, the linear aliphatic hydrocarbon group, the branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group may have an etheric oxygen atom and may be substituted with a halogen atom. Ar represents an aromatic ring containing two or more carbon atoms as ring members and not containing a nitrogen atom as a ring member. The aromatic ring represented by Ar may be substituted with a substituent selected from the substituent group T or a halogen atom. When the aromatic ring represented by Ar has a substituent selected from the substituent group T, R ３ The substituent selected from the substituent group T represented by and the substituent selected from the substituent group T that the aromatic ring represented by Ar has may be bonded to each other to form a non-aromatic ring. When a plurality of substituents selected from the substituent group T are substituted on the aromatic ring represented by Ar, the plurality of substituents may be bonded to each other to form a non-aromatic ring. In formula (2b), Z １ to Z ６ , R Ｌ４ and R Ｌ５ are synonymous with Z １ to Z ６ , R Ｌ４ and R Ｌ５ in the formula (2a). R ３ and Ar are the same as R in the formula (X). ３ and Ar have the same meaning as

24. A step of reacting a compound represented by formula (2a) with a compound represented by formula (X) to produce a compound represented by formula (2b); In the compound represented by the formula (2b), R Ｌ４ and the group represented by R Ｌ５ are converted into a formyl group, *-Sn(R Ｓｎ ), ３ *, -B(R Ｂ１ ), ２ or *-B － (R Ｂ２ ), ３ M ＋ A method for producing a compound, comprising the step of R Ｓｎ , R Ｂ１ and R Ｂ２ each independently represents a substituent, and a plurality of R Ｓｎ , R Ｂ１ and R Ｂ２ may be the same as or different from each other. R Ｂ１ among themselves, and R Ｂ２ among themselves may be bonded to each other to form a ring structure. M ＋ represents a monovalent metal cation. * represents a bonding position. 【Chemical Formula 9】 In formula (2a), Z １ to Z ６ each independently represents -CR Ｘ１ = or a nitrogen atom. R Ｘ１ represents a hydrogen atom or a substituent. Z １ ~Z ６ Of these, when two adjacent ones are -CR Ｘ１ =, the two Rs Ｘ１ may be bonded to each other to form a ring. R Ｌ４ and R Ｌ５ each independently represents *-O-S(=O) ２ R ｆ , a bromine atom, a chlorine atom, or a fluorine atom. X １ and X ２ each independently represents an iodine atom, *-O-S(=O) ２ R ｆ , a bromine atom, or a chlorine atom. R ｆ represents a perfluoroalkyl group having 1 to 6 carbon atoms. However, R Ｌ４ , R Ｌ５ , X １ and X ２ shall meet the following requirements. Requirement: Ranking the iodine atom as the first position, *-O-S(=O) ２ R ｆ as the second position, the bromine atom as the third position, the chlorine atom as the fourth position, and the fluorine atom as the fifth position. When the ranking becomes higher from the first position to the fifth position, Ｌ４ the ranking of the group represented by R Ｌ５ and the ranking of the group represented by R １ are both higher than the ranking of the group represented by X ２ and higher than the ranking of the group represented by X. In formula (X), R ３ represents a substituent selected from the substituent group T. Substituent group T: a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and substituent group R Ａｒ３ An aromatic ring group containing no nitrogen atom which may have a substituent selected from In the substituent group T, the linear aliphatic hydrocarbon group, the branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group may have an etheric oxygen atom. Substituent group R Ａｒ３ : A linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, a halogen atom, and an aromatic ring group not containing a nitrogen atom. The substituent group R Ａｒ３ Among them, the linear aliphatic hydrocarbon group, the branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group may have an etheric oxygen atom and may be substituted with a halogen atom. Ar represents an aromatic ring containing two or more carbon atoms as ring members and not containing a nitrogen atom as a ring member. The aromatic ring represented by Ar may be substituted with a substituent selected from the substituent group T or a halogen atom. When the aromatic ring represented by Ar has a substituent selected from the substituent group T, R ３ The substituent selected from the substituent group T represented by and the substituent selected from the substituent group T that the aromatic ring represented by Ar has may be bonded to each other to form a non-aromatic ring. When a plurality of substituents selected from the substituent group T are substituted on the aromatic ring represented by Ar, the plurality of substituents may be bonded to each other to form a non-aromatic ring. In formula (2b), Z １ to Z ６ , R Ｌ４ and R Ｌ５ are synonymous with Z １ to Z ６ , R Ｌ４ and R Ｌ５ in the formula (2a). R ３ and Ar are the R in the formula (X) ３ and have the same meaning as Ar.

25. A compound represented by formula (3). 【Chemical Formula 10】 In formula (3), Z １ to Z ６ each independently represents -CR Ｘ１ = or a nitrogen atom. R Ｘ１ represents a hydrogen atom or a substituent. Z １ ~Z ６ When two adjacent ones of them are -CR Ｘ１ =, the two Rs Ｘ１ may be bonded to each other to form a ring. Q represents an oxygen atom or a sulfur atom. R ６ represents a substituent selected from the substituent group U. 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.

26. Reacting the compound represented by formula (3a) with the compound represented by formula (A) to obtain a compound represented by formula (3b) having a protecting group represented by SiR Ｙ１ ３ Step 1 of obtaining a compound represented by formula (3b) having a protecting group represented by: Step 2 of reacting the compound represented by formula (3b) with a metallating reagent, then reacting a formylating agent, and further deprotecting the protecting group to obtain a compound represented by formula (3c); A process for producing a compound, comprising Step 3 of reacting the compound represented by formula (3c) with a compound represented by formula (C) to obtain a compound represented by formula (3). 【Chemical 11】 In formulas (3a) to (3c), Z １ to Z ６ each independently represents -CR Ｘ１ = or a nitrogen atom. R Ｘ１ represents a hydrogen atom or a substituent. Z １ to Z ６ When two adjacent ones of them are -CR Ｘ１ =, the two Rs Ｘ１ may be bonded to each other to form a ring. X ３ and X ４ each independently represents an iodine atom, *-O-S(=O) ２ R ｆ , a bromine atom, or a chlorine atom. R ｆ represents a perfluoroalkyl group having 1 to 6 carbon atoms. In formula (3), Z １ to Z ６ is synonymous with Z in the formulas (3a) to (3c). １ to Z ６ is synonymous with. Q represents an oxygen atom or a sulfur atom. R ６ represents a substituent selected from the substituent group U. 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. In formula (A), L １ represents a leaving group. In formula (3b) and formula (A), R Ｙ１ represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. [

27. ] A compound represented by formula (3c). 【Chemical 12】 In formula (3c), Z １ to Z ６ each independently represents -CR Ｘ１ = or a nitrogen atom. R Ｘ１ represents a hydrogen atom or a substituent. Z １ ~Z ６ When two adjacent ones of them are -CR Ｘ１ =, the two Rs Ｘ１ may be bonded to each other to form a ring. In formula (C), Q and R6 have the same meanings as Q and R6 in the above formula (3). L ２ represents a leaving group.

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