Photoelectric conversion element, imaging element, photosensor, method for manufacturing imaging element, compound

Abstract

Provided is a photoelectric conversion element having a small dependence of quantum efficiency on electric field strength when receiving blue-green light. The photoelectric conversion element of the present invention sequentially has a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein the photoelectric conversion film contains a compound represented by formula (1).

Description

Technical Field

[0001] This invention relates to a photoelectric conversion element, a camera element, a light sensor, a method for manufacturing a camera element, and a compound. Background Technology

[0002] In recent years, a device with a photoelectric conversion film (e.g., a camera element) has been developed.

[0003] For example, in Patent Document 1, an organic compound with a specific structure is disclosed as a compound that can be applied to organic electronic components and photoelectric conversion components.

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2019-038759 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] With the increasing demand for improved performance in imaging elements and optical sensors, there is a need for photoelectric conversion elements that exhibit superior characteristics. For example, a required characteristic of photoelectric conversion elements is that their quantum efficiency remains relatively constant even when the electric field strength is changed; that is, the quantum efficiency has a low dependence on the electric field strength.

[0009] Under such requirements, the inventors fabricated and investigated a photoelectric conversion element comprising the compound disclosed in Patent Document 1. The results showed that the electric field strength dependence of the quantum efficiency when receiving blue-green light did not meet the desired level and there was room for improvement.

[0010] In addition, the aforementioned blue-green light refers to light with wavelengths of 400–560 nm.

[0011] Therefore, the objective of this invention is to provide a photoelectric conversion element with low electric field intensity dependence on quantum efficiency when receiving blue-green light.

[0012] Furthermore, the objective of this invention is also to provide an imaging element, a light sensor, a method for manufacturing the imaging element, and a compound related to the aforementioned photoelectric conversion element.

[0013] means for solving technical problems

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the problems can be solved by the following structure.

[0015] [1] A photoelectric conversion element having, in sequence, a conductive film, a photoelectric conversion film and a transparent conductive film, wherein the photoelectric conversion film comprises a compound represented by formula (1) described later.

[0016] [2] According to the photoelectric conversion element described in [1], wherein,

[0017] The basis represented by the formula (A-1) described later is the basis represented by the formula (C-1) described later or the basis represented by the formula (C-2) described later.

[0018] [3] According to the photoelectric conversion element described in [1] or [2], wherein,

[0019] C A ~C D At least one ring in the ring is selected from an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, an aliphatic heterocyclic group that may have substituents, or a -SiR group. Si At least one substituent in the group consisting of 3 and halogen atoms.

[0020] R Si Each can be independently represented as an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, or an aliphatic heterocyclic group that may have substituents.

[0021] [4] The photoelectric conversion element according to any one of [1] to [3], wherein,

[0022] R X1 ~R X5 They can be, independently, aliphatic hydrocarbon groups that can have substituents, aromatic cyclic groups that can have substituents, or aliphatic heterocyclic groups that can have substituents.

[0023] [5] The photoelectric conversion element according to any one of [1] to [4], wherein,

[0024] R Z Each is independently a hydrogen atom, a halogen atom, or a -SiR atom. Si 3. It can be an aliphatic hydrocarbon group with substituents, an aromatic cyclic group with substituents, or an aliphatic heterocyclic group with substituents.

[0025] R Si Each can be independently represented as an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, or an aliphatic heterocyclic group that may have substituents.

[0026] [6] The photoelectric conversion element according to any one of [1] to [5], wherein,

[0027] C D The ring is represented by equation (4-1) as described later.

[0028] [7] The photoelectric conversion element according to any one of [1] to [6], wherein,

[0029] C A Let be the ring represented by equation (2-2) as described later.

[0030] [8] The photoelectric conversion element according to any one of [1] to [7], wherein,

[0031] C B and C C At least one of them is the ring represented by equation (3-5) or equation (3-4) described later.

[0032] [9] The photoelectric conversion element according to any one of [1] to [8], wherein,

[0033] The compound represented by formula (1) above is the compound represented by formula (1-1) or formula (1-2) described later.

[0034]

[10] The photoelectric conversion element according to any one of [1] to [9], wherein,

[0035] The compound represented by formula (1) above is the compound represented by formula (5) described later.

[0036]

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

[10] , wherein,

[0037] The aforementioned photoelectric conversion film also contains an n-type organic semiconductor.

[0038] The photoelectric conversion film described above has a bulk hetero structure formed in the state of the compound represented by the above formula (1) mixed with the above n-type organic semiconductor.

[0039]

[12] According to the photoelectric conversion element described in

[11] , wherein,

[0040] The aforementioned n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and their derivatives.

[0041]

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

[12] , wherein,

[0042] The aforementioned photoelectric conversion film also contains a p-type organic semiconductor.

[0043]

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

[13] , wherein,

[0044] The aforementioned photoelectric conversion film also contains pigments.

[0045]

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

[14] , wherein,

[0046] Between the conductive film and the transparent conductive film, there is one or more intermediate layers in addition to the photoelectric conversion film.

[0047]

[16] A camera element having any one of the photoelectric conversion elements described in [1] to

[15] .

[0048]

[17] An optical sensor having a photoelectric conversion element as described in any one of [1] to

[15] .

[0049]

[18] A method for manufacturing an image sensor, comprising the steps of manufacturing the photoelectric conversion element as described in any one of [1] to

[15] .

[0050]

[19] A compound represented by formula (1) as described below.

[0051]

[20] According to the compound described in

[19] , wherein,

[0052] The basis represented by the following formula (A-1) is the basis represented by the following formula (C-1) or the basis represented by the following formula (C-2).

[0053]

[21] According to the compound described in

[19] or

[20] , wherein,

[0054] C A ~C D At least one ring in the ring is selected from an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, an aliphatic heterocyclic group that may have substituents, or a -SiR group. Si At least one substituent in the group consisting of 3 and halogen atoms.

[0055] R Si Each can be independently represented as an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, or an aliphatic heterocyclic group that may have substituents.

[0056]

[22] The compound according to any one of

[19] to

[21] , wherein,

[0057] R X1 ~R X5 They can be, independently, aliphatic hydrocarbon groups that can have substituents, aromatic cyclic groups that can have substituents, or aliphatic heterocyclic groups that can have substituents.

[0058]

[23] The compound according to any one of

[19] to

[22] , wherein,

[0059] RZ Each is independently a hydrogen atom, a halogen atom, or a -SiR atom. Si 3. It can be an aliphatic hydrocarbon group with substituents, an aromatic cyclic group with substituents, or an aliphatic heterocyclic group with substituents.

[0060] R Si Each can be independently represented as an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, or an aliphatic heterocyclic group that may have substituents.

[0061]

[24] The compound according to any one of

[19] to

[23] , wherein,

[0062] C D The ring is represented by equation (4-1) as described later.

[0063]

[25] The compound according to any one of

[19] to

[24] , wherein,

[0064] C A Let be the ring represented by equation (2-2) as described later.

[0065]

[26] The compound according to any one of

[19] to

[25] , wherein,

[0066] C B and C C At least one of them is the ring represented by equation (3-5) or the ring represented by equation (3-4) described later.

[0067]

[27] The compound according to any one of

[19] to

[26] , wherein,

[0068] The compound represented by formula (1) above is the compound represented by formula (1-1) or formula (1-2) described later.

[0069]

[28] The compound according to any one of

[19] to

[27] , wherein,

[0070] The compound represented by formula (1) above is the compound represented by formula (5) described later.

[0071] Invention Effects

[0072] According to the present invention, a photoelectric conversion element with low electric field intensity dependence on quantum efficiency when receiving blue-green light can be provided.

[0073] Furthermore, according to the present invention, it is also possible to provide an imaging element, a light sensor, a method for manufacturing the imaging element, and a compound related to the above-mentioned photoelectric conversion element. Attached Figure Description

[0074] Figure 1 This is a cross-sectional schematic diagram showing a structural example of a photoelectric conversion element.

[0075] Figure 2 This is a cross-sectional schematic diagram showing a structural example of a photoelectric conversion element. Detailed Implementation

[0076] The present invention will now be described in detail.

[0077] Sometimes, the constituent elements described below are explained based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0078] In this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0079] In this specification, a hydrogen atom can be any of a light hydrogen atom (the usual hydrogen atom) or a deuterium atom (e.g., a dihydrogen atom).

[0080] In this specification, when there are multiple substituents and linking groups (hereinafter also referred to as "substituents, etc.") represented by specific symbols, or when multiple substituents, etc. are specified simultaneously, it means that each substituent, etc., may be the same as or different from each other. The same applies to the number of substituents, etc.

[0081] In this specification, unless otherwise specified, “substituent” can refer to the groups exemplified in Substituent W below.

[0082] (Substituent W)

[0083] The substituent W in this specification is described.

[0084] Regarding substituents W, examples include halogen atoms (e.g., fluorine, chlorine, bromine, and iodine atoms), alkyl groups (including cycloalkyl, bicycloalkyl, and tricycloalkyl), alkenyl groups (including cycloalkenyl and bicycloalkenyl), alkynyl, aryl, heterocyclic (heteroaryl or aliphatic heterocyclic), cyano, nitro, alkoxy, aryloxy, silylalkyl, silanoxy, heterocyclic, acyloxy, carbamoyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, primary, secondary, or tertiary amino groups (including aniline), alkylthio, arylthio, heterocyclic thio, alkyl or arylsulfinyl, alkyl or arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, aryl or heterocyclic azo, imide, phosphonyl, oxophosphonyl, oxophosphonyloxy, oxophosphonylamino, phosphonyl, carboxyl, phosphate, sulfonic acid, hydroxyl, thiol, amide, carbamoyl, and borate. Where possible, each of the above-mentioned groups may further have substituents (e.g., one or more of the above-mentioned groups). For example, as a substituent W, an alkyl group that may have substituents may also be included.

[0085] When the substituent W has carbon atoms, the number of carbon atoms in the substituent W is, for example, 1 to 20.

[0086] The number of atoms other than hydrogen atoms in the substituent W is, for example, 1 to 30.

[0087] Furthermore, for the specific compounds described later, it is also preferable that the substituents do not have a carboxyl group, a salt of a carboxyl group, a phosphate group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxyl group, a thiol group, an amide group, a carbamoyl group, a urea group, a borate group (-B(OH)2) and / or a primary amide group.

[0088] In this specification, halogen atoms, for example, include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0089] Unless otherwise specified in this specification, aliphatic hydrocarbon groups can be any of the following: straight-chain, branched, and cyclic.

[0090] Examples of aliphatic hydrocarbon groups mentioned above include alkyl, alkenyl, and alkynyl groups.

[0091] 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.

[0092] Unless otherwise specified, alkyl groups can be any of the following: straight-chain, branched, and cyclic.

[0093] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, cyclopropyl, and cyclopentyl.

[0094] The cyclic alkyl group can be any of the cycloalkyl, bicycloalkyl, and tricycloalkyl groups, and the alkyl group can have these rings as part of its structure.

[0095] Among the alkyl groups that can have substituents, the substituents that the alkyl group can have include, for example, the groups exemplified in substituent W. Among them, aryl (preferably having 6 to 18 carbon atoms, more preferably 6 carbon atoms), heteroaryl (preferably having 5 to 18 carbon atoms, more preferably 5 to 6 carbon atoms) or halogen atom (preferably fluorine atom or chlorine atom) are preferred.

[0096] Unless otherwise specified in this specification, the alkyl portion of the alkoxy and alkylthio groups is preferably the alkyl group described above.

[0097] Among alkoxy groups that can have substituents, examples of substituents that can be present in alkoxy groups are the same as those in alkyl groups that can have substituents.

[0098] Among alkylthio groups that can have substituents, examples of substituents that can be present in alkyl groups are the same as those in alkyl groups that can have substituents.

[0099] In this specification, unless otherwise specified, the alkenyl group can be any of the linear, branched, and cyclic forms. The alkenyl group preferably has 2 to 20 carbon atoms. Examples of alkenyl groups that can have substituents include those found in alkyl groups that can also have substituents.

[0100] In this specification, unless otherwise specified, the alkynyl group can be any of the following: linear, branched, and cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20. Examples of alkynyl groups that can have substituents include those identical to those in alkyl groups that can have substituents.

[0101] In this specification, unless otherwise specified, the aromatic ring or the aromatic ring constituting the aromatic ring group can be any of a monocyclic or polycyclic (e.g., 2 to 6 rings). A monocyclic aromatic ring is an aromatic ring having only one ring. A polycyclic aromatic ring (e.g., 2 to 6 rings) is an aromatic ring formed by the fusion of multiple (e.g., 2 to 6 rings) aromatic rings.

[0102] The number of ring members in the above-mentioned aromatic ring is preferably 5 to 15.

[0103] Unless otherwise specified in this specification, the aromatic ring may be any of the aromatic hydrocarbon rings and aromatic heterocycles.

[0104] When the aromatic ring is an aromatic heterocycle, the number of heteroatoms that are ring member atoms is, for example, 1 to 10. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron.

[0105] Examples of aromatic hydrocarbon rings mentioned above include benzene rings, naphthalene rings, anthracene rings, pyrene rings, phenanthrene rings, and fluorene rings.

[0106] Examples of aromatic heterocycles include, for example, pyridine rings, pyrimidine rings, pyridazine rings, pyrazine rings, triazine rings (e.g., 1,2,3-triazine rings, 1,2,4-triazine rings, and 1,3,5-triazine rings), tetrazine rings (e.g., 1,2,4,5-tetrazine rings), quinoxaline rings, pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, thiazole rings, benzopyrrole rings, benzofuran rings, benzothiophene rings, benzoimidazolium rings, benzoxazole rings, benzothiazole rings, benzoxazole rings, naphthopyrrole rings, naphthofuran rings, naphthothiophene rings, naphthoimidazolium rings, naphthooxazole rings, pyrroloimidazolium rings (e.g., 5H-pyrrolo[1,2-a]imidazolium rings), imidazoxazole rings (e.g., imidazo[2,1-b]oxazole rings), and thienothiazole rings (e.g., thieno[1,2-a]imidazolium rings). [2,3-d]thiazole ring, etc.), benzothiadiazole ring, benzodithiophene ring (e.g., benzo[1,2-b:4,5-b']dithiophene ring, etc.), thieno[3,2-b]thiophene ring, etc., thiazo[5,4-d] ... [b'] dithiophene ring, naphtho[2,1-b:6,5-b'] dithiophene ring, naphtho[1,2-b:5,6-b'] dithiophene ring and 1,8-dithiadicyclopentane[b,g]naphthylene ring, benzothiophene and benzothiophene ring, dithiophene[3,2-b:2',3'-d] thiophene ring and 3,4,7,8-tetrathiadicyclopentane[a,e]cyclopentadiene ring.

[0107] In this specification, when the group is an aromatic ring group, examples include groups formed by removing one or more (e.g., 1 to 5) hydrogen atoms from the aromatic ring. In this specification, when the group is an aromatic hydrocarbon group, examples include groups formed by removing one or more (e.g., 1 to 5) hydrogen atoms from the aromatic hydrocarbon ring; and when the group is an aromatic heterocyclic group, examples include groups formed by removing one or more (e.g., 1 to 5) hydrogen atoms from the aromatic heterocyclic ring.

[0108] In this specification, when it is aryl, for example, a group formed by removing one hydrogen atom from the ring corresponding to the aromatic hydrocarbon ring in the above-mentioned aromatic ring can be cited.

[0109] In this specification, when it is a heteroaryl group, for example, a group formed by removing one hydrogen atom from the ring corresponding to the aromatic heterocycle in the above-mentioned aromatic ring can be cited.

[0110] In this specification, when it is an arylene group, for example, a group formed by removing two hydrogen atoms from the ring corresponding to the aromatic hydrocarbon ring in the above-mentioned aromatic ring can be cited.

[0111] In this specification, when it is a heteroarylene, for example, a group formed by removing two hydrogen atoms from the ring corresponding to the aromatic heterocycle in the above-mentioned aromatic ring can be cited.

[0112] Among the aromatic cycloalcohols, aryl groups, heteroaryl groups, arylene groups, and heteroarylene groups that can have substituents, the types of substituents that these groups can have include, for example, the groups exemplified in Substituent W. The number of substituents when these groups have substituents is only 1 or more (e.g., 1 to 4, etc.).

[0113] In this specification, non-aromatic rings refer to rings that do not correspond to aromatic rings, such as aliphatic hydrocarbon rings and aliphatic heterocycles.

[0114] Examples of aliphatic hydrocarbon rings mentioned above include cycloalkanes, cycloalkenes, and cycloalkynes.

[0115] Examples of the aforementioned aliphatic heterocycles include pyrrolidine rings, oxopentyl rings, thiopentyl rings, piperidine rings, tetrahydropiperanyl rings, thiaran rings, piperazine rings, morpholine rings, quinine rings, acridine rings, oxobutane rings, acridine rings, dioxane rings, and γ-butyrolactone rings.

[0116] In this specification, when it is an aliphatic hydrocarbon cyclic group, for example, a group formed by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the ring corresponding to the aliphatic hydrocarbon ring can be cited.

[0117] In this specification, when it is an aliphatic heterocyclic group, for example, a group formed by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from a ring corresponding to an aliphatic heterocycle can be cited.

[0118] In this specification, when there are multiple identical symbols representing the same type or number of bases in a single formula representing a chemical structure, unless otherwise specified, the contents of these multiple identical symbols are independent of each other, and the contents of the identical symbols may be the same or different.

[0119] In this specification, when multiple groups of the same kind (e.g., alkyl groups, etc.) exist in a single formula representing a chemical structure, unless otherwise specified, the specific contents of these multiple groups of the same kind are independent of each other, and the specific contents of groups of the same kind may be the same or different.

[0120] Unless otherwise specified, the bonding direction of the divalent groups (e.g., -CO-O-, etc.) described in this specification is not limited. For example, when Y in a compound represented by the formula "XYZ" is -CO-O-, the compound can be either "XO-CO-Z" or "X-CO-OZ".

[0121] In this specification, for ease of explanation, compounds that may have geometric isomers (cis-trans isomers) are sometimes described using only the cis or trans isomer in terms of their general formula or structural formula. Even in such cases, unless otherwise specified, the compound is not limited to either the cis or trans isomer; the compound can be either the cis or trans isomer.

[0122] Furthermore, in this specification, for ease of explanation, the general formula or structural formula representing compounds having asymmetric atoms is sometimes described without distinguishing between stereoisomers. Even in such cases, unless otherwise specified, the form of the compounds is not limited to any one form; they can be any form or a mixture. For example, unless otherwise specified, compounds having asymmetric carbon atoms can be either the S-form or the R-form, or a mixture thereof.

[0123] Furthermore, in this specification, for ease of explanation, compounds or structures having resonance structures are sometimes described using only one resonance structural formula to represent the general formula or structural formula of the aforementioned compounds. Even in such cases, unless otherwise specified, the aforementioned compounds and structures, within the scope of molecular compatibility, include compounds and structures represented by other resonance structural formulas that can be used to represent the aforementioned compounds and structures.

[0124] Unless otherwise specified, the asterisk (*) in this specification indicates the bonding position.

[0125] Unless otherwise specified, the bonding direction is not particularly limited when there are two or more bonding positions indicated by * in the formula. For example, when Y is a group represented by *-AB-* in a compound constituting "XYZ", the compound can be either "XABZ" or "XBAZ". Furthermore, for example, the structure formed by the fusion of the ring represented by formula (X1) and the ring represented by formula (X2) at the bonding positions indicated by * can be either the structure represented by formula (X3) or the structure represented by formula (X4).

[0126] [Chemical Formula 1]

[0127]

[0128] Photoelectric conversion element

[0129] The photoelectric conversion element of the present invention comprises a conductive film, a photoelectric conversion film and a transparent conductive film in sequence, wherein the photoelectric conversion film comprises a compound represented by formula (1) described later (hereinafter also referred to as "specific compound").

[0130] While the reason why the photoelectric conversion element with the above structure can solve the problem of the present invention is not yet clear, the inventors speculate as follows.

[0131] Furthermore, the following speculations do not limit the mechanism by which the effect is achieved. In other words, even situations where the effect is achieved through mechanisms other than those described below are included within the scope of this invention.

[0132] The specific compounds are so-called DA-type pigment compounds having a donor portion (D) and an acceptor portion (A). These specific compounds possess defined donor and acceptor structures, thus suppressing excessive aggregation of the compounds and carrier trapping caused by localized dipoles in the photoelectric conversion film. As a result, it is believed that efficient charge separation can be achieved even under low electric field strength, and carriers can move efficiently, thus exhibiting low field strength dependence on quantum efficiency.

[0133] Hereinafter, the fact that the electric field strength dependence of quantum efficiency is smaller when receiving blue-green light will also be referred to as "the effect of the present invention is better".

[0134] Figure 1 The figure shows a cross-sectional schematic diagram of one embodiment of the photoelectric conversion element of the present invention.

[0135] Figure 1The photoelectric conversion element 10a shown has a structure consisting of a conductive film (hereinafter also referred to as "lower electrode") 11, which functions 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 "upper electrode") 15, which functions as an upper electrode, stacked in sequence.

[0136] Figure 2 The diagram shows an example of the structure of another photoelectric conversion element. Figure 2 The photoelectric conversion element 10b shown has a structure formed by sequentially stacking an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 on a lower electrode 11. Furthermore, Figure 1 and Figure 2 The stacking order of the electron blocking film 16A, photoelectric conversion film 12 and hole blocking film 16B can be appropriately changed according to the application and characteristics.

[0137] In the photoelectric conversion element 10a (or 10b), light is preferably incident on the photoelectric conversion film 12 via the upper electrode 15.

[0138] Furthermore, when using photoelectric conversion element 10a (or 10b), a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and preferably a voltage of 1×10⁻⁶ is applied between these pairs of electrodes. -5 ~1×10 7 A voltage of V / cm. From the viewpoint of performance and power consumption, an applied voltage of 1×10 V / cm is more preferable. -4 ~1×10 7 V / cm, further preferably 1×10 -3 ~5×10 6 V / cm.

[0139] In addition, regarding the method of voltage application, in Figure 1 and Figure 2 In this process, it is preferable to apply the voltage with the electron blocking film 16A side as the cathode and the photoelectric conversion film 12 side as the anode. When the photoelectric conversion element 10a (or 10b) is used as a light sensor, and when it is assembled into an imaging element, the voltage can also be applied in the same way.

[0140] As detailed in the following section, the photoelectric conversion element 10a (or 10b) can be preferably used for imaging element applications.

[0141] The following describes in detail the manner in which each layer of the photoelectric conversion element constitutes the present invention.

[0142] [Photoconversion film]

[0143] Photoelectric conversion elements have photoelectric conversion films.

[0144] <Specific Compound>

[0145] The photoelectric conversion film includes the compound represented by formula (1), i.e., the specific compound.

[0146] [Chemical Formula 2]

[0147]

[0148] In equation (1), C A C represents the ring represented by the expression in the group consisting of free expression (2-1), expression (2-2), and expression (2-3). B and C C Let C represent the rings represented by the formulas in the groups consisting of formulas (3-1), (3-2), (3-3), and (3-4), respectively. D Let represent the ring represented by the expression in the group consisting of the free expression (4-1) and expression (4-2).

[0149] In equations (2-1) to (2-3), (3-1) to (3-4), and (4-1) to (4-2), X independently represents oxygen atom, sulfur atom, selenium atom, and -NR atom, respectively. X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, R X1 ~R X5 Each can be used to represent a hydrogen atom or a substituent independently.

[0150] Z represents -CR independently. Z = or nitrogen atom. R Z Indicates a hydrogen atom or does not contain an azo group, -NR N 2. The base represented by formula (N) and any of the substituents in -CH=A. R N Each can be represented independently as a hydrogen atom or a substituent. A represents the base represented by formula (A-1).

[0151] *, *1, and *2 represent the bonding positions. Where C B The ring represented by the formula in the group consisting of the above formulas (3-1), (3-2), (3-3), and (3-4) has two *1 bonding positions with C. A The ring and C are represented C The ring fusion of one of the rings is represented by two * 2 bonding sites with C. A The ring and C are represented C The rings of the other ring represented are fused. Furthermore, CC The ring represented by the formula in the group consisting of the above formulas (3-1), (3-2), (3-3), and (3-4) has two *1 bonding positions with C. B The ring and C are represented D The ring fusion of one of the rings is represented by two * 2 bonding sites with C. B The ring and C are represented D The rings of the other rings represented are fused.

[0152] In equation (3-4), Y represents an oxygen atom, a sulfur atom, or -NR. Y1 -. R Y1 It represents a hydrogen atom or a substituent.

[0153] R can represent either a hydrogen atom or a substituent independently.

[0154] In equations (4-1) and (4-2), A represents the basis represented by the above equation (A-1).

[0155] In equation (A-1), C 1 This indicates a ring containing at least two carbon atoms and which may have substituents.

[0156] Q represents oxygen atom, sulfur atom, =NR Q1 or =CR Q2 R Q3 R Q1 Represents a hydrogen atom or a substituent. R Q2 and R Q3 Representing cyano and -SO2R independently, respectively. Q4 -COOR Q5 or -COR Q6 R Q4 ~R Q6 Each can be independently represented as an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, or an aliphatic heterocyclic group that may have substituents.

[0157] * indicates the bonding location.

[0158] In formula (N), C N This indicates a ring containing nitrogen atoms. R N2 Each substituent can be represented independently. m represents an integer greater than or equal to 0. In R... N2 When there are more than two, R N2 They can bond together to form rings that can have substituents.

[0159] * indicates the bonding location.

[0160] Among them, the compound represented by the above formula (1) satisfies at least one of the following requirements A to D.

[0161] Requirement A: C A The ring represented by equation (2-1) or equation (2-3) above.

[0162] Requirement B: C B and C C At least one of them is the ring represented by formula (3-1) or the ring represented by formula (3-4) above, and X in the ring represented by formula (3-1) above represents an oxygen atom, a sulfur atom, a selenium atom, or a -SiR atom. X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -.

[0163] Among them, C B and C C Except for the case of the ring represented by the above formula (3-1).

[0164] Requirement C: C B and C C All are rings represented by the above equation (3-1), and C B and C C In one of them, X represents oxygen atom, selenium atom, -NR. X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -.

[0165] Requirement D: C D The ring represented by equation (4-1) above, where X in the ring represented by equation (4-1) above represents an oxygen atom, a sulfur atom, or -NR. X1 -、-CR X4 2- or -C (=CR) X5 2) -.

[0166] In equation (1), C A This represents the ring represented by the formula in the group consisting of formulas (2-1), (2-2), and (2-3). From the perspective of superior manufacturing suitability, C... A The preferred ring is the one represented by formula (2-2). Furthermore, manufacturing suitability refers to the characteristic that the performance of the photoelectric conversion element does not easily deteriorate even when the film deposition rate is accelerated.

[0167] C B and C CLet each independently represent the ring represented by the formula in the group consisting of formulas (3-1), (3-2), (3-3), and (3-4). From the perspective of superior quantum efficiency, C... B and C C At least one of them is preferably the ring represented by formula (3-1) or the ring represented by formula (3-4), more preferably the ring represented by formula (3-5) or the ring represented by formula (3-4) as described later, and even more preferably the ring represented by formula (3-5).

[0168] Among them, C B and C C Both are preferably the rings represented by formula (3-1), and more preferably one is the ring represented by formula (3-5) and the other is the ring represented by formula (3-1).

[0169] C D This represents the ring represented by the formula in the group consisting of formulas (4-1) and (4-2). From the perspective of superior manufacturing suitability, C... D The preferred one is the ring represented by formula (4-1).

[0170] C A ~C D At least one ring in the ring preferably has a substituent, C B and C C At least one of the rings preferably has a substituent.

[0171] Regarding C A Having substituents, specifically, refers to C A A ring represented by equation (2-1) or equation (2-3) that satisfies at least one of the following conditions R1 and R2, or a ring represented by equation (2-2) that satisfies the following condition R1.

[0172] Regarding C B Having substituents, specifically, refers to C B A ring that satisfies requirement R2, represented by equation (3-1), or a ring that satisfies requirement R1, represented by equation (3-2) or equation (3-3), or a ring that satisfies requirement R3, represented by equation (3-4).

[0173] Regarding C C Having substituents, specifically, refers to C C A ring that satisfies requirement R2, represented by equation (3-1), or a ring that satisfies requirement R1, represented by equation (3-2) or equation (3-3), or a ring that satisfies requirement R3, represented by equation (3-4).

[0174] Regarding C D Having substituents, specifically, refers to CD A ring represented by equation (4-1) that satisfies at least one of the following conditions R1 and R2, or a ring represented by equation (4-2) that satisfies the following condition R1.

[0175] Requirement R1: At least one representation of Z - CR S =. R S This indicates a substituent. Additionally, R... S The meaning of R Z The indicated group does not contain azo or -NR. N 2. The base represented by formula (N) and any of the substituents in -CH=A have the same meaning.

[0176] Requirement R2: X indicates -NR T -、-SiR T R X2 -、-GeR T R X3 -or-CR T R X4 -、-C(=CR T R X5 )-。 R T Indicates a substituent. R X2 ~R X5 It represents a hydrogen atom or a substituent.

[0177] Requirement R3: At least one of R represents a substituent or Y represents -NR. Y -and R Y Indicates a substituent.

[0178] As substituents that can be present in the aforementioned ring, examples of substituents W can be cited. From the viewpoint of better effects of the present invention, aliphatic hydrocarbon groups that can have substituents, aromatic cyclic groups that can have substituents, aliphatic heterocyclic groups that can have substituents, and -SiR groups are preferred. Si 3. Halogen atom, cyano group, acyl group that may have substituents, alkoxy group that may have substituents, or aryloxy group that may have substituents, more preferably aliphatic hydrocarbon group that may have substituents, aromatic cyclic group that may have substituents, aliphatic heterocyclic group that may have substituents, -SiR Si 3 or halogen atoms, more preferably aliphatic hydrocarbon group that may have substituents, aromatic cyclic group that may have substituents, or -SiR Si 3.

[0179] The aforementioned aliphatic hydrocarbon groups can be any of the following: straight-chain, branched, or cyclic.

[0180] Examples of aliphatic hydrocarbon groups include alkyl, alkenyl, and alkynyl groups, with alkyl being the most preferred.

[0181] The number of carbon atoms in the linear aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 4, and especially preferably 1 or 2.

[0182] The branched aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 10, even more preferably 3 to 7, and especially preferably 3 to 5.

[0183] The cyclic aliphatic hydrocarbon group can be any of a monocyclic or polycyclic ring. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 6.

[0184] The aromatic cyclic group mentioned above can be any of the aromatic hydrocarbon group and the aromatic heterocyclic group.

[0185] The aromatic ring group mentioned above can be any of monocyclic or polycyclic, preferably monocyclic.

[0186] The number of ring-membered atoms of the above-mentioned aromatic ring group is preferably 5 to 18, more preferably 5 to 10, and even more preferably 5 to 8.

[0187] Regarding the definition and specific examples of the aromatic hydrocarbon group mentioned above, as described above, it is preferably phenyl or naphthyl, and more preferably phenyl.

[0188] Examples of heteroatoms present in the aforementioned aromatic heterocyclic groups include sulfur atoms, oxygen atoms, nitrogen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and boron atoms, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred.

[0189] Regarding the definition and specific examples of the above-mentioned aromatic heterocyclic groups, as mentioned above, thiophene cyclic group, furan cyclic group or pyridine cyclic group are preferred.

[0190] Regarding the aromatic ring group, as mentioned above, it may have substituents. When the aromatic ring group has substituents, there is no particular limitation on the number of substituents, but 1 to 3 are preferred.

[0191] The aforementioned aliphatic heterocyclic group can be any of monocyclic or polycyclic, preferably monocyclic.

[0192] The number of ring-membered atoms in the above-mentioned aliphatic heterocyclic group is preferably 3 to 18, more preferably 5 to 10, and even more preferably 5 to 8.

[0193] Examples of heteroatoms present in the aforementioned aliphatic heterocyclic groups include sulfur atoms, oxygen atoms, nitrogen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and boron atoms, with sulfur atoms or oxygen atoms being preferred.

[0194] Regarding the definition and specific examples of the aforementioned aliphatic heterocyclic groups, as described above, the preferred groups are thiopentyl, tetrahydrofuranyl, or tetrahydropyranyl.

[0195] Regarding the aliphatic heterocyclic group, as described above, it may have substituents. When the aliphatic heterocyclic group has substituents, there is no particular limitation on the number of substituents, but 1 to 3 are preferred.

[0196] -SiR Si In the basis represented by 3, R Si Each can be independently represented as an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, or an aliphatic heterocyclic group that may have substituents.

[0197] R Si The definitions and preferred methods of aliphatic hydrocarbon groups, aromatic cyclic groups, and aliphatic heterocyclic groups that can have substituents, and as if C A ~C D If at least one of the substituents is present, then the substituents exemplified are the same as those of the substituents.

[0198] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine or chlorine atoms being preferred.

[0199] The acyl group mentioned above can be any of aliphatic or aromatic hydrocarbon groups.

[0200] The preferred manner of the aliphatic hydrocarbon group and aromatic hydrocarbon group of the above-mentioned acyl group and as a C A ~C D If at least one of the substituents is present, then the substituents exemplified are the same as those of the substituents.

[0201] The number of carbon atoms in the acyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[0202] The alkyl group in the above-mentioned alkoxy group can be any of the straight-chain, branched, and cyclic forms.

[0203] The number of carbon atoms in the above-mentioned alkoxy group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 to 3.

[0204] The aryl group in the above-mentioned aryloxy group can be any of a monocyclic or polycyclic compound.

[0205] The number of carbon atoms in the aryloxy group is preferably 5 to 18, more preferably 6 to 10, and even more preferably 6 to 8.

[0206] As examples of substituents that can be present in each of the aforementioned substituent groups, the substituents exemplified in the substituent W above are preferably substituents selected from the substituent group S.

[0207] Substituent group S: straight-chain aliphatic hydrocarbon group with 1-3 carbon atoms, branched aliphatic hydrocarbon group with 3-7 carbon atoms, cyclic aliphatic hydrocarbon group with 3-6 carbon atoms, aromatic cyclic group with 3-20 ring members that may have substituents, alkoxy group that may have substituents, acyl group that may have substituents, -SiR Si 3 and halogen atoms.

[0208] The number of carbon atoms in the straight-chain aliphatic hydrocarbon group in the above-mentioned substituent group S is 1 to 3, more preferably 1 or 2.

[0209] The branched aliphatic hydrocarbon group in the above-mentioned substituent group S has 3 to 7 carbon atoms, more preferably 3 or 4.

[0210] The cyclic aliphatic hydrocarbon group in the above substituent group S is preferably a monocyclic group.

[0211] The aromatic ring group in the above substituent group S can be any of monocyclic or polycyclic, preferably monocyclic.

[0212] The aromatic cyclic group can be any of an aromatic hydrocarbon group or an aromatic heterocyclic group, preferably an aromatic hydrocarbon group. The heteroatom contained in the above-mentioned aromatic heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.

[0213] The number of ring members in the above-mentioned aromatic ring group is 3 to 20, preferably 5 to 12, and more preferably 5 or 6.

[0214] As substituents that can be present in the aforementioned aromatic ring group, examples of substituents exemplified in substituent W are provided. Preferably, substituents are selected from the substituent group S, and more preferably, straight-chain aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 7 carbon atoms, or -SiR. Si 3. Alkoxy or halogen atoms with 1 to 4 carbon atoms.

[0215] When the aromatic ring group has substituents, the number of substituents is preferably 1 to 3.

[0216] The number of carbon atoms of the alkoxy group in the above-mentioned substituent group S is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0217] The acyl group in the above-mentioned substituent group S can be any of aliphatic hydrocarbon groups and aromatic hydrocarbon groups, preferably aliphatic hydrocarbon groups.

[0218] The number of carbon atoms in the acyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0219] Substituents that can be present in the above-mentioned alkoxy and acyl groups include those exemplified in the substituent W above, preferably substituents selected from the substituent group S, and more preferably -SiR. Si 3. Alkoxy or halogen atoms with 1 to 4 carbon atoms.

[0220] -SiR in the above substituent group S Si In the basis represented by 3, regarding R Si The definition and preferred method are as described above.

[0221] Examples of halogen atoms in the substituent group S include fluorine, chlorine, bromine, and iodine atoms, with fluorine or chlorine atoms being preferred.

[0222] The substituents that the above-mentioned ring may have preferably not include azo groups or -NR groups. N 2. Any of the bases represented by equation (N) and -CH=A.

[0223] [Chemical Formula 3]

[0224]

[0225] Substituents do not include azo groups or -NR groups. N 2. The base represented by formula (N) and any one of -CH=A means that it does not contain any of the above bases as substituents, either as part or all of them.

[0226] More specifically, the fact that the substituent does not contain an azo group means that the substituent does not contain a divalent linking group as represented by -N=N-.

[0227] Substituents do not contain -NR N 2 refers to the substituent being -NR. N 2 different groups, and with -NR as part of the substituent N The groups 2 are also different. The groups that do not include the group represented by formula (N) and the groups that do not include the group represented by -CH=A are also the same.

[0228] -NR N In 2, R N Each can be used to represent a hydrogen atom or a substituent independently.

[0229] In formula (N), C N This indicates a ring containing nitrogen atoms. (C) N The nitrogen atom included is the nitrogen atom explicitly stated in formula (N). C N The ring represented can be any of the aromatic or non-aromatic rings.

[0230] R N2 Substituents are represented independently.

[0231] m represents an integer greater than or equal to 0. In R... N2 When there are more than two, R N2 They can bond with each other to form rings that can have substituents. R N2 The rings formed by mutual bonding can be either aromatic or non-aromatic rings.

[0232] * indicates the bonding location.

[0233] Examples of groups represented by formula (N) include carbazole cyclogroup, pyrrole cyclogroup, piperidine cyclogroup, and indole cyclogroup.

[0234] In -CH=A, A represents the basis represented by equation (A-1). Equation (A-1) will be discussed later.

[0235] In equations (2-1) to (2-3), (3-1) to (3-4), and (4-1) to (4-2), X independently represents oxygen atom, sulfur atom, selenium atom, and -NR atom, respectively. X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -.

[0236] In equations (2-1) and (2-3), X is preferably an oxygen atom, a sulfur atom, or -NR. X1 - or selenium atom, more preferably oxygen atom or sulfur atom, and even more preferably sulfur atom.

[0237] In formula (3-1), X is preferably a sulfur atom, an oxygen atom, a selenium atom, or -NR. X1 -、-SiR X2 2- or -CR X4 2-, more preferably sulfur atom, oxygen atom, -SiR X2 2-、-NR X1 -or-CR X4 2-, more preferably sulfur atom, oxygen atom or -CR X4 2-.

[0238] In formula (4-1), X is preferably a sulfur atom, an oxygen atom, or a selenium atom, more preferably a sulfur atom or an oxygen atom, and even more preferably a sulfur atom.

[0239] R X1 ~R X5 The hydrogen atom or the substituent can be represented independently, but from the viewpoint of better performance of the present invention, the substituent is preferred.

[0240] Examples of substituents described above include those exemplified in substituent W, preferably aliphatic hydrocarbon groups, aromatic cyclic groups, or aliphatic heterocyclic groups that may have substituents, and more preferably aliphatic hydrocarbon groups or aromatic cyclic groups that may have substituents.

[0241] R X1 ~R X5 The definitions and preferred methods of aliphatic hydrocarbon groups, aromatic cyclic groups, and aliphatic heterocyclic groups that can have substituents, and as if C A ~C D If at least one of the substituents is present, then the substituents exemplified are the same as those of the substituents.

[0242] R X1 ~R X5 The substituents indicated preferably do not contain azo groups or -NR groups. N 2. Any of the bases represented by equation (N) and -CH=A.

[0243] In equations (2-1) to (2-3), (3-1) to (3-4), and (4-1) to (4-2), Z independently represents -CR. Z = or nitrogen atom.

[0244] As Z, -CR is preferred. Z =.

[0245] R Z Indicates a hydrogen atom or does not contain an azo group, -NR N 2. The base represented by formula (N) and any of the substituents in -CH=A.

[0246] Through R Z By excluding the aforementioned specified groups, this invention effectively suppresses charge trapping and aggregation of specific compounds within the photoelectric conversion film, demonstrating superior performance. Regarding the absence of azo groups and -NR groups... N 2. The meaning of any of the bases represented by equation (N) and -CH=A is as described above.

[0247] R Z The substituents represented, for example, include those exemplified in the above-described substituent W that do not contain an azo group or -NR. N 2. From the viewpoint of better performance of the present invention, the base represented by formula (N) and any of the bases in -CH=A are preferably halogen atoms or -SiR. Si3. The substituent may be an aliphatic hydrocarbon group, an aromatic cyclic group, an aliphatic heterocyclic group, a cyano group, an acyl group, an alkoxy group, or an aryloxy group, preferably a halogen atom, -SiR. Si 3. It may be an aliphatic hydrocarbon group with substituents, an aromatic cyclic group with substituents, or an aliphatic heterocyclic group with substituents, and is more preferably -SiR. Si 3. It can be an aliphatic hydrocarbon group or an aromatic cyclic group that can have substituents.

[0248] As R Z The preferred manner of each substituent exemplified by the substituents and as if C A ~C D If at least one of the substituents is present, then the substituents exemplified are the same as those of the substituents.

[0249] In equations (2-1) to (2-3), (3-1) to (3-4), and (4-1) to (4-2), *, *1, and *2 represent the bonding positions.

[0250] Among them, C B The ring represented by the group consisting of equations (3-1), (3-2), (3-3), and (3-4) has two *1 bonding positions with C. A The ring and C are represented C The ring fusion of one of the rings is represented by two * 2 bonding sites with C. A The ring and C are represented C The rings of the other rings represented are fused. Furthermore, C C The ring represented by the group consisting of equations (3-1), (3-2), (3-3), and (3-4) has two *1 bonding positions with C. B The ring and C are represented D The ring fusion of one of the rings is represented by two * 2 bonding sites with C. B The ring and C are represented D The rings of the other rings represented are fused.

[0251] In equation (3-4), Y represents an oxygen atom, a sulfur atom, or -NR. Y1 - As for Y, from the viewpoint of achieving better results in this invention, oxygen atoms are preferred.

[0252] R Y1 Represents a hydrogen atom or a substituent. R Y1 The definition and preferred method of the substituent are the same as those of R mentioned above. x1 The substituents represented are the same.

[0253] In equations (4-1) to (4-2), A represents the basis represented by equation (A-1). The basis represented by equation (A-1) will be described later.

[0254] From the viewpoint that the present invention offers superior results, C B and C C At least one of them is preferably the ring represented by equation (3-5).

[0255] [Chemical Formula 4]

[0256]

[0257] In equation (3-5), W represents -NR X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) - R X1 ~R X5 R in equation (3-1) X1 ~R X5 same.

[0258] *1 and *2 indicate the bonding location. Additionally, C... B When the ring is represented by equation (3-5), the two *1 bonding positions are with C. A The ring and C are represented C The ring fusion of one of the rings is represented by two * 2 bonding sites with C. A The ring and C are represented C The rings of the other rings represented are fused. C C When the ring is represented by equation (3-5), the two *1 bonding positions are with C. B The ring and C are represented D The ring fusion of one of the rings is represented by two * 2 bonding sites with C. B The ring and C are represented D The rings of the other rings represented are fused.

[0259] A specific compound satisfies at least one of the following requirements A through D.

[0260] Requirement A: C A The ring represented by equation (2-1) or equation (2-3) above.

[0261] Requirement B: C B and C CAt least one of them is the ring represented by formula (3-1) or the ring represented by formula (3-4) above, and X in the ring represented by formula (3-1) above represents an oxygen atom, a sulfur atom, a selenium atom, or a -SiR atom. X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -.

[0262] Among them, C B and C C Except for the case of the ring represented by the above formula (3-1).

[0263] Requirement C: C B and C C All are rings represented by the above equation (3-1), and C B and C C In one of them, X represents oxygen atom, selenium atom, -NR. X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -.

[0264] Requirement D: C D The ring represented by equation (4-1) above, where X in the ring represented by equation (4-1) above represents an oxygen atom, a sulfur atom, or -NR. X1 -、-CR X4 2- or -C (=CR) X5 2) -.

[0265] A particular compound preferably satisfies requirement B or requirement C, and more preferably satisfies both requirement B or C and requirement D.

[0266] In a specific compound, C B and C C At least one of them is preferably the ring represented by equation (3-5), and R X1 ~R X5 Indicates a substituent.

[0267] From the viewpoint of achieving better results from the present invention, the specific compound is preferably a compound represented by formula (1-1) or formula (1-2).

[0268] [Chemical Formula 5]

[0269]

[0270] In equations (1-1) and (1-2), C A C B C CA, X and Z and C in equation (1) A C B C C A, X and Z are the same.

[0271] W is the same as W in equation (3-5).

[0272] Furthermore, the compound represented by formula (1-1) is the following compound: In formula (1), C B For the ring represented by equation (3-5), C D For the ring represented by equation (4-1), C B and C D Bonded in the bonding direction shown in formula (1-1). Furthermore, the compound represented by formula (1-2) is a compound as follows: In formula (1), C C For the ring represented by equation (3-5), C D For the ring represented by equation (4-1), C C and C D Bonding is performed in the bonding direction shown in equation (1-2).

[0273] From the viewpoint of superior manufacturing suitability, the specific compound is more preferably the compound represented by formula (5).

[0274] [Chemical Formula 6]

[0275]

[0276] In equation (5), X, Z and A are the same as X, Z and A in equation (1).

[0277] W is the same as W in equation (3-5).

[0278] The basis represented by equation (A-1) will be explained in detail below.

[0279] [Chemical Formula 7]

[0280]

[0281] In equation (A-1), C 1 This indicates a ring containing at least two carbon atoms and which may have substituents. The above C... 1 The two carbon atoms contained are the two carbon atoms explicitly stated in formula (A-1).

[0282] The number of carbon atoms in the aforementioned 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 aforementioned ring is the number of two carbon atoms explicitly stated in the formula.

[0283] The aforementioned ring can be any of the aromatic rings or non-aromatic rings.

[0284] The aforementioned ring can be any of a single ring or a multi-ring, preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring. The number of carbon atoms in the aforementioned fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10.

[0285] The aforementioned ring may contain heteroatoms. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, nitrogen, or oxygen atoms being preferred.

[0286] The number of heteroatoms in the above-mentioned ring is preferably 0 to 10, more preferably 0 to 5.

[0287] Comprising the above C 1 In the ring represented, carbon atoms other than the carbon atoms at the bonding positions marked with * in formula (A-1) and the carbon atoms bonded to Q can be replaced by carbonyl carbon (>C=O) or thiocarbonyl carbon (>C=S).

[0288] As mentioned above, C 1 The ring may have substituents, for example, those exemplified in the above substituent W, preferably halogen atoms, alkyl groups, aromatic cycloalkanes, cyano groups or silyl groups, more preferably halogen atoms or alkyl groups.

[0289] The alkyl group can be any of the straight-chain, branched, and cyclic forms, preferably straight-chain.

[0290] The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 3.

[0291] As mentioned above, C 1 The ring represented is preferably a ring used as an acidic nucleus (e.g., an acidic nucleus in anthocyanins, etc.), and the following nuclei can be cited as examples.

[0292] (a) 1,3-dicarbonyl core: for example, 1,3-indanedion core, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione and 1,3-dioxane-4,6-dione, etc.

[0293] (b) Pyrazolinone core: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one and 1-(2-benzothiazole)-3-methyl-2-pyrazolin-5-one, etc.

[0294] (c) Isoxazolinone core: for example, 3-phenyl-2-isooxazolin-5-one and 3-methyl-2-isooxazolin-5-one, etc.

[0295] (d) Oxindole core: for example, 1-alkyl-2,3-dihydro-2-indole, etc.

[0296] (e) 2,4,6-Trioxohexahydropyrimidine nucleus: For example, barbituric acid, 2-thiobarbituric acid and its derivatives. Examples of the above derivatives include, for example, 1-alkyl bodies such as 1-methyl and 1-ethyl, 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, 1,3-diphenyl, 1,3-di(p-chlorophenyl) and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1-aryl bodies such as 1-ethyl-3-phenyl and 1,3-diheteroaryl bodies such as 1,3-di(2-pyridyl).

[0297] (f) 2-Thio-2,4-thiazolidinedione core: For example, ragumine and its derivatives. Examples of the above derivatives include 3-alkyl ragumine such as 3-methyl ragumine, 3-ethyl ragumine and 3-allyl ragumine, 3-aryl ragumine such as 3-phenyl ragumine, and 3-heteroaryl ragumine such as 3-(2-pyridyl) ragumine.

[0298] (g) 2-Thio-2,4-oxazolidinedione core (2-Thio-2,4-(3H,5H)-oxazolidinedione core): for example, 3-ethyl-2-thio-2,4-oxazolidinedione, etc.

[0299] (h) Thianaphthenone core: for example, 3(2H)-thiaphthenone-1,1-dioxide, etc.

[0300] (i) 2-Thio-2,5-thiazolidinedione core: for example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc.

[0301] (j) 2,4-Thiazolidinedione core: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione and 3-phenyl-2,4-thiazolidinedione, etc.

[0302] (k) Thiazolin-4-one core: for example, 4-thiazolinone and 2-ethyl-4-thiazolinone, etc.

[0303] (l) 2,4-Imidazolidinedione (hydantoin) core: for example, 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione, etc.

[0304] (m) 2-Thio-2,4-imidazolidinedione (2-thiohydantoin) core: for example, 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione, etc.

[0305] (n) Imidazolin-5-one core: for example, 2-propylmercapto-2-imidazolin-5-one, etc.

[0306] (o) 3,5-pyrazolidinedione core: for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione, etc.

[0307] (p) Benzothiophene-3(2H)-one core: for example, benzothiophene-3(2H)-one, oxobenzothiophene-3(2H)-one and dioxobenzothiophene-3(2H)-one, etc.

[0308] (q) Indanone core: for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone and 3,3-dimethyl-1-indanone, etc.

[0309] (r) Benzofuran-3-(2H)-one core: for example, benzofuran-3-(2H)-one, etc.

[0310] (s) 2,2-dihydro-1,3-dione nucleus, etc.

[0311] In formula (A-1), Q represents oxygen atom, sulfur atom, and =NR Q1 or =CR Q2 R Q3 .

[0312] From the viewpoint of achieving better results in this invention, Q is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

[0313] R Q1 This represents a hydrogen atom or a substituent. Examples of substituents include those exemplified in the above description of substituent W.

[0314] R Q2 and R Q3 Representing cyano and -SO2R independently, respectively. Q4 -COOR Q5 or -COR Q6 .

[0315] R Q4 ~R Q6 Each can be independently represented as an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, or an aliphatic heterocyclic group that may have substituents.

[0316] Regarding the definition of aliphatic hydrocarbon groups, as mentioned above, aliphatic hydrocarbon groups with 1 to 3 carbon atoms are preferred.

[0317] Regarding the definition of aromatic cyclic groups, as described above, they are preferably aromatic hydrocarbon groups, and more preferably phenyl groups.

[0318] Regarding the definition of aliphatic heterocyclic groups, as described above, the heteroatoms present in the aforementioned aliphatic heterocyclic groups are preferably sulfur atoms, oxygen atoms, or nitrogen atoms.

[0319] As R Q4 ~R Q6 The substituents that each base may have are exemplified by the substituents shown in the above-mentioned substituent W.

[0320] * indicates the bonding location.

[0321] From the viewpoint of achieving better results in this invention, the basis represented by formula (A-1) is preferably the basis represented by formula (A-2).

[0322] [Chemical Formula 8]

[0323]

[0324] In equation (A-2), C 2 This indicates a ring containing at least 3 carbon atoms and which may have substituents.

[0325] The above C 2 The three carbon atoms contained are the three carbon atoms explicitly stated in formula (A-2).

[0326] The number of carbon atoms in the aforementioned 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 aforementioned ring is the number of 3 carbon atoms explicitly stated in the formula.

[0327] The aforementioned ring can be any of the aromatic rings or non-aromatic rings.

[0328] The aforementioned ring can be any of a single ring or a multi-ring, preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring. The number of carbon atoms in the aforementioned fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10.

[0329] The aforementioned ring may contain heteroatoms. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, nitrogen, or oxygen atoms being preferred.

[0330] The number of heteroatoms in the aforementioned ring is preferably 0 to 10, more preferably 0 to 5.

[0331] Comprising the above C 2 The carbon atoms in the ring represented, except for the carbon atoms at the bonding positions marked with * in formula (A-2) and those bonded to Q. 2 and Q 3Carbon atoms other than the bonded carbon atoms can be replaced by carbonyl carbon (>C=O) or thiocarbonyl carbon (>C=S).

[0332] The preferred manner in which the substituents that the above-mentioned ring may have are the same as those of the above-mentioned ring C. 1 They can have the same substituents.

[0333] In equation (A-2), Q 2 and Q 3 Each of the following can be used independently to represent an oxygen atom, a sulfur atom, and =NR. Q1 or =CR Q2 R Q3 Regarding R Q1 R Q2 and R Q3 As mentioned above.

[0334] From the viewpoint that the present invention offers superior performance, Q 2 and Q 3 Preferably, it contains oxygen atoms or sulfur atoms, and more preferably oxygen atoms.

[0335] From the viewpoint of achieving better results in this invention, the basis represented by formula (A-1) is preferably the basis represented by formula (C-1) or the basis represented by formula (C-2).

[0336] [Chemical Formula 9]

[0337]

[0338] In equation (C-1), X c1 and X c2 Each of the following can be used independently to represent an oxygen atom, a sulfur atom, and =NR. Q1 or =CR Q2 R Q3 Regarding R Q1 R Q2 and R Q3 As mentioned above.

[0339] From the viewpoint that the present invention offers superior performance, X c1 and X c2 Preferably, it contains oxygen atoms or sulfur atoms, and more preferably oxygen atoms.

[0340] C 3 This indicates that an aromatic ring can have substituents.

[0341] The aromatic rings mentioned above can be either monocyclic or polycyclic.

[0342] The number of ring-member atoms in the aforementioned aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 5 to 8. The number of ring-member atoms in the aforementioned aromatic ring includes the number of two carbon atoms explicitly stated in the formula.

[0343] Furthermore, the aromatic ring can be any of the aromatic hydrocarbon rings and aromatic heterocycles, preferably an aromatic hydrocarbon ring.

[0344] As mentioned above, C 3 The aromatic ring represented, as described above, is preferably a benzene ring, a naphthyl ring, an anthracene ring, a pyrene ring, a thiophene ring, a furan ring, a thiazole ring, an oxazole ring, a pyridine ring, a thiophene ring, a benzothiophene ring, a benzofuran ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring, more preferably a benzene ring, a naphthyl ring, or a thiophene ring, and even more preferably a benzene ring.

[0345] Substituents that can be present in the above-mentioned aromatic ring include, for example, the groups exemplified in the above-mentioned substituent W, preferably alkyl or halogen atoms.

[0346] The number of substituents that the aromatic ring may have is not particularly limited, but is preferably 0 to 8, more preferably 0 to 4.

[0347] In equation (C-2), X c3 ~X c5 Each of the following can be used independently to represent an oxygen atom, a sulfur atom, and =NR. Q1 or =CR Q2 R Q3 Regarding R Q1 R Q2 and R Q3 As mentioned above.

[0348] From the viewpoint that the present invention offers superior performance, X c3 ~X c5 Preferably, it contains oxygen atoms or sulfur atoms, and more preferably oxygen atoms.

[0349] Z c1 and Z c2 Represent -NR independently c1 -or-CR c2 2- From the viewpoint of achieving better results in this invention, -NR is preferred. c1 -

[0350] R C1 and R C2 Each can be used to represent a hydrogen atom or a substituent independently.

[0351] As the above-mentioned substituent, examples include the groups exemplified in the above-mentioned substituent W, preferably alkyl or aryl, more preferably alkyl.

[0352] The alkyl group can be any of the following: straight-chain, branched, or cyclic, preferably straight-chain. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2.

[0353] The aryl group described above can be any of a monocyclic or polycyclic ring, preferably phenyl. The aryl group may further have substituents, such as those exemplified in the substituent W example.

[0354] Specific examples of particular compounds are shown below, but the invention is not limited to these. In the following chemical formulas, Me represents a methyl group.

[0355] [Chemical Formula 10]

[0356]

[0357] [Chemical Formula 11]

[0358]

[0359] [Chemical Formula 12]

[0360]

[0361] [Chemical Formula 13]

[0362]

[0363] A in the specific compounds illustrated above represents any of the following groups.

[0364] [Chemical Formula 14]

[0365]

[0366] [Chemical Formula 15]

[0367]

[0368] [Chemical Formula 16]

[0369]

[0370] The molecular weight of the specific compound is preferably 400 to 1200, more preferably 400 to 1000, and even more preferably 400 to 900.

[0371] It is speculated that when the molecular weight is as described above, the sublimation temperature of a particular compound becomes lower and its manufacturing suitability is excellent.

[0372] From the viewpoint of stability when used as a p-type organic semiconductor and energy level matching with n-type organic semiconductors, the ionization potential of a particular compound in a single film is preferably -5.0 to -6.5 eV.

[0373] The maximum absorption wavelength of a particular compound is preferably in the range of 400 to 650 nm, and more preferably in the range of 400 to 600 nm.

[0374] The aforementioned maximum absorption wavelength is obtained by adjusting the absorption spectrum of a specific compound to a concentration with an absorbance of approximately 0.5 to 1.0 and measuring it in solution (solvent: chloroform). When the specific compound is insoluble in chloroform, the following value is used as the maximum absorption wavelength of the specific compound; this value is obtained by measuring the specific compound using a film formed by vapor deposition.

[0375] Certain compounds are particularly useful as materials for photoelectric conversion films used in imaging elements, light sensors, or photovoltaic cells. These compounds often function as pigments within photoelectric conversion films. Furthermore, they can also be used as coloring materials, liquid crystal materials, organic semiconductor materials, charge transport materials, medical materials, and fluorescent diagnostic materials.

[0376] Specific compounds can be purified as needed.

[0377] Examples of purification methods for specific compounds include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, purification using adsorbents such as activated carbon, and recrystallization purification.

[0378] The content of a specific compound in the photoelectric conversion film (= film thickness of the specific compound in monolayer conversion / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 5 to 75% by volume, more preferably 10 to 50% by volume, and even more preferably 15 to 40% by volume.

[0379] A specific compound may be used in only one form or in two or more forms. When two or more are used, the total amount of these compounds is preferably within the range described above.

[0380] <n-type organic semiconductor>

[0381] In addition to the specific compounds mentioned above, the photoelectric conversion film preferably contains an n-type organic semiconductor.

[0382] n-type organic semiconductors are compounds that are different from the specific compounds mentioned above.

[0383] n-type organic semiconductors are acceptor organic semiconductor materials (compounds), referring to organic compounds that readily accept electrons. In other words, an n-type organic semiconductor is an organic compound with the greater electron affinity when two organic compounds are brought into contact. Therefore, as an acceptor organic semiconductor, any organic compound with electron affinity can be used.

[0384] Examples of n-type organic semiconductors include, for example, fullerenes selected from the group consisting of fullerenes and their derivatives; condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, condensed tetraphenyl derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); heterocyclic compounds having at least one 5- to 7-membered ring selected from the group consisting of nitrogen, oxygen, and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, borazine, isoquinoline, pteridine, acridine, phenazine, phenazine, tetrazolium, pyrazole, imidazole, and thiazole); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silicon-based compounds; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid diimide derivatives; anthraquinone dimethyl ester derivatives; and diphenylquinone. quinone derivatives; bathocuproine, bathophenanthroline and their derivatives; triazole compounds; distyrylarylene derivatives; metal complexes having nitrogen-containing heterocyclic compounds as ligands; silicone heterocyclopentadiene compounds; 3,4,9,10-perylenetetracarboxylic acid dianhydride; 3,4,9,10-perylenetetracarboxylic acid diimide derivatives; compounds described in paragraphs

[0056] to

[0057] of Japanese Patent Application Publication No. 2006-100767.

[0385] As an n-type organic semiconductor (compound), it is preferably a fullerene selected from the group consisting of fullerenes and their derivatives.

[0386] As a fullerene, for example, fullerene C 60 Fullerene C 70 Fullerene C 76 Fullerene C 78 Fullerene C 80 Fullerene C 82 Fullerene C 84 Fullerene C 90 Fullerene C 96 Fullerene C 240 Fullerene C 540 and mixed fullerenes.

[0387] Examples of fullerene derivatives include compounds in which substituents have been added to the fullerene. The substituents are preferably alkyl, aryl, or heterocyclic groups. The compounds described in Japanese Patent Application Publication No. 2007-123707 are preferred as fullerene derivatives.

[0388] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0389] The maximum absorption wavelength of n-type organic semiconductors is preferably below 400 nm or in the range of 400–600 nm.

[0390] The photoelectric conversion film preferably has a bulk heterostructure formed in a state where a specific compound and an n-type organic semiconductor are mixed. The bulk heterostructure is a layer in which a specific compound and an n-type organic semiconductor are mixed and dispersed within the photoelectric conversion film. The photoelectric conversion film having a bulk heterostructure can also be formed by either a wet process or a dry process. Furthermore, the bulk heterostructure is described in detail in paragraphs

[0013] to

[0014] of Japanese Patent Application Publication No. 2005-303266.

[0391] The difference in electron affinity between a specific compound and an n-type organic semiconductor is preferably 0.1 eV or higher.

[0392] n-type organic semiconductors can be used alone or in combination with two or more types.

[0393] When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (the thickness of the n-type organic semiconductor as a single layer / the thickness of the photoelectric conversion film × 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 20 to 50% by volume.

[0394] When the n-type organic semiconductor contains fullerenes, the content of fullerenes relative to the total content of the n-type organic semiconductors (film thickness of fullerenes in monolayer conversion / total film thickness of each n-type organic semiconductor in monolayer conversion × 100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume. One type of fullerene may be used alone, or two or more types may be used.

[0395] From the viewpoint 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 of the specific compound in monolayer form / (film thickness of the specific compound in monolayer form + film thickness of the n-type organic semiconductor in monolayer form) × 100) is preferably 20 to 80% by volume, more preferably 40 to 80% by volume.

[0396] When the photoelectric conversion film contains both n-type and p-type organic semiconductors, the content of the specific compound (film thickness of the specific compound in monolayer form / (film thickness of the specific compound in monolayer form + film thickness of the n-type organic semiconductor in monolayer form + film thickness of the p-type organic semiconductor in monolayer form) × 100) is preferably 10 to 75% by volume, more preferably 15 to 50% by volume.

[0397] Furthermore, the photoelectric conversion film is preferably composed of a specific compound, an n-type organic semiconductor, and a p-type organic semiconductor as needed. The total content of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor is substantially 90-100% by volume relative to the total mass of the photoelectric conversion film, preferably 95-100% by volume, and more preferably 99-100% by volume.

[0398] <p-type organic semiconductor>

[0399] In addition to the specific compounds mentioned above, the photoelectric conversion film preferably contains a p-type organic semiconductor.

[0400] p-type organic semiconductors are compounds that are different from the specific compounds mentioned above.

[0401] p-type organic semiconductors are donor organic semiconductor materials (compounds), referring to organic compounds that readily donate electrons. In other words, a p-type organic semiconductor is an organic compound with the lower ionization potential when two organic compounds are brought into contact for use.

[0402] p-type organic semiconductors can be used alone or in combination with two or more types.

[0403] Examples of p-type organic semiconductors include triarylamine compounds (e.g., N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), compounds described in paragraphs

[0128] to

[0148] of Japanese Patent Application Publication No. 2011-228614, compounds described in paragraphs

[0052] to

[0063] of Japanese Patent Application Publication No. 2011-176259, compounds described in paragraphs

[0119] to

[0158] of Japanese Patent Application Publication No. 2011-225544, and Japanese Patent Application Publication No. 2015-153910). Compounds described in paragraphs

[0044] to

[0051] of this publication and compounds described in paragraphs

[0086] to

[0090] of Japanese Patent Application Publication No. 2012-094660, etc.), pyrazolene compounds, styreneamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (e.g., thiophene-thiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithiophene-thiophene derivatives, [1]benzothiophene-[3,2-b][1]benzothiophene (BTBT) derivatives, thiophene-[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivatives, and compounds described in paragraphs

[0031] to

[0036] of Japanese Patent Application Publication No. 2018-014474). The compounds described in paragraphs

[0043] to

[0045] of WO2016 / 194630, the compounds described in paragraphs

[0025] to

[0037] and

[0099] to

[0109] of WO2017 / 159684, the compounds described in paragraphs

[0029] to

[0034] of Japanese Patent Application Publication No. 2017-076766, the compounds described in paragraphs

[0015] to

[0025] of WO2018 / 207722, the compounds described in paragraphs

[0045] to

[0053] of Japanese Patent Application Publication No. 2019-054228, and the compounds described in paragraphs

[0045] to

[0055] of WO2019 / 058995. The compounds described herein, the compounds described in paragraphs

[0063] to

[0089] of Japanese Patent Application Publication No. 2019 / 081416, the compounds described in paragraphs

[0033] to

[0036] of Japanese Patent Application Publication No. 2019-080052, the compounds described in paragraphs

[0044] to

[0054] of Japanese Patent Application Publication No. 2019 / 054125, the compounds described in paragraphs

[0041] to

[0046] of Japanese Patent Application Publication No. 2019 / 093188, the compounds described in paragraphs

[0034] to

[0037] of Japanese Patent Application Publication No. 2019-050398, and the compounds described in paragraphs

[0033] to

[0036] of Japanese Patent Application Publication No. 2018-206878.The compounds described in paragraph

[0038] of Japanese Patent Application Publication No. 2018-190755, the compounds described in paragraphs

[0019] to

[0021] of Japanese Patent Application Publication No. 2018-026559, the compounds described in paragraphs

[0031] to

[0056] of Japanese Patent Application Publication No. 2018-170487, the compounds described in paragraphs

[0036] to

[0041] of Japanese Patent Application Publication No. 2018-078270, and the compounds described in Japanese Patent Application Publication No. 2018-16620 The compounds described in paragraphs

[0055] to

[0082] of Japanese Patent Application Publication No. 0, the compounds described in paragraphs

[0041] to

[0050] of Japanese Patent Application Publication No. 2018-113425, the compounds described in paragraphs

[0044] to

[0048] of Japanese Patent Application Publication No. 2018-085430, the compounds described in paragraphs

[0041] to

[0045] of Japanese Patent Application Publication No. 2018-056546, and the compounds described in paragraphs

[0055] to

[0048] of Japanese Patent Application Publication No. 2018-046267. Compounds described in paragraphs

[42] to

[0049] , compounds described in paragraphs

[0031] to

[0036] of Japanese Patent Application Publication No. 2018-014474, compounds described in paragraphs

[0036] to

[0046] of WO2018 / 016465, and compounds described in paragraphs

[0045] to

[0048] of Japanese Patent Application Publication No. 2020-010024, etc.), anthocyanin compounds, oxacyanine compounds, polyamine compounds, indole compounds, pyrrole compounds, etc. Compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, condensed tetraphenylene derivatives, condensed pentaphenylene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives, etc.), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylene alkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes with nitrogen-containing heterocyclic compounds as ligands.

[0404] Furthermore, examples of p-type organic semiconductors include benzoxazole compounds (e.g., the compounds described in Figures 3-7 of Japanese Patent Application Publication No. 2022-123944) and dicarbazole compounds (e.g., those described in Japanese Patent Application Publication No. 2022-122839). Figure 2 Compounds described in paragraphs 5-5), benzoquinazoline compounds (e.g., compounds described in paragraphs

[0053] -

[0056] of Japanese Patent Application Publication No. 2022-120323), azazine compounds (e.g., compounds described in paragraphs

[0041] -

[0042] of Japanese Patent Application Publication No. 2022-120273), and compounds described in Japanese Patent Application Publication No. 2022-115832. Figure 2-1The compounds described in 0, indole-parabens (e.g., the compounds described in paragraphs

[0065] to

[0072] of Japanese Patent Application Publication No. 2022-108268), and indole-carbazole compounds (e.g., the compounds described in paragraphs

[0052] to

[0073] of Japanese Patent Application Publication No. 2023-005703 and paragraph

[0028] of Japanese Patent Application Publication No. 2022-100258). Compounds), tricarbazolylphenyl compounds (e.g., compounds described in paragraphs

[0038] to

[0040] of Japanese Patent Application Publication No. 2022-181226), compounds described in paragraphs

[0070] to

[0082] of Japanese Patent Application Publication No. 2022-027575, and compounds described in paragraphs

[0051] to

[0064] of Japanese Patent Application Publication No. 2021-163968, etc.

[0405] As a p-type organic semiconductor, for example, compounds with an ionization potential lower than that of an n-type organic semiconductor can be used. As long as this condition is met, organic pigments, exemplified as n-type organic semiconductors, can be used.

[0406] The following are examples of compounds that can be used as p-type organic semiconductor compounds.

[0407] [Chemical Formula 17]

[0408]

[0409] [Chemical Formula 18]

[0410]

[0411] [Chemical Formula 19]

[0412]

[0413] [Chemical Formula 20]

[0414]

[0415] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or higher.

[0416] p-type organic semiconductor materials can be used alone or in combination with two or more types.

[0417] When the photoelectric conversion film contains p-type organic semiconductors, the content of p-type organic semiconductors in the photoelectric conversion film (film thickness of p-type organic semiconductors in monolayer conversion / film thickness of photoelectric conversion film × 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 25 to 50% by volume.

[0418] Photoelectric conversion films containing specific compounds are non-luminescent films, possessing characteristics distinct from organic light-emitting diodes (OLEDs). A non-luminescent film is defined as a film with a luminous quantum efficiency of less than 1%, preferably less than 0.5%, more preferably less than 0.1%. Cases with a lower limit of 0% or higher are more common.

[0419] <pigment>

[0420] In addition to the specific compounds mentioned above, the photoelectric conversion film preferably contains pigments.

[0421] The pigment is a compound that is different from the specific compound mentioned above.

[0422] Organic pigments are preferred as pigments.

[0423] Examples of organic pigments include, for example, anthocyanins, styrene pigments, hemicyanins, partial anthocyanins (including zero-methylene partial anthocyanins (simple partial anthocyanins)), rhodane anthocyanins, aloporapis, oxacyanins, hemicyanins, squaric acid cyanins, ketone pigments, nitrogen-containing methylene pigments, coumarin pigments, aryl pigments, anthraquinone pigments, triphenylmethane pigments, azo pigments, methylene azo pigments, metallocene pigments, fluorenone pigments, benzoic acid anhydride pigments, perylene pigments, phenazine pigments, phenothiazine pigments, quinone pigments, diphenylmethane pigments, polyene pigments, acridine pigments, and acridine ketone pigments. The pigments include: phthalocyanine pigments, diphenylamine pigments, quinoline yellow pigments, phenoxazine pigments, perylene pigments, dioxane pigments, porphyrin pigments, chlorophyll pigments, phthalocyanine pigments, subphthalocyanine pigments, metal complex pigments, imidazoline quinoxaline pigments described in WO2020 / 013246, WO2022 / 168856, Japanese Patent Application Publication Nos. 2023-010305 and 2023-010299, as well as acceptor-donor-acceptor type pigments formed by the bonding of two acidic nuclei with a donor and donor-acceptor-donor type pigments, etc.

[0424] As organic pigments, anthocyanins, imidazoquinoxaline pigments, and receptor-donor-receptor type pigments are preferred.

[0425] The maximum absorption wavelength of the pigment is preferably in the visible light region, more preferably in the wavelength range of 400 to 650 nm, and even more preferably in the wavelength range of 450 to 650 nm.

[0426] Pigments can be used alone or in combination with two or more.

[0427] The pigment content in the photoelectric conversion film is preferably 5 to 75% by volume, more preferably 5 to 60% by volume, and even more preferably 5 to 50% by volume, relative to the total content of the specific compound and the pigment (= (film thickness of pigment in monolayer conversion / (film thickness of specific compound in monolayer conversion + film thickness of pigment in monolayer conversion) × 100)).

[0428] <Film Formation Method>

[0429] For example, a dry film formation method can be used as a method for forming the aforementioned photoelectric conversion film.

[0430] Examples of dry film deposition methods include physical vapor deposition (PVD) methods such as evaporation (especially vacuum evaporation), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization. Vacuum evaporation is preferred. When forming a photoelectric conversion film by vacuum evaporation, manufacturing conditions such as vacuum level and evaporation temperature can be set using conventional methods.

[0431] The thickness of the photoelectric conversion film is preferably 10-1000 nm, more preferably 50-800 nm, and even more preferably 50-500 nm.

[0432] 〔electrode〕

[0433] The photoelectric conversion element preferably has electrodes.

[0434] The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of conductive materials. Examples of conductive materials include metals, alloys, metal oxides, conductive compounds, and mixtures thereof.

[0435] Since light is incident from the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected. Being transparent to the light to be detected means that the average transmittance of the light in the wavelength range to be detected is 50% or more, preferably 60% or more, and more preferably 70% or more. Specifically, it is preferably transparent to light with wavelengths of 400 to 800 nm.

[0436] The aforementioned transmittance can be measured using a spectrophotometer.

[0437] Examples of materials constituting the upper electrode 15 include conductive metal oxides such as tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO): doped with antimony or fluorine; thin films of metals 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, as well as nanomaterials such as carbon nanotubes and graphene. From the viewpoint of high conductivity and transparency, conductive metal oxides are preferred.

[0438] Typically, if the conductive film is formed to be thinner than a certain range, the resistance value often increases sharply. In solid-state imaging elements assembled with the photoelectric conversion element of this embodiment, the sheet resistance can be 100 to 10000 Ω / □, and there is a high degree of freedom in the range of film thickness that can be thinned.

[0439] Furthermore, the thinner the upper electrode (transparent conductive film) 15, the less light is absorbed, and the higher the transmittance is generally. Increased transmittance leads to increased light absorption in the photoelectric conversion film and increases the photoelectric conversion energy, which is therefore preferable. Considering the suppression of leakage current, the increase in film resistance, and the increase in transmittance associated with thinning, the thickness of the upper electrode 15 is preferably 5–100 nm, more preferably 5–20 nm.

[0440] The lower electrode 11 may be transparent or opaque and reflect light, depending on the application. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO), zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) doped with antimony or fluorine; 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 with conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and graphene.

[0441] The method for forming electrodes can be appropriately selected depending on the electrode material. Specifically, examples include wet methods such as printing and coating; physical methods such as vacuum evaporation, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD.

[0442] When the electrode material is ITO, methods such as electron beam method, sputtering method, resistance heating evaporation method, chemical reaction method (sol-gel method, etc.) and coating of indium tin oxide dispersions can be cited.

[0443] [Charge blocking membrane: electron blocking membrane, hole blocking membrane]

[0444] The photoelectric conversion element preferably has one or more intermediate layers other than the photoelectric conversion film between the conductive film and the transparent conductive film.

[0445] As an intermediate layer, a charge-blocking film can be cited as an example. When a photoelectric conversion element has this film, the characteristics of the obtained photoelectric conversion element (quantum efficiency, response speed, etc.) are superior. As charge-blocking films, electron-blocking films and hole-blocking films can be cited as examples.

[0446] <Electron blocking membrane>

[0447] The electron blocking film is a donor organic semiconductor material (compound) that can use the above-mentioned p-type organic semiconductor.

[0448] Furthermore, polymer materials can also be used as electron blocking films.

[0449] Examples of polymer materials include, for example, polyphenylene oxide, fluorene, carbazole, indole, pyrene, pyrrole, methylpyridine, thiophene, acetylene and diacetylene polymers and their derivatives.

[0450] In addition, electron blocking films can be composed of multiple films.

[0451] Electron blocking films can be made of inorganic materials. Generally, because inorganic materials have a higher dielectric constant than organic materials, a higher voltage can be applied to the photoelectric conversion film when inorganic materials are used in electron blocking films, resulting in higher quantum efficiency. Examples of inorganic materials that can serve as electron blocking films include calcium oxide, chromium oxide, copper chromium oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, copper gallium oxide, copper strontium oxide, niobium oxide, molybdenum oxide, copper indium oxide, silver indium oxide, and iridium oxide.

[0452] <Cavity blocking membrane>

[0453] Hole blocking membranes are acceptor organic semiconductor materials (compounds) that can utilize the aforementioned n-type organic semiconductors.

[0454] In addition, hole-blocking membranes can be composed of multiple membranes.

[0455] Examples of methods for manufacturing charge-blocking films include dry film deposition and wet film deposition. Examples of dry film deposition methods include vapor deposition and sputtering. Vapor deposition can be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition methods such as vacuum vapor deposition being preferred. Examples of wet film deposition methods include inkjet printing, spraying, nozzle printing, spin coating, dip coating, casting, molding, roller coating, bar coating, and gravure coating; from the viewpoint of high-precision patterning, inkjet printing is preferred.

[0456] The thickness of the charge blocking film (electron blocking film and hole blocking film) is preferably 3-200 nm, more preferably 5-100 nm, and even more preferably 5-30 nm.

[0457] [Substrate]

[0458] Photoelectric conversion elements can also have a substrate.

[0459] Examples of substrates include semiconductor substrates, glass substrates, and plastic substrates.

[0460] In addition, the substrate is usually positioned such that a conductive film, a photoelectric conversion film, and a transparent conductive film are stacked sequentially on the substrate.

[0461] [Sealing layer]

[0462] Photoelectric conversion elements can also have a sealing layer.

[0463] Photoelectric conversion materials can sometimes experience significant performance degradation due to the presence of degrading factors such as water molecules. Therefore, the photoelectric conversion film can be completely sealed by covering it with a dense sealing layer of water-impermeable metal oxides, metal nitrides, or metal nitride ceramics or diamond-like carbon (DLC) to prevent such degradation.

[0464] In addition, as a sealing layer, for example, the sealing layer described in paragraphs

[0210] to

[0215] of Japanese Patent Application Publication No. 2011-082508 can be cited, and these contents are incorporated into this specification.

[0465] [Manufacturing Method of Photoelectric Conversion Components]

[0466] As a method for manufacturing photoelectric conversion elements, well-known manufacturing methods can be cited.

[0467] Specifically, for example, a method for manufacturing a photoelectric conversion element may include the following steps: forming a conductive film on a substrate; forming a photoelectric conversion film; and forming a transparent conductive film.

[0468] The manufacturing method of the photoelectric conversion element may include other processes besides those mentioned above (e.g., the process of forming a charge blocking film and the process of forming a sealing layer).

[0469] The method for forming each layer is as described above.

[0470] [Camera Components]

[0471] Its use as a photoelectric conversion element is, for example, in the case of a camera element.

[0472] A camera element is a component that converts the light information of an image into electrical signals. It typically refers to a matrix of multiple photoelectric conversion elements arranged on the same plane. Each photoelectric conversion element (pixel) converts the light signal into an electrical signal and outputs the electrical signal sequentially to the outside of the camera element for each pixel. Therefore, each pixel consists of one or more photoelectric conversion elements and one or more transistors.

[0473] There are no particular limitations on the manufacturing method of the camera element; examples include the aforementioned process for manufacturing photoelectric conversion elements.

[0474] [Optical Sensor]

[0475] Other applications of the photoelectric conversion element include, for example, photovoltaic cells and optical sensors. The photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element can be used alone, or it can be used as a line sensor with the photoelectric conversion element arranged in a straight line, or as a two-dimensional sensor arranged on a plane.

[0476] [Compound]

[0477] This invention also includes the invention of specific compounds.

[0478] Example

[0479] The present invention will now be described in further detail with reference to embodiments.

[0480] The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0481] [Compounds used in photoelectric conversion films]

[0482] The following shows the materials used in photoelectric conversion films.

[0483] [Synthesis of compound 3-1]

[0484] Compound 3-1 was synthesized according to the following scheme.

[0485] [Chemical Formula 21]

[0486]

[0487] <Synthesis of Compound 3-1-1>

[0488] After purging the container containing 2'-bromoacetophenone (3.0 g, 15.1 mmol), 2-tributyltin-thiophene[2,3-b]thiophene (7.1 g, 16.6 mmol), and DMF (N,N-dimethylformamide, 45 mL) with nitrogen, tetrakis(triphenylphosphine)palladium(0) (523 mg, 0.45 mmol) was added, and the mixture was stirred at 100 °C for 7 hours. The reaction mixture was allowed to cool naturally to room temperature and then concentrated under reduced pressure. The crude product was purified by silica gel chromatography (eluent (v / v): hexane / ethyl acetate = 7 / 3) to obtain compound 3-1-1 (3.55 g, 92%).

[0489] <Synthesis of Compound 3-1-2>

[0490] Compound 3-1-1 (3.6 g, 13.8 mmol), a 0.6 M lanthanum(III) bis(lithium chloride) complex solution in 0.6 min THF (30 mL, 15.2 mmol), and THF (tetrahydrofuran, 53 mL) were mixed and stirred in an ice bath. Then, 1.0 M magnesium ethyl bromide solution in THF (21 mL, 20.6 mmol) was slowly added dropwise, and the mixture was stirred in an ice bath for 30 min. After slowly adding saturated ammonium chloride aqueous solution (50 mL), ethyl acetate (30 mL) and 1 N hydrochloric acid (50 mL) were added, and the mixture was stirred at room temperature for 10 min. After removing the aqueous layer using a separatory funnel, the resulting organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel chromatography (eluent: hexane / ethyl acetate = 3 / 1) to obtain compound (3-1-2) (3.5 g, 88%).

[0491] <Synthesis of Compound 3-1-3>

[0492] Compound 3-1-2 (3.5 g, 12.0 mmol) was mixed with dichloromethane (240 mL) and stirred in an ice bath. Methanesulfonic acid (4.8 mL, 73 mmol) was then added, and the mixture was stirred at room temperature for 1 hour. Water (70 mL) was added to the reaction mixture, and the mixture was stirred at room temperature for 10 minutes. Then, 1 N sodium hydroxide aqueous solution (100 mL) was added, and the mixture was stirred further at room temperature for 1 hour. The mixture was extracted with dichloromethane using a separatory funnel. The resulting organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel chromatography (eluent: hexane / ethyl acetate = 98 / 2) to obtain compound (3-1-3) (2.2 g, 67%).

[0493] <Synthesis of Compound 3-1-4>

[0494] Compound 3-1-3 (2.2 g, 8.1 mmol) and DMF (22 mL) were mixed and stirred at room temperature. Then, (chloromethylene)dimethylammonium chloride (2.1 g, 16.2 mmol) was added, and the mixture was stirred at 60 °C for 3 hours. After cooling to room temperature, 1 N sodium hydroxide aqueous solution (33 mL) and ice (33 g) were mixed. The reaction mixture was then added dropwise, and the mixture was stirred at room temperature for 30 minutes. The precipitate was then filtered off. The crude product was purified by silica gel chromatography (eluent (v / v): toluene / ethyl acetate = 95 / 5) to obtain compound 3-1-4 (2.1 g, 86%).

[0495] <Synthesis of Compound 3-1>

[0496] Compound 3-1-4 (1.0 g, 3.4 mmol), 1,3-dimethylbarbituric acid (630 mg, 4.0 mmol), toluene (30 mL), and piperidine (66 μL, 0.67 mmol) were mixed and stirred at 100 °C for 1 hour. The mixture was then allowed to cool naturally to room temperature and concentrated under reduced pressure. The concentrate was recrystallized from dichloromethane / methanol, and the crude product obtained by filtering the precipitate was purified by sublimation to give compound 3-1 (992 mg, 66%).

[0497] The structure of the obtained compound 3-1 was identified by NMR (Nuclear Magnetic Resonance).

[0498] Compound 3-1: 1H NMR (400MHz, CDCl3); δ=8.77 (1H,s), 8.13 (1H,s), 7.51-7.57 (1H,m), 7.40-7.44 (1H,m), 7.34-7.40 (2H,m), 3.47 (3H,s), 3.44 (3H,s), 2.07-2.30 (2H,m), 1.60 (3H,s), 0.43 (3H,t)

[0499] The compounds used in the photoelectric conversion films, except for compound 3-1, in the various examples and comparative examples were synthesized according to the synthesis method of compound 3-1.

[0500] [Specific compound]

[0501] The following shows specific compounds used in photoelectric conversion films and comparative compounds of comparative examples.

[0502] In addition, compounds 1-1 to 1-5, 2-1 to 2-6, 3-1 to 3-17 and 4-1 to 4-2 are specific compounds, and compounds C-1 to C-8 are comparative compounds.

[0503] [Chemical Formula 22]

[0504]

[0505] [Chemical Formula 23]

[0506]

[0507] [Chemical Formula 24]

[0508]

[0509] [Chemical Formula 25]

[0510]

[0511] [Chemical Formula 26]

[0512]

[0513] [n-type organic semiconductor]

[0514] • C60: Fullerene (C 60 )

[0515] [p-type organic semiconductor]

[0516] [Chemical Formula 27]

[0517]

[0518] [evaluate]

[0519] The following methods were used to evaluate the quantum efficiency, electric field strength dependence of quantum efficiency, response speed, electric field strength dependence of response speed, and fabrication suitability of the photoelectric conversion element when receiving blue-green light (wavelength 460 nm).

[0520] [Fabrication of photoelectric conversion elements]

[0521] It was made using the various ingredients shown above. Figure 2 The photoelectric conversion element is a photoelectric conversion element consisting of a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15.

[0522] Specifically, a lower electrode 11 (thickness: 30 nm) is formed on a glass substrate by sputtering an amorphous ITO film, and a planar electron blocking film 16A (thickness: 30 nm) is formed on the lower electrode 11 by vacuum heating evaporation of a compound (EB-1).

[0523] Next, with the glass substrate at room temperature, the specific compounds or comparative compounds shown in Table 1, and the n-type organic semiconductor (fullerene (C)) were deposited on the electron blocking film 16A by vacuum evaporation. 60 The p-type organic semiconductor (P-1) and the p-type organic semiconductor (P-1) were co-deposited in a manner equivalent to 80 nm in single-layer conversion, thereby forming a film. Thus, a 240 nm photoelectric conversion film 12 with a bulk heterostructure was formed. At this time, the deposition rate of the photoelectric conversion film 12 was set to 1.0 Å / s.

[0524] Subsequently, a hole-blocking film 16B (thickness: 10 nm) was formed by evaporating a compound (EB-2) onto the photoelectric conversion film 12. An upper electrode 15 (transparent conductive film) (thickness: 10 nm) was then formed on the hole-blocking film 16B by sputtering an amorphous ITO film. After forming a SiO film as a sealing layer on the upper electrode 15 by vacuum evaporation, an aluminum oxide (Al2O3) layer was formed on it using ALCVD (Atomic Layer Chemical Vapor Deposition). The resulting laminate was then heated at 150°C for 30 minutes in a glove box to obtain the photoelectric conversion element.

[0525] [Chemical Formula 28]

[0526]

[0527] [Dark Current]

[0528] The dark current of each obtained photoelectric conversion element was measured using the following method.

[0529] A voltage of 2.5 × 10⁻⁶ is applied to the lower and upper electrodes of each photoelectric conversion element. 5 The electric field strength was measured at V / cm, and the current value in the dark chamber (dark current) was also measured. The results confirmed that the dark current is 50 nA / cm in any photoelectric conversion element. 2 The following shows a sufficiently low dark current.

[0530] [Quantum efficiency]

[0531] The quantum efficiency of each photoelectric conversion element when receiving blue-green light was measured using the following method.

[0532] A voltage is applied to each photoelectric conversion element to achieve a voltage of 2.0 × 10⁻⁶. 5 After applying an electric field strength of V / 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 quantum efficiency (relative comparison) was calculated according to equation (S1). The quantum efficiency was evaluated based on the obtained values ​​according to the following evaluation criteria. A quantum efficiency of C or higher is preferred.

[0533] Equation (S1): Quantum efficiency (relative comparison) = (Photovoltaic conversion efficiency of each photoelectric conversion element) / (Photovoltaic conversion efficiency of the photoelectric conversion elements in Examples 1-8)

[0534] A: Quantum efficiency (relative ratio) is above 1.6.

[0535] B: Quantum efficiency (relative ratio) is 1.2 or higher and less than 1.6.

[0536] C: Quantum efficiency (relative ratio) is 0.8 or higher and less than 1.2.

[0537] D: Quantum efficiency (relative ratio) is 0.4 or higher and less than 0.8.

[0538] E: Quantum efficiency (relative ratio) is less than 0.4

[0539] [Electric field strength dependence of quantum efficiency]

[0540] For each photoelectric conversion element, the electric field intensity dependence of the quantum efficiency when receiving blue-green light was evaluated using the following method.

[0541] Using the same procedures as those used for evaluating [quantum efficiency], the electric field strength of 7.0 × 10⁻⁶ was measured. 4 Quantum efficiency (photoelectric conversion efficiency) at V / cm.

[0542] The electric field intensity dependence of the quantum efficiency was calculated according to formula (S2), and the electric field intensity dependence of the quantum efficiency was evaluated according to the following evaluation criteria. In formula (S2), the numerator and denominator are values ​​obtained by measurement for the same photoelectric conversion element in the same embodiment or comparative example. Furthermore, both the numerator and denominator are quantum efficiencies measured at 460 nm. The evaluation of the electric field intensity dependence of the quantum efficiency is preferably B or higher.

[0543] Equation (S2): Electric field strength dependence of quantum efficiency = (Electric field strength dependence of each photoelectric conversion element at an electric field strength of 7.0 × 10⁻⁶) 4 Quantum efficiency at V / cm / (Quantum efficiency of each photoelectric conversion element at an electric field strength of 2.0 × 10⁻⁶ V / cm) 5 Quantum efficiency at V / cm

[0544] A: The electric field strength dependence of quantum efficiency is above 0.85.

[0545] B: The electric field strength dependence of quantum efficiency is greater than 0.80 and less than 0.85.

[0546] C: The electric field strength dependence of quantum efficiency is greater than 0.70 and less than 0.80.

[0547] D: The electric field strength dependence of quantum efficiency is greater than 0.60 and less than 0.70.

[0548] E: The electric field strength dependence of quantum efficiency is less than 0.60.

[0549] [Response speed]

[0550] The response speed of each photoelectric conversion element when receiving blue-green light was evaluated using the following method.

[0551] A voltage was applied to the photoelectric conversion element to achieve a voltage of 2.0 × 10⁻⁶. 5 The electric field strength was measured in V / cm. Then, the LED (light emitting diode) was instantaneously lit and light was irradiated from the upper electrode (transparent conductive film) side. The photocurrent at a wavelength of 460nm was measured using an oscilloscope, and the rise time from 0% signal strength to 97% signal strength was measured. The relative response speed was calculated according to equation (S3). The response speed was evaluated based on the obtained values ​​according to the following evaluation criteria. A response speed evaluation of B or higher is preferred.

[0552] Equation (S3): Relative response speed = (rise time of each photoelectric conversion element) / (rise time of the photoelectric conversion element in Comparative Example 1-1)

[0553] A: Relative response speed is less than 0.5

[0554] B: Relative response speed is 0.5 or higher and less than 1.0.

[0555] C: Relative response speed is 1.0 or higher and less than 1.5.

[0556] D: Relative response speed is 1.5 or higher and less than 2.0.

[0557] E: Relative response speed is 2.0 or higher.

[0558] [Electric field strength dependence of response speed]

[0559] For each photoelectric conversion element, the electric field intensity dependence of the response speed when receiving blue-green light was evaluated using the following method.

[0560] In the above evaluation of [response speed], the voltage applied to each photoelectric conversion element was changed to 7.5 × 10⁻⁶. 4 V / cm, in addition, 7.5 × 10 was determined using the same procedure. 4 Rise time at V / cm.

[0561] The electric field intensity dependence of the response speed was calculated according to equation (S4), and the electric field intensity dependence of the response speed was evaluated according to the following evaluation criteria. In equation (S4), the numerator and denominator are values ​​obtained by measurement for the same photoelectric conversion element of the same embodiment or comparative example. Furthermore, both the numerator and denominator are response speeds measured at 460 nm. The electric field intensity dependence of the response speed is preferably evaluated as B or higher.

[0562] Equation (S4): Electric field strength dependence of response speed = (Electric field strength dependence of each photoelectric conversion element at 7.5 × 10⁻⁶) 4 Rise time at V / cm / (rise time of each photoelectric conversion element at an electric field strength of 2.0 × 10⁻⁶) 5 (rise time at V / cm)

[0563] A: The electric field strength dependence of the response speed is less than 2.0.

[0564] B: The electric field strength dependence of the response speed is greater than 2.0 and less than 3.0.

[0565] C: The electric field strength dependence of the response speed is greater than 3.0 and less than 4.0.

[0566] D: The electric field strength dependence of the response speed is greater than 4.0 and less than 5.0.

[0567] E: The electric field strength dependence of the response speed is above 5.0.

[0568] [Manufacturing suitability]

[0569] The manufacturing suitability of each photoelectric conversion element was evaluated using the following methods.

[0570] In the above-described fabrication of the photoelectric conversion element, the film deposition rate of the photoelectric conversion film 12 was set to 3.0 Å / s. Otherwise, the photoelectric conversion elements (B) of each embodiment or comparative example were fabricated using the same steps. The quantum efficiency (photoelectric conversion efficiency) of the obtained photoelectric conversion element (B) was measured using the same method as described above for the quantum efficiency.

[0571] The photoelectric conversion element with a film deposition rate of 1.0 Å / s obtained in the above-described fabrication of the photoelectric conversion element 12 is designated as photoelectric conversion element (A), and the relative ratio B / A of the quantum efficiency (photoelectric conversion efficiency) is calculated according to equation (S5). The manufacturing suitability is evaluated based on the obtained values ​​according to the following evaluation criteria. In addition, in equation (S5), the photoelectric conversion elements (B) and (A) in the numerator and denominator are photoelectric conversion elements made of the same material.

[0572] The closer the B / A value is to 1, the less likely the performance of the photoelectric conversion element will deteriorate even when the film deposition rate is accelerated; that is, the manufacturing suitability is excellent. A manufacturing suitability rating of C or higher is preferred.

[0573] Equation (S5): Relative ratio B / A = (Photoelectric conversion efficiency of photoelectric conversion element (B)) / (Photoelectric conversion efficiency of photoelectric conversion element (A))

[0574] A: The ratio of B / A is above 0.90.

[0575] B: The relative B / A ratio is greater than 0.85 and less than 0.90.

[0576] C: The relative ratio of B / A is greater than 0.80 and less than 0.85.

[0577] D: The relative ratio of B / A is greater than 0.75 and less than 0.80.

[0578] E: The relative ratio B / A is less than 0.75

[0579] [result]

[0580] The evaluation results are shown in Table 1 below.

[0581] In the table, in the "C-1 or C-2" column, the case where the base represented by formula (A-1) for a specific compound is the base represented by formula (C-1) or the base represented by formula (C-2) is set as "A", and the other cases are set as "B".

[0582] In the table, in the "R" column, the C values ​​for a specific compound will be displayed. A~C D At least one ring in the ring is selected from an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, an aliphatic heterocyclic group that may have substituents, or a -SiR group. Si The case of at least one substituent in the group consisting of 3 and halogen atoms is designated as "A", and the case other than the above is designated as "B".

[0583] In the table, under "R" X In the "R" column, information about a specific compound will be included. X1 ~R X5 The cases that can have substituents, such as aliphatic hydrocarbon groups, aromatic cyclic groups, or aliphatic heterocyclic groups, are designated as "A" and the cases other than those mentioned above are designated as "B".

[0584] In the table, under "R" Z In the "R" column, information about a specific compound will be included. Z Each is independently a hydrogen atom, a halogen atom, or a -SiR atom. Si 3. Cases that can have substituents, such as aliphatic hydrocarbon groups, aromatic cyclic groups, or aliphatic heterocyclic groups, are designated as "A". Cases other than those mentioned above are designated as "B".

[0585] In the table, under "C" D In the "C" column, information about a specific compound will be included. D Let “A” represent the ring as shown in equation (4-1), and let “B” represent the other cases.

[0586] In the table, under "C" A In the "C" column, information about a specific compound will be included. A Let “A” represent the ring as shown in equation (2-2), and let “B” represent the other cases.

[0587] In the table, under "C" B C D In the "C" column, information about a specific compound will be included. B and C D The case where at least one of them is a ring represented by equation (3-5) or a ring represented by equation (3-3) is designated as “A”, and the case other than the above is designated as “B”.

[0588] In the table, in the column “(1-1)(1-2)”, the case where the specific compound is the compound represented by formula (1-1) or formula (1-2) is marked as “A”, and the case where it is not the above is marked as “B”.

[0589] In the table, in column “(5)”, the case where the specific compound is the compound represented by formula (5) is set as “A”, and the case other than the above is set as “B”.

[0590] [Table 1]

[0591]

[0592] The results shown in Table 1 confirm that the quantum efficiency of the photoelectric conversion element of the present invention has a small dependence on the electric field strength when receiving blue-green light. Furthermore, it is confirmed that the photoelectric conversion element of the present invention exhibits excellent quantum efficiency and response speed when receiving blue-green light, with a small dependence on the electric field strength of the response speed, thus resulting in excellent manufacturability.

[0593] The comparison of Examples 1-6 to 1-9 confirms that when A is a basis represented by Formula (C-1) or Formula (C-2), the quantum efficiency and response speed are superior, and the electric field strength dependence of both quantum efficiency and response speed is smaller.

[0594] A comparison of Examples 1-1 to 1-5 confirms that C A ~C D At least one ring in the ring is selected from an aliphatic hydrocarbon group that may have substituents, an aromatic cyclic group that may have substituents, an aliphatic heterocyclic group that may have substituents, or a -SiR group. Si When at least one substituent is found in the group consisting of 3 and halogen atoms, the quantum efficiency and response speed are superior, and the electric field strength dependence of both quantum efficiency and response speed is smaller.

[0595] A comparison of Examples 1-6 to 1-7 and 1-10 confirms that, in R Z Each is independently a hydrogen atom, a halogen atom, or a -SiR atom. Si 3. The quantum efficiency is even better when the aliphatic hydrocarbon group, the aromatic cyclic group, or the aliphatic heterocyclic group can have substituents.

[0596] A comparison of Examples 1-6 to 1-7 and 1-11 confirms that when C B and C D The quantum efficiency is superior when at least one of them is a ring represented by equation (3-5) or a ring represented by equation (3-3).

[0597] Comparison of Examples 1-14, 1-20 to 1-24 and 1-28 to 1-29 with other examples confirms that when the specific compound is the compound represented by formula (5), the electric field strength dependence of the response speed is smaller.

[0598] Using specific or comparative compounds, n-type organic semiconductors (fullerenes (C)60 A photoelectric conversion film with a thickness of 400 nm was formed by co-deposition of a specific compound: pigment: n-type organic semiconductor: p-type organic semiconductor in a ratio of 1:1:2:2 (thickness conversion) using a vacuum evaporation method. In the steps other than those described above, each photoelectric conversion element was fabricated using the same steps as those described for fabricating the photoelectric conversion element, and the aforementioned evaluations were performed. Furthermore, photoelectric conversion elements were fabricated for all combinations of each specific compound and each pigment, and each evaluation was performed.

[0599] As a result, even when pigments are used, the same results as those shown in the table above can be obtained. Specifically, for example, the photoelectric conversion element prepared using compound 1-1 and according to the method described above showed evaluation results equivalent to those of Example 1 in Table 1.

[0600] [Chemical Formula 29]

[0601]

[0602] Symbol Explanation

[0603] 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, comprising, in sequence, a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein, The photoelectric conversion film comprises the compound represented by formula (1), In equation (1), C A C represents the ring represented by the expression in the group consisting of free expression (2-1), expression (2-2), and expression (2-3). B and C C Let C represent the rings represented by the formulas in the groups consisting of formulas (3-1), (3-2), (3-3), and (3-4), respectively. D Let the ring be represented by the expression in the group consisting of the free expression (4-1) and expression (4-2). In equations (2-1) to (2-3), (3-1) to (3-4), and (4-1) to (4-2), X independently represents oxygen atom, sulfur atom, selenium atom, and -NR atom, respectively. X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, R X1 ~R X5 Each can be used independently to represent a hydrogen atom or a substituent. Z represents -CR independently. Z = or nitrogen atom, R Z Indicates a hydrogen atom or does not contain an azo group, -NR N 2. The base represented by formula (N) and any of the substituents in -CH=A, R N Each can independently represent a hydrogen atom or a substituent, where A represents the group represented by formula (A-1). *, *1, and *2 represent the bonding positions, where C B The ring represented by the formula selected from the group consisting of formulas (3-1), (3-2), (3-3), and (3-4) has two *1 bonding positions with C. A The ring and C are represented C The ring fusion of one of the rings is represented by two * 2 bonding sites with C. A The ring and C are represented C The rings of the other rings represented are fused, and C C The ring represented by the formula selected from the group consisting of formulas (3-1), (3-2), (3-3), and (3-4) has two *1 bonding positions with C. B The ring and C are represented D The ring fusion of one of the rings is represented by two * 2 bonding sites with C. B The ring and C are represented D The rings of the other rings represented are fused. In equation (3-4), Y represents an oxygen atom, a sulfur atom, or -NR. Y1 -, R Y1 Represents a hydrogen atom or a substituent. R can represent either a hydrogen atom or a substituent independently. In equations (4-1) and (4-2), A represents the basis represented by equation (A-1). In equation (A-1), C 1 This indicates a ring containing at least two carbon atoms and optionally having substituents. Q represents oxygen atom, sulfur atom, =NR Q1 or =CR Q2 R Q3 R Q1 R represents a hydrogen atom or substituent. Q2 and R Q3 Representing cyano and -SO2R independently, respectively. Q4 -COOR Q5 or -COR Q6 R Q4 ~R Q6 Each can be independently represented as an aliphatic hydrocarbon group with optional substituents, an aromatic cyclic group with optional substituents, or an aliphatic heterocyclic group with optional substituents. * indicates the bonding location. In formula (N), C N R represents a ring containing nitrogen atoms. N2 Each substituent can be represented independently, and m represents an integer greater than or equal to 0 in R. N2 When there are more than two, R N2 They can be optionally bonded together to form rings with optional substituents. * indicates the bonding location. Wherein, the compound represented by formula (1) satisfies at least one of the following requirements A to D, Requirement A: C A The ring represented by equation (2-1) or the ring represented by equation (2-3) Requirement B: C B and C C At least one of them is the ring represented by formula (3-1) or the ring represented by formula (3-4), and X in the ring represented by formula (3-1) represents an oxygen atom, a sulfur atom, a selenium atom, or a -SiR atom. X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, Among them, C B and C C Except for the case where all are rings represented by equation (3-1), Requirement C: C B and C C All are rings represented by equation (3-1), and C B and C C In one of them, X represents oxygen atom, selenium atom, -NR. X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, Requirement D: C D The ring represented by equation (4-1), where X in the ring represented by equation (4-1) represents an oxygen atom, a sulfur atom, or -NR. X1 -、-CR X4 2- or -C (=CR) X5 2) -.

2. The photoelectric conversion element according to claim 1, wherein, The basis represented by equation (A-1) is either the basis represented by equation (C-1) or the basis represented by equation (C-2). In equation (C-1), X c1 and X c2 Each of the following can be used independently to represent an oxygen atom, a sulfur atom, and =NR. Q1 or =CR Q2 R Q3 R Q1 R Q2 and R Q3 The meanings are respectively related to R in the above formula (1). Q1 R Q2 and R Q3 The meaning is the same. C 3 This indicates an aromatic ring with optional substituents. * indicates the bonding location. In equation (C-2), X c3 ~X c5 Each of the following can be used independently to represent an oxygen atom, a sulfur atom, and =NR. Q1 or =CR Q2 R Q3 R Q1 R Q2 and R Q3 The meanings are respectively related to R in the above formula (1). Q1 R Q2 and R Q3 The meaning is the same. Z c1 and Z c2 Represent -NR independently c1 -or-CR c2 2-, R C1 and R C2 Each can be used independently to represent a hydrogen atom or a substituent. * indicates the bonding location.

3. The photoelectric conversion element according to claim 1, wherein, C A ~C D At least one ring in the ring has a substituent aliphatic hydrocarbon group, a substituent aromatic ring group, a substituent aliphatic heterocyclic group, or -SiR. Si At least one substituent in the group consisting of 3 and halogen atoms, R Si Each can be independently represented as an aliphatic hydrocarbon group, an aromatic cyclic group, or an aliphatic heterocyclic group with optional substituents.

4. The photoelectric conversion element according to claim 1, wherein, R X1 ~R X5 Each can be independently an aliphatic hydrocarbon group with a substituent, an aromatic cyclic group with a substituent, or an aliphatic heterocyclic group with a substituent.

5. The photoelectric conversion element according to claim 1, wherein, R Z Each is independently a hydrogen atom, a halogen atom, or a -SiR atom. Si 3. Optionally, an aliphatic hydrocarbon group, an aromatic cyclic group, or an aliphatic heterocyclic group with substituents. R Si Each can be independently represented as an aliphatic hydrocarbon group, an aromatic cyclic group, or an aliphatic heterocyclic group with optional substituents.

6. The photoelectric conversion element according to claim 1, wherein, C D Let be the ring represented by equation (4-1).

7. The photoelectric conversion element according to claim 1, wherein, C A Let be the ring represented by equation (2-2).

8. The photoelectric conversion element according to any one of claims 1 to 7, wherein, C B and C C At least one of them is the ring represented by equation (3-5) or the ring represented by equation (3-4). In equation (3-5), W represents -NR X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, R X1 ~R X5 Each can be used independently to represent a hydrogen atom or a substituent. *1 and *2 indicate the bonding location, C B When the ring is represented by equation (3-5), at the two *1 bonding positions with C A The ring and C are represented C The ring fusion of one of the rings is represented by two * 2 bonding sites with C. A The ring and C are represented C The rings of the other ring represented by C are fused. C When the ring is represented by equation (3-5), at the two *1 bonding positions with C B The ring and C are represented D The ring fusion of one of the rings is represented by two * 2 bonding sites with C. B The ring and C are represented D The rings of the other rings represented are fused.

9. The photoelectric conversion element according to claim 8, wherein, The compound represented by formula (1) is the compound represented by formula (1-1) or formula (1-2). In equations (1-1) and (1-2), C A C B C C A, X, and Z are related to C in equation (1). A C B C C A, X, and Z are the same. W indicates -NR X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, R X1 ~R X5 Each can be used to represent a hydrogen atom or a substituent independently.

10. The photoelectric conversion element according to any one of claims 1 to 7, wherein, The compound represented by formula (1) is the same as the compound represented by formula (5). In equation (5), X, Z, and A are the same as X, Z, and A in equation (1). W indicates -NR X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, R X1 ~R X5 Each can be used to represent a hydrogen atom or a substituent independently.

11. The photoelectric conversion element according to any one of claims 1 to 7, wherein, The photoelectric conversion film also contains an n-type organic semiconductor. The photoelectric conversion film has a bulk heterostructure formed in the state of the compound represented by formula (1) mixed with the n-type organic semiconductor.

12. The photoelectric conversion element according to claim 11, wherein, The n-type organic semiconductor includes fullerenes selected from the group consisting of fullerenes and their derivatives.

13. The photoelectric conversion element according to any one of claims 1 to 7, wherein, The photoelectric conversion film also contains a p-type organic semiconductor.

14. The photoelectric conversion element according to any one of claims 1 to 7, wherein, The photoelectric conversion film also contains pigments.

15. The photoelectric conversion element according to any one of claims 1 to 7, wherein, Between the conductive film and the transparent conductive film, there is one or more intermediate layers in addition to the photoelectric conversion film.

16. A camera element having a photoelectric conversion element according to any one of claims 1 to 7.

17. An optical sensor having a photoelectric conversion element according to any one of claims 1 to 7.

18. A method for manufacturing a camera element, comprising the step of manufacturing a photoelectric conversion element according to any one of claims 1 to 7.

19. A compound represented by formula (1), In equation (1), C A C represents the ring represented by the expression in the group consisting of free expression (2-1), expression (2-2), and expression (2-3). B and C C Let C represent the rings represented by the formulas in the groups consisting of formulas (3-1), (3-2), (3-3), and (3-4), respectively. D Let the ring be represented by the expression in the group consisting of the free expression (4-1) and expression (4-2). In equations (2-1) to (2-3), (3-1) to (3-4), and (4-1) to (4-2), X independently represents oxygen atom, sulfur atom, selenium atom, and -NR atom, respectively. X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, R X1 ~R X5 Each can be used independently to represent a hydrogen atom or a substituent. Z represents -CR independently. Z = or nitrogen atom, R Z Indicates a hydrogen atom or does not contain an azo group, -NR N 2. The base represented by formula (N) and any of the substituents in -CH=A, R N Each can independently represent a hydrogen atom or a substituent, where A represents the group represented by formula (A-1). *, *1, and *2 represent the bonding positions, where, C B The ring represented by the formula selected from the group consisting of formulas (3-1), (3-2), (3-3), and (3-4) has two *1 bonding positions with C. A The ring and C are represented C The ring fusion of one of the rings is represented by two * 2 bonding sites with C. A The ring and C are represented C The rings of the other rings represented are fused, and C C The ring represented by the formula selected from the group consisting of formulas (3-1), (3-2), (3-3), and (3-4) has two *1 bonding positions with C. B The ring and C are represented D The ring fusion of one of the rings is represented by two * 2 bonding sites with C. B The ring and C are represented D The rings of the other rings represented are fused. In equation (3-4), Y represents an oxygen atom, a sulfur atom, or -NR. Y1 -, R Y1 Represents a hydrogen atom or a substituent. R can represent either a hydrogen atom or a substituent independently. In equations (4-1) and (4-2), A represents the basis represented by equation (A-1). In equation (A-1), C 1 This indicates a ring containing at least two carbon atoms and optionally having substituents. Q represents oxygen atom, sulfur atom, =NR Q1 or =CR Q2 R Q3 R Q1 R represents a hydrogen atom or substituent. Q2 and R Q3 Representing cyano and -SO2R independently, respectively. Q4 -COOR Q5 or -COR Q6 R Q4 ~R Q6 Each can be independently represented as an aliphatic hydrocarbon group with optional substituents, an aromatic cyclic group with optional substituents, or an aliphatic heterocyclic group with optional substituents. * indicates the bonding location. In formula (N), C N R represents a ring containing nitrogen atoms. N2 Each substituent can be represented independently, and m represents an integer greater than or equal to 0 in R. N2 When there are more than two, R N2 They can be optionally bonded together to form rings with optional substituents. * indicates the bonding location. Wherein, the compound represented by formula (1) satisfies at least one of the following requirements A to D, Requirement A: C A The ring represented by equation (2-1) or the ring represented by equation (2-3) Requirement B: C B and C C At least one of them is the ring represented by formula (3-1) or the ring represented by formula (3-4), and X in the ring represented by formula (3-1) represents an oxygen atom, a sulfur atom, a selenium atom, or a -SiR atom. X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, Among them, C B and C C Except for the case where all are rings represented by equation (3-1), Requirement C: C B and C C All are rings represented by equation (3-1), and C B and C C In one of them, X represents oxygen atom, selenium atom, -NR. X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, Requirement D: C D The ring represented by equation (4-1), where X in the ring represented by equation (4-1) represents an oxygen atom, a sulfur atom, or -NR. X1 -、-CR X4 2- or -C (=CR) X5 2) -.

20. The compound according to claim 19, wherein, The basis represented by equation (A-1) is either the basis represented by equation (C-1) or the basis represented by equation (C-2). In equation (C-1), X c1 and X c2 Each of the following can be used independently to represent an oxygen atom, a sulfur atom, and =NR. Q1 or =CR Q2 R Q3 R Q1 R Q2 and R Q3 The meanings are respectively related to R in the above formula (1). Q1 R Q2 and R Q3 The meaning is the same. C 3 This indicates an aromatic ring with optional substituents. * indicates the bonding location. In equation (C-2), X c3 ~X c5 Each of the following can be used independently to represent an oxygen atom, a sulfur atom, and =NR. Q1 or =CR Q2 R Q3 R Q1 R Q2 and R Q3 The meanings are respectively related to R in the above formula (1). Q1 R Q2 and R Q3 The meaning is the same. Z c1 and Z c2 Represent -NR independently c1 -or-CR c2 2-, R C1 and R C2 Each can be used independently to represent a hydrogen atom or a substituent. * indicates the bonding location.

21. The compound according to claim 19, wherein, C A ~C D At least one ring in the ring has a substituent aliphatic hydrocarbon group, a substituent aromatic ring group, a substituent aliphatic heterocyclic group, or -SiR. Si At least one substituent in the group consisting of 3 and halogen atoms, R Si Each can be independently represented as an aliphatic hydrocarbon group, an aromatic cyclic group, or an aliphatic heterocyclic group with optional substituents.

22. The compound according to claim 19, wherein, R X1 ~R X5 Each can be independently an aliphatic hydrocarbon group with a substituent, an aromatic cyclic group with a substituent, or an aliphatic heterocyclic group with a substituent.

23. The compound according to claim 19, wherein, R Z Each is independently a hydrogen atom, a halogen atom, or a -SiR atom. Si 3. Optionally, an aliphatic hydrocarbon group, an aromatic cyclic group, or an aliphatic heterocyclic group with substituents. R Si Each can be independently represented as an aliphatic hydrocarbon group, an aromatic cyclic group, or an aliphatic heterocyclic group with optional substituents.

24. The compound according to claim 19, wherein, C D Let be the ring represented by equation (4-1).

25. The compound according to claim 19, wherein, C A Let be the ring represented by equation (2-2).

26. The compound according to any one of claims 19 to 25, wherein, C B and C C At least one of them is the ring represented by equation (3-5) or the ring represented by equation (3-4). In equation (3-5), W represents -NR X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, R X1 ~R X5 Each can be used independently to represent a hydrogen atom or a substituent. *1 and *2 indicate the bonding location, C B When the ring is represented by equation (3-5), at the two *1 bonding positions with C A The ring and C are represented C The ring fusion of one of the rings is represented by two * 2 bonding sites with C. A The ring and C are represented C The rings of the other ring represented by C are fused. C When the ring is represented by equation (3-5), at the two *1 bonding positions with C B The ring and C are represented D The ring fusion of one of the rings is represented by two * 2 bonding sites with C. B The ring and C are represented D The rings of the other rings represented are fused.

27. The compound according to claim 26, wherein, The compound represented by formula (1) is the compound represented by formula (1-1) or formula (1-2). In equations (1-1) and (1-2), C A C B C C A, X, and Z are related to C in equation (1). A C B C C A, X, and Z are the same. W indicates -NR X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, R X1 ~R X5 Each can be used to represent a hydrogen atom or a substituent independently.

28. The compound according to any one of claims 19 to 25, wherein, The compound represented by formula (1) is the same as the compound represented by formula (5). In equation (5), X, Z, and A are the same as X, Z, and A in equation (1). W indicates -NR X1 -、-SiR X2 2-、-GeR X3 2-、-CR X4 2- or -C (=CR) X5 2) -, R X1 ~R X5 Each can be used to represent a hydrogen atom or a substituent independently.

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