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

Abstract

The present invention provides a photoelectric conversion element in which the responsiveness to blue / green light has a low dependence on electric field strength. The present invention also provides an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound that are related to the photoelectric conversion element. The photoelectric conversion element according to the present invention comprises a conductive film, a photoelectric conversion film, and a transparent conductive film in the stated order, the photoelectric conversion film comprising a compound represented by formula (1).

Description

Photoelectric conversion element, image sensor, light sensor, method for manufacturing an image sensor, compound

[0001] The present invention relates to a photoelectric conversion element, an image sensor, a light sensor, a method for manufacturing an image sensor, and a compound.

[0002] In recent years, the development of devices having photoelectric conversion films (for example, image sensors) has progressed. For example, Patent Document 1 discloses a compound with a specific structure that can be applied to organic semiconductor materials such as organic solar cells.

[0003] European Patent Application Publication No. 3333170

[0004] With the increasing demand for improved performance in image sensors and optical sensors, there is a need for photoelectric conversion elements that exhibit superior characteristics. One characteristic required of a photoelectric conversion element is that its responsiveness (response speed) does not change significantly when the electric field strength is altered; in other words, its responsiveness has low dependence on electric field strength. Under these requirements, the present inventors fabricated and investigated a photoelectric conversion element containing the compound disclosed in Patent Document 1. While Patent Document 1 discloses a predetermined donor structure, they found that, depending on the type of acceptor, the electric field strength dependence of the response speed (responsiveness) to blue-green light is high, indicating room for improvement. In this specification, blue-green light refers to light with a wavelength of 400 to 530 nm.

[0005] Therefore, the present invention aims to provide a photoelectric conversion element that exhibits low dependence of electric field strength on responsiveness to blue-green light. Furthermore, the present invention also aims to provide an image sensor, a light sensor, a method for manufacturing the image sensor, and a compound related to the above-mentioned photoelectric conversion element.

[0006] As a result of diligent research to solve the above problems, the inventors have found that the problems can be solved by the following configuration.

[0007] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1) described later. [2] The photoelectric conversion element according to [1], wherein the other is a group represented by formula (A2-1). [3] The photoelectric conversion element according to [1] or [2], wherein the other is a group represented by formula (A2-3) or formula (A2-4) described later. [4] The photoelectric conversion element according to any one of [1] to [3], wherein one of the above is a group represented by either formula (A1-1) or formula (A1-2). [5] The photoelectric conversion element according to [3], wherein one of the above is a group represented by either formula (A1-1) or formula (A1-2), and the other is a group represented by formula (A2-3). [6] The photoelectric conversion element according to any one of [1] to [5], wherein the photoelectric conversion film further comprises an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed when the compound represented by formula (1) and the n-type organic semiconductor are mixed. [7] The photoelectric conversion element according to [6], wherein the n-type organic semiconductor comprises fullerenes selected from the group consisting of fullerenes and their derivatives. [8] The photoelectric conversion element according to any one of [1] to [7], wherein the photoelectric conversion film further comprises a p-type organic semiconductor. [9] The photoelectric conversion element according to any one of [1] to [8], wherein the photoelectric conversion film further comprises a dye.

[10] The photoelectric conversion element according to any one of [1] to [9], wherein there is one or more intermediate layers between the conductive film and the transparent conductive film in addition to the photoelectric conversion film.

[11] An image sensor having the photoelectric conversion element according to any one of [1] to

[10] .

[12] A light sensor having a photoelectric conversion element described in any one of [1] to

[10] .

[13] A method for manufacturing an image sensor, comprising a step of manufacturing a photoelectric conversion element described in any one of [1] to

[10] .

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

[15] The compound according to

[14] , wherein the other is a group represented by formula (A2-1) described later.

[16] The compound according to

[14] or

[15] , wherein the other is a group represented by formula (A2-3) described later or formula (A2-4) described later.

[17] The compound according to

[14] or

[15] , wherein one of the above is a group represented by either formula (A1-1) or formula (A1-2).

[18] The compound according to

[16] , wherein one of the above is a group represented by either formula (A1-1) or formula (A1-2), and the other is a group represented by formula (A2-3).

[0008] According to the present invention, a photoelectric conversion element can be provided that exhibits low dependence of electric field strength on responsiveness to blue-green light. Furthermore, according to the present invention, an image sensor, a light sensor, a method for manufacturing the image sensor, and a compound related to the above-mentioned photoelectric conversion element can also be provided.

[0009] This is a schematic cross-sectional diagram showing one example of the configuration of a photoelectric conversion element.

[0010] The present invention will be described in detail below. The following descriptions of constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0012] In this specification, a hydrogen atom may be either a light hydrogen atom (a normal hydrogen atom) or a deuterium atom (for example, a double hydrogen atom). In this specification, when there are multiple substituents and linking groups, etc. (hereinafter also referred to as "substituents, etc.") indicated by a specific symbol, or when multiple substituents, etc. are specified simultaneously, it means that each substituent, etc. may be identical or different from the others. The same applies to the specification of the number of substituents, etc.

[0013] In this specification, unless otherwise specified, "substituent" refers to the group exemplified by the substituent W below.

[0014] (Substituent W) The substituent W in this specification is described below. Substituent W is, for example, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, and iodine atom), an alkyl group (including cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups), an alkenyl group (including cycloalkenyl groups and bicycloalkenyl groups), an alkynyl group, an aryl group, a heterocyclic group (heteroaryl group or aliphatic heterocyclic group), a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyl Examples include oxy groups, primary, secondary, or tertiary amino groups (including anilino groups), alkylthio groups, arylthio groups, heterocyclic thio groups, alkyl or arylsulfinyl groups, alkyl or arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, carboxyl groups, phosphoric acid groups, sulfonic acid groups, hydroxyl groups, thiol groups, acylamino groups, carbamoyl groups, ureido groups, and boronic acid groups. Each of the above groups may, if possible, have further substituents (for example, one or more of the above groups). For example, an alkyl group which may have substituents is also included as one form of substituent W. If substituent W has carbon atoms, the number of carbon atoms in substituent W is, for example, 1 to 20. The number of atoms other than hydrogen atoms in substituent W is, for example, 1 to 30. The specific compounds described later may have substituents such as carboxyl group, carboxyl group salt, phosphate group, phosphate group salt, sulfonic acid group, sulfonic acid group salt, hydroxyl group, thiol group, acylamino group, carbamoyl group, ureido group, or boronic acid group (-B(OH)). ２ ) and / or the absence of a primary amino group is also preferable.

[0015] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0016] In this specification, unless otherwise specified, aliphatic hydrocarbon groups may be linear, branched, or cyclic. Examples of aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups. In this specification, unless otherwise specified, the number of carbon atoms in an alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Unless otherwise specified, alkyl groups may be linear, branched, or cyclic. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, cyclopropyl, and cyclopentyl groups. Cyclic alkyl groups may be cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups, and alkyl groups may have these ring structures as partial structures. In alkyl groups that may have substituents, examples of substituents that the alkyl group may have include the group exemplified by substituent W. Among these, aryl groups (preferably having 6 to 18 carbon atoms, more preferably 6 carbon atoms), heteroaryl groups (preferably having 5 to 18 carbon atoms, more preferably 5 to 6 carbon atoms), or halogen atoms (preferably fluorine atoms or chlorine atoms) are preferred.

[0017] In this specification, unless otherwise specified, the alkyl portion of the alkoxy group and alkylthio group is preferably the alkyl group described above. In an alkoxy group which may have substituents, examples of substituents that the alkoxy group may have are the same as examples of substituents in an alkyl group which may have substituents. In an alkylthio group which may have substituents, examples of substituents that the alkylthio group may have are the same as examples of substituents in an alkyl group which may have substituents.

[0018] In this specification, unless otherwise specified, the alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group is preferably 2 to 20. In an alkenyl group which may have substituents, examples of substituents that the alkenyl group may have are the same as examples of substituents in an alkyl group which may have substituents. In this specification, unless otherwise specified, the alkynyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20. In an alkynyl group which may have substituents, examples of substituents that the alkynyl group may have are the same as examples of substituents in an alkyl group which may have substituents.

[0019] In this specification, unless otherwise specified, the aromatic ring or aromatic ring group may be monocyclic or polycyclic (e.g., 2 to 6 rings). A monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as its ring structure. A polycyclic (e.g., 2 to 6 rings) aromatic ring is an aromatic ring in which multiple (e.g., 2 to 6) aromatic ring structures are fused together as its ring structure. The number of ring members of the above aromatic ring is preferably 5 to 15, and more preferably 5 to 6. In this specification, unless otherwise specified, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle. When the above aromatic ring is an aromatic heterocycle, the number of heteroatoms having as ring member atoms is, for example, 1 to 10. Examples of the above heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron. Examples of the aromatic hydrocarbon rings mentioned above include benzene rings, naphthalene rings, anthracene rings, pyrene rings, phenanthrene rings, and fluorene rings.Examples of the above aromatic heterocycles include 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, etc.), tetrazine rings (e.g., 1,2,4,5-tetrazine rings, etc.), quinoxaline rings, pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, thiazole rings, benzopyrrole rings, benzofuran rings, benzothiophene rings, benzimidazole rings, benzoxazole rings, benzothiazole rings, naphthopyrrole rings, naphthofuran rings, naphthothiophene rings, naphtoimidazole rings, naphthoxazole rings, pyrroloimidazole rings (e.g., 5H-pyrrolo[1,2-a]imidazole rings, etc.), imidazoxazole rings (e.g., imidazo[2,1-b]oxazole rings, etc.), Thienothiazole rings (e.g., thieno[2,3-d]thiazole rings, etc.), benzothiadiazole rings, benzodithiophene rings (e.g., benzo[1,2-b:4,5-b']dithiophene rings, etc.), thienothiophene rings (e.g., thieno[3,2-b]thiophene rings, etc.), thiazolothiazole rings (e.g., thiazolo[5,4-d]thiazole rings, etc.), naphthodithiophene rings (e.g., naphtho[2,3- Examples include the [b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring and 1,8-dithiadicyclopenta[b,g]naphthalene ring, etc., benzothienobenzothiophene ring, dithieno[3,2-b:2',3'-d]thiophene ring, and 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring.

[0020] In this specification, when referring to an aromatic ring group, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from the above-mentioned aromatic ring is included. In this specification, when referring to an aromatic hydrocarbon group, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from the above-mentioned aromatic hydrocarbon ring is included, and when referring to an aromatic heterocyclic group, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from the above-mentioned aromatic heterocyclic ring is included. In this specification, when referring to an aryl group, for example, a group obtained by removing one hydrogen atom from the ring corresponding to the aromatic hydrocarbon ring among the above-mentioned aromatic ring is included. In this specification, when referring to a heteroaryl group, for example, a group obtained by removing one hydrogen atom from the ring corresponding to the aromatic heterocyclic ring among the above-mentioned aromatic ring is included. In this specification, when referring to an arylene group, for example, a group obtained by removing two hydrogen atoms from the ring corresponding to the aromatic hydrocarbon ring among the above-mentioned aromatic ring is included. In this specification, when referring to a heteroarylene group, for example, it refers to a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the aromatic rings mentioned above. In an optionally substituted aromatic ring group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted arylene group, and an optionally substituted heteroarylene group, the types of substituents that these groups may have include, for example, the group exemplified by substituent W. When these groups have substituents, the number of substituents may be one or more (for example, 1 to 4, etc.).

[0021] In this specification, a non-aromatic ring refers to a ring structure that does not fall under the category of aromatic, and examples include aliphatic hydrocarbon rings and aliphatic heterocycles. Examples of aliphatic hydrocarbon rings include cycloalkanes, cycloalkenes, and cycloalkynes. Examples of aliphatic heterocycles include pyrrolidine rings, oxolane rings, thiolane rings, piperidine rings, tetrahydropyran rings, thiane rings, piperazine rings, morpholine rings, quinuclidine rings, azetidine rings, oxetane rings, aziridine rings, dioxane rings, and γ-butyrolactone rings. In this specification, when referring to an aliphatic hydrocarbon ring group, examples include a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from a ring that corresponds to an aliphatic hydrocarbon ring. In this specification, when referring to an aliphatic heterocycle group, examples include a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5) from a ring that corresponds to an aliphatic heterocycle.

[0022] In this specification, if a single formula representing a chemical structure contains multiple identical symbols indicating the type or number of groups, unless otherwise specified, the meanings of these multiple identical symbols are independent of each other, and the meanings of these identical symbols may be the same or different. In this specification, if a single formula representing a chemical structure contains multiple groups of the same kind (e.g., alkyl groups), unless otherwise specified, the specific meanings of these multiple groups of the same kind are independent of each other, and the specific meanings of these groups of the same kind may be the same or different.

[0023] In this specification, the bonding direction of the divalent group (e.g., -CO-O-) is not limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", if Y is -CO-O-, the compound may be either "X-O-CO-Z" or "X-CO-O-Z".

[0024] In this specification, with respect to compounds that may have geometric isomers (cis-trans isomers), the general formula or structural formula representing the compound may, for convenience, be described only in either the cis or trans form. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form.

[0025] In this specification, unless otherwise specified, the asterisk (*) in formulas indicates a bonding position.

[0026] [Photoelectric Conversion Element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in that order, wherein the photoelectric conversion film contains a compound represented by formula (1) (hereinafter also referred to as the "specific compound").

[0027] The reason why the photoelectric conversion element having the above configuration can solve the problems of the present invention is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than those described below, it is included within the scope of the present invention. The specific compound is a so-called ADA-type dye compound having a donor portion (D) and an acceptor portion (A). Because the specific compound has a predetermined donor structure and acceptor structure, excessive aggregation of the specific compound and carrier trapping by local dipoles are suppressed in the photoelectric conversion film. As a result, efficient charge separation can be achieved even at low electric field strengths, and carriers can move efficiently; that is, the electric field strength dependence of the response speed (responsiveness) is considered to be small. Hereinafter, a smaller electric field strength dependence of the response speed (responsiveness) to blue-green light is also referred to as "the effect of the present invention is superior."

[0028] Figure 1 shows a schematic cross-sectional view of one embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in Figure 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 that 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 the "upper electrode") 15 that functions as an upper electrode are stacked in this order. Figure 2 shows an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in Figure 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked on the lower electrode 11 in this order. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in Figures 1 and 2 may be appropriately changed depending on the application and characteristics.

[0029] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15. Furthermore, when using the 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 between this pair of electrodes, 1 × 10⁻¹⁰ －５ ~1 x 10 ７ It is preferable to apply a voltage of V / cm. In terms of performance and power consumption, the applied voltage should be 1 × 10⁻⁶. －４ ~1 x 10 ７ V / cm is more preferable, 1 × 10 －３ ~5 x 10 ６ A voltage of V / cm is even more preferable. Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side becomes the cathode and the photoelectric conversion film 12 side becomes the anode, as shown in Figures 1 and 2. The same method can be used to apply the voltage when the photoelectric conversion element 10a (or 10b) is used as a light sensor or when it is incorporated into an image sensor. As will be described in detail later, the photoelectric conversion element 10a (or 10b) is suitably applicable to image sensor applications. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

[0030] [Photoelectric conversion film] The photoelectric conversion element has a photoelectric conversion film.

[0031] <Specific Compound> The photoelectric conversion film contains a specific compound, which is a compound represented by formula (1).

[0032]

[0033] In formula (1), R ｘ１ and R ｘ２ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. R ｘ１ and R ｘ２ may be linked to each other to form a ring. R １ and R ２ each independently represents a hydrogen atom or a substituent. One of A １ and A ２ represents a group represented by any one of formulas (A1-1) to (A1-3) detailed later, and the other represents a group represented by any one of formulas (A2-1) and (A2-2) detailed later. However, A １ and A ２ represent different groups from each other.

[0034] R ｘ１ and R ｘ２ are each independently preferably a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent, more preferably a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent, and still more preferably both are aliphatic hydrocarbon groups which may have a substituent. Examples of the substituent that the aliphatic hydrocarbon group, the aromatic ring group, or the aliphatic heterocyclic group may have include the substituents exemplified by the above-mentioned substituent W, and a substituent selected from the substituent group S described later is preferred.

[0035] The above aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the above aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The number of carbon atoms in a linear aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 4, and particularly preferably 1 or 2. The number of carbon atoms in a branched aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, even more preferably 3 to 7, and particularly preferably 3 to 5. The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in a cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 6.

[0036] The above aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The above aromatic ring group may be monocyclic or polycyclic, with monocyclic being preferred. The number of ring members of the above aromatic ring group is preferably 5 to 18, more preferably 5 to 10, and even more preferably 5 to 6. The definition and specific examples of the above aromatic hydrocarbon group are as described above, with a phenyl group or a naphthyl group being preferred, and a phenyl group being more preferred. Examples of heteroatoms that the above aromatic heterocyclic group may have include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, an oxygen atom, or a nitrogen atom being preferred. The definition and specific examples of the above aromatic heterocyclic group are as described above, with a thiophene ring group, a furan ring group, a pyrrole ring group, a thiazole ring group, an imidazole ring, an oxazole ring, or a pyridine ring group being preferred. As described above, the aromatic ring group may have substituents. If the aromatic ring group has substituents, the number is not particularly limited, but 1 to 3 is preferred.

[0037] The definition of an aliphatic heterocyclic group is as described above. In an aliphatic heterocyclic group that may have substituents, the number of ring members of the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 5 to 8. The number of carbon atoms in the aliphatic heterocyclic group is preferably 1 to 20. Examples of heteroatoms that the aliphatic heterocyclic group may have include sulfur, oxygen, nitrogen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, oxygen, or nitrogen atoms being preferred.

[0038] As described above, in equation (1), R ｘ１ and R ｘ２ These atoms may be linked to each other to form a ring. The ring may be either an aromatic ring or a non-aromatic ring, but a non-aromatic ring is preferred, and an aliphatic hydrocarbon ring is more preferred. The ring may also be monocyclic or polycyclic. The ring may have heteroatoms. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, nitrogen, or oxygen atoms being preferred. The number of ring member atoms in the ring is preferably 3 to 20, more preferably 5 to 12, and even more preferably 5 to 8. The ring may have substituents. Examples of substituents that the ring may have include those exemplified by substituent W above, and substituents selected from substituent group S described later are preferred.

[0039] In the above formula (1), R １ and R ２ Each of these independently represents a hydrogen atom or a substituent. In terms of the superior effects of the present invention, R １ and R ２ A hydrogen atom is preferred.

[0040] As described above, in equation (1) above, A １ and A ２ One of them represents a group represented by any of formulas (A1-1) to (A1-3), and the other represents a group represented by either formula (A2-1) or formula (A2-2). However, A １ and A ２The symbols represent distinct groups. In formulas (A1-1) to (A1-3), (A2-1), and (A2-2), * represents a bond position.

[0041]

[0042] In terms of achieving superior effects of the present invention, it is preferable that one of the above is a group represented by either formula (A1-1) or formula (A1-2). Furthermore, in terms of achieving superior effects of the present invention, it is preferable that the other is a group represented by formula (A2-1), more preferably a group represented by formula (A2-3) or formula (A2-4) described later, and even more preferably a group represented by formula (A2-3) described later. Among these, A １ and A ２ Preferably, one of the groups represents a group represented by either formula (A1-1) or formula (A1-2), and the other represents a group represented by formula (A2-3), which will be described later.

[0043] • Equations (A1-1) to (A1-3) The following details equations (A1-1) to (A1-3). In equations (A1-1) and (A1-2), R Ｗ１ and R Ｗ２ Each of these independently represents an aliphatic hydrocarbon group which may have substituents. The above aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the above aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The number of carbon atoms in a linear aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 4, and particularly preferably 1 or 2. The number of carbon atoms in a branched aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, even more preferably 3 to 7, and particularly preferably 3 to 5. The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in a cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 6. Examples of substituents which the above aliphatic hydrocarbon group may have include the substituents exemplified by substituent W above, and substituents selected from the substituent group S described later are preferred.

[0044] In formula (A1-3), Y１ ~Y ４ Each of these is independently -CR Ｙ１ = or represents a nitrogen atom. R Ｙ１ Each of these independently represents a hydrogen atom or a substituent. １ ~Y ４ Three or more of them are -CR Ｙ１ It is preferable to represent Y １ ~Y ４ All of them are -CR Ｙ１ It is preferable to represent it as equals (=).

[0045] R Ｙ１ represents a hydrogen atom or a substituent. Examples of substituents include those exemplified by substituent W above, and groups selected from the substituent group S below are preferred, with optionally substituted aliphatic hydrocarbon groups, optionally substituted aromatic ring groups, or fluorine atoms being more preferred.

[0046] (Substituent group S) A substituted aliphatic hydrocarbon group, a substituted aromatic ring group, a substituted aliphatic heterocyclic group, a substituted alkoxy group, a substituted aryloxy group, a substituted amino group, a substituted cyano group, or a halogen atom. Examples of substituents that each of the above substituted groups may have include the substituents exemplified by substituent W above, and preferred are linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 7 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, aromatic ring groups having 3 to 20 members that may have substituents, or halogen atoms.

[0047] R Ｙ１ The definition and preferred embodiments of an optionally substituted aliphatic hydrocarbon group, optionally substituted aromatic ring group, and optionally substituted aliphatic heterocyclic group represented by R ｘ１ and R ｘ２ This is the same as an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, and an optionally substituted aliphatic heterocyclic group represented by .

[0048] The alkyl group of the alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a t-butoxy group, and a cyclopropoxy group.

[0049] The aryl group in the above aryloxy group may be monocyclic or polycyclic. The number of carbon atoms in the above aryloxy group is preferably 5 to 18, more preferably 6 to 10, and even more preferably 6 to 8. An example of the above aryloxy group is a phenoxy group.

[0050] The above amino group may be a primary amino group, a secondary amino group, or a tertiary amino group, with a tertiary amino group being preferred. In the above secondary and tertiary amino groups, the substituent that replaces the nitrogen atom is preferably a hydrocarbon group, and more preferably an alkyl group (preferably having 1 to 5 carbon atoms) or an aryl group (preferably a phenyl group).

[0051] Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or chlorine atoms being preferred.

[0052] Y １ ~Y ４ Two of them are R Ｙ１ -CR is a substituent Ｙ１ If =, R Ｙ１The substituents represented by may bond to each other to form a ring which may have substituents. The ring may be either an aromatic ring or a non-aromatic ring, but an aromatic ring is preferred, and an aromatic hydrocarbon ring is more preferred. The ring may also be monocyclic or polycyclic. The ring may have heteroatoms. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, nitrogen, or oxygen atoms being preferred. The number of ring member atoms of the ring is preferably 5 to 20, more preferably 5 to 12, and even more preferably 5 to 8. Among the rings, a benzene ring or a naphthalene ring is preferred. Examples of substituents which the ring may have include the substituents exemplified by substituent W above, and substituents selected from the substituent group S are preferred.

[0053] • Equation (A2-1) Next, we will explain in detail about equation (A2-1). In the above equation (A2-1), C １ C represents a ring containing two or more carbon atoms, which may have substituents. １ The two carbon atoms included are the two carbon atoms explicitly shown in formula (A2-1). The number of carbon atoms in the above 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 above ring is the number including the two carbon atoms explicitly shown in the formula. The above ring may be either an aromatic ring or a non-aromatic ring. The above ring may be either a monocyclic or polycyclic ring, and 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 is preferred. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The above ring may have heteroatoms. Examples of the above heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, nitrogen, or oxygen atoms being preferred. The number of heteroatoms in the above ring is preferably 0 to 10, and more preferably 0 to 5. １ Among the carbon atoms constituting the ring represented by formula (A2-1), the carbon atoms at the bond positions marked with * and W１ Carbon atoms other than those bonded to may be substituted with carbonyl carbons (>C=O) or thiocarbonyl carbons (>C=S).

[0054] The above CC １ Examples of substituents that the ring represented by may have include the groups exemplified by substituent W above, and are preferably halogen atoms, alkyl groups, aromatic ring groups, cyano groups, or silyl groups, with halogen atoms or alkyl groups being more preferred. The alkyl group may be linear, branched, or cyclic, with linear being preferred. The alkyl group has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0055] The above CC １The rings represented are preferably those used as acidic nuclei (for example, merocyanine dyes as acidic nuclei), and examples of nuclei include the following: (a) 1,3-dicarbonyl nuclei: for example, 1,3-indanedione nuclei, 1,3-cyclopentanedione, 1,3-cyclopentendione, 4,5-dimethyl-1,3-cyclopentendione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxan-4,6-dione. (b) Pyrazolinone nuclei: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, and 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one. (c) Isoxazolinone nuclei: For example, 3-phenyl-2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one. (d) Oxindole nuclei: For example, 1-alkyl-2,3-dihydro-2-oxindole. (e) 2,4,6-trioxohexahydropyrimidine nuclei: For example, barbituric acid, 2-thiobarbituric acid, and their derivatives. Examples of the above derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl, and 1,3-dibutyl, 1,3-diaryl compounds such as 1,3-diphenyl, 1,3-di(p-chlorophenyl), and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, and 1,3-diheteroaryl compounds such as 1,3-di(2-pyridyl). (f) 2-thio-2,4-thiazolidinedione core: for example, rhodanine and its derivatives. Examples of the above derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-allylrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and 3-heteroarylrhodanines such as 3-(2-pyridyl)rhodanine. (g) 2-thio-2,4-oxazolidinedione nuclei (2-thio-2,4-(3H,5H)-oxazoledione nuclei): e.g., 3-ethyl-2-thio-2,4-oxazolidinedione. (h) thianaphthenone nuclei: e.g., 3(2H)-thianaphthenone-1,1-dioxide.(i) 2-thio-2,5-thiazolidinedione nuclei: e.g., 3-ethyl-2-thio-2,5-thiazolidinedione, etc. (j) 2,4-thiazolidinedione nuclei: e.g., 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, and 3-phenyl-2,4-thiazolidinedione, etc. (k) thiazolin-4-one nuclei: e.g., 4-thiazolinone and 2-ethyl-4-thiazolinone, etc. (l) 2,4-imidazolidinedione (hydantoin) nuclei: e.g., 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione, etc. (m) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) core: e.g., 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione, etc. (n) imidazolin-5-one core: e.g., 2-propylmercapto-2-imidazolin-5-one, etc. (o) 3,5-pyrazolidinedione core: e.g., 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione, etc. (p) benzothiophen-3(2H)-one core: e.g., benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, and dioxobenzothiophen-3(2H)-one, etc. (q) Indanone nuclei: e.g., 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, and 3,3-dimethyl-1-indanone, etc. (r) Benzofuran-3-(2H)-one nuclei: e.g., benzofuran-3-(2H)-one, etc. (s) 2,2-dihydrophenalen-1,3-dione nuclei, etc.

[0056] In formula (A2-1), W １ This consists of an oxygen atom, a sulfur atom, and =NR Ｗ３ , or =CR Ｗ４ R Ｗ５ Represents W １ In terms of superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ３ R represents a hydrogen atom or a substituent. Examples of substituents include the group exemplified by substituent W above. Ｗ４ and R Ｗ５ These are, independently, a cyano group and -SO２ R Ｗ６ , -COOR Ｗ７ , or -COR Ｗ８ Represents R Ｗ６ ~R Ｗ８ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. The definition of an aliphatic hydrocarbon group is as described above, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred. The definition of an aromatic ring group is as described above, and an aromatic hydrocarbon group is preferred, with a phenyl group being more preferred. The definition of an aliphatic heterocyclic group is as described above, and the heteroatom of the above aliphatic heterocyclic group is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. Ｗ６ ~R Ｗ８ Examples of substituents that each group represented by the above substituent W may have include the substituents exemplified by substituent W.

[0057] The group represented by formula (A2-1) is preferably the group represented by formula (A-3) in that the effects of the present invention are superior. In formula (A-3), * represents the bond position.

[0058]

[0059] In formula (A-3), C ２ This represents a ring containing at least three carbon atoms, which may have substituents. ２The three carbon atoms included are the three carbon atoms explicitly shown in formula (A-3). The number of carbon atoms in the above 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 above ring is the number including the three carbon atoms explicitly shown in the formula. The above ring may be either an aromatic ring or a non-aromatic ring. The above ring may be either a monocyclic or polycyclic ring, and a fused ring containing a 5-membered ring, a 6-membered ring, or at least one of a 5-membered ring and a 6-membered ring is preferred. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The above ring may have heteroatoms. Examples of the above heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron, with sulfur, nitrogen, or oxygen being preferred. The number of heteroatoms in the above ring is preferably 0 to 10, and more preferably 0 to 5. ２ Among the carbon atoms constituting the ring represented by, the carbon atoms at the bond positions marked with * in formula (A-3), and W ２ or W ３ Carbon atoms other than the carbon atom bonded to the ring may be substituted with carbonyl carbons (>C=O) or thiocarbonyl carbons (>C=S). Preferred embodiments of substituents that the ring may have are the ring C １ This is similar to the substituents that may be present.

[0060] In formula (A-3), W ２ and W ３ These are, independently, an oxygen atom, a sulfur atom, and =NR Ｗ３ , or =CR Ｗ４ R Ｗ５ The oxygen atom is preferred because it represents the present invention and provides superior effects. Ｗ３ ~R Ｗ５ The definition and preferred embodiment are as described above.

[0061] The group represented by formula (A2-1) is more preferably the group represented by formula (A2-3) or the group represented by formula (A2-4) in terms of superior effects of the present invention. In formulas (A2-3) and (A2-4), * represents the bond position.

[0062]

[0063] In formula (A2-3), W ２ and W ３ each independently represents an oxygen atom or a sulfur atom. In terms of the more excellent effects of the present invention, it is preferable that at least one of W ２ and W ３ is an oxygen atom, and it is more preferable that W ２ and W ３ are oxygen atoms. Y ５ and Y ６ each independently represents -CR Ｙ２ = or a nitrogen atom. R Ｙ２ represents a hydrogen atom or a substituent. It is preferable that at least one of Y ５ and Y ６ represents -CR Ｙ１ =, and it is more preferable that both Y ５ and Y ６ represent -CR Ｙ１ =. Examples of the above-mentioned substituent include the substituents exemplified by the above-mentioned substituent W, and a group selected from the above-mentioned substituent group S is preferable, and an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or a fluorine atom is more preferable.

[0064] Y ５ and Y ６ When R Ｙ１ is a substituent and is -CR Ｙ１ =, R Ｙ１The substituents represented by may be bonded to each other to form a ring which may have substituents. The ring may be either an aromatic ring or a non-aromatic ring, but an aromatic ring is preferred, and an aromatic hydrocarbon ring is more preferred. The ring may also be monocyclic or polycyclic. The number of ring member atoms of the ring is preferably 5 to 30, more preferably 5 to 12, and even more preferably 5 to 10. The ring may be a benzene ring, naphthalene ring, anthracene ring, pyrene ring, thiophene ring, furan ring, thiazole ring, oxazole ring, pyridine ring, thienothiophene ring, benzothiophene ring, benzofuran ring, pyrazine ring, pyrimidine ring, or pyridazine ring, more preferably a benzene ring, naphthalene ring, or thiophene ring, and even more preferably a benzene ring. Examples of substituents that the ring may have include the group exemplified by substituent W, and a group selected from the substituent group S is preferred, with alkyl groups (preferably having 1 to 5 carbon atoms) or halogen atoms being more preferred. The number of substituents that the above ring may have is not particularly limited, but is preferably 0 to 8, and more preferably 0 to 4.

[0065] In formula (A2-4), W ４ ~W ６ Each of these independently represents either an oxygen atom or a sulfur atom. In terms of the superior effects of the present invention, W ４ and W ５ It is preferable that is an oxygen atom, W ４ ~W ６ It is more preferable that it is an oxygen atom. Ｗ３ and R Ｗ４ Each of these independently represents an optionally substituted aliphatic hydrocarbon group. The optionally substituted aliphatic hydrocarbon group may be linear, branched, or cyclic, with linear being preferred. The carbon number of the optionally substituted aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. Examples of substituents that the aliphatic hydrocarbon group may have include those exemplified by substituent W above, and substituents selected from the substituent group S are preferred. Among the optionally substituted aliphatic hydrocarbon groups, alkyl groups are particularly preferred.

[0066] ・Formula (A2-2) In the above formula (A2-2), R Ａ１ is a cyano group, -COR Ａ２ , or -COOR Ａ３ It represents a cyano group, and a cyano group is preferred. Ａ２ and R Ａ３ Each of these independently represents an aromatic ring group which may have substituents or an aliphatic hydrocarbon group which may have substituents. The definition of an aromatic ring group is as described above, with aromatic hydrocarbon groups preferred and phenyl groups more preferred. The definition of an aliphatic hydrocarbon group is as described above, with aliphatic hydrocarbon groups having 1 to 3 carbon atoms preferred. Above R Ａ２ and R Ａ３ Examples of substituents that each group represented by the above substituent W may have include the substituents exemplified by the above substituent group S, and groups selected from the above substituent group S are preferred, with alkyl groups (preferably having 1 to 5 carbon atoms) or halogen atoms being more preferred.

[0067] From the following specific compounds (compounds represented by formula (1)), R １ , R ２ A １ and A ２ Specific examples of residues excluding R are shown, but the present invention is not limited to these. １ and R ２ A hydrogen atom is preferred as the element.

[0068]

[0069] The following are specific examples of the group represented by formula (A2-1) in the specified compound, but the present invention is not limited to these groups. Some of the groups shown below correspond to any of the groups represented by formulas (A1-1) to (A1-3).

[0070]

[0071]

[0072]

[0073] The following are specific examples of the group represented by formula (A2-2) in the specified compound, but the present invention is not limited to these groups.

[0074]

[0075] The molecular weight of the specific compound is preferably 300 to 1000, more preferably 350 to 900, and even more preferably 400 to 800. It is presumed that when the molecular weight is as described above, the sublimation temperature of the specific compound will be lower, resulting in excellent manufacturability.

[0076] The specific compound is preferably one with a single-film ionization potential of -5.0 to -6.0 eV, in terms of stability when used as a p-type organic semiconductor and energy level matching with an n-type organic semiconductor.

[0077] The maximum absorption wavelength of the specific compound is preferably in the range of 400 to 600 nm, and more preferably in the range of 400 to 500 nm. The above maximum absorption wavelength is the value measured in solution (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1.0. However, if the specific compound does not dissolve in chloroform, the maximum absorption wavelength of the specific compound is determined by measuring the value obtained using the specific compound in the form of a film after deposition.

[0078] The specific compound is particularly useful as a material for photoelectric conversion films used in image sensors, optical sensors, or photocells. The specific compound often functions as a dye within the photoelectric conversion film. Furthermore, the specific compound can also be used as a coloring material, liquid crystal material, organic semiconductor material, charge transport material, pharmaceutical material, and fluorescent diagnostic agent material.

[0079] The specific compound may be purified as needed. Examples of purification methods for the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, slurry washing, reprecipitation purification, purification using adsorbents such as activated carbon, and recrystallization purification.

[0080] The content of the specific compound in the photoelectric conversion film (= film thickness of the specific compound on a single-layer basis / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 5 to 75 volume%, more preferably 10 to 50 volume%, and even more preferably 15 to 40 volume%. Only one specific compound may be used, or two or more may be used. When two or more are used, it is preferable that their total amount is within the above range.

[0081] <n-type organic semiconductor> The photoelectric conversion film preferably contains an n-type organic semiconductor in addition to the specified compounds mentioned above. The n-type organic semiconductor is a compound different from the specified compounds mentioned above. The n-type organic semiconductor is an acceptor organic semiconductor material (compound), and refers to an organic compound that has the property of readily accepting electrons. In other words, the n-type organic semiconductor is the organic compound with the greater electron affinity when two organic compounds are used in contact. In other words, any organic compound that has electron-accepting properties can be used as an acceptor organic semiconductor. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and their derivatives; condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives); and heterocyclic compounds of 5 to 7 membered rings having at least one atom selected from the group consisting of nitrogen, oxygen, and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole, etc.). ); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic acid dianhydride; 1,4,5,8-naphthalenetetracarboxylic acid diimide derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and their derivatives; triazole compounds; distylyl arylene derivatives; metal complexes having nitrogen-containing heterocyclic compounds as ligands; silole compounds; 3,4,9,10-perylenetetracarboxylic acid dianhydride; 3,4,9,10-perylenetetracarboxylic acid diimide derivatives; and the compounds described in paragraphs

[0056] to

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

[0082] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerenes and their derivatives are preferred. 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 Examples include , and mixed fullerenes. Fullerene derivatives include, for example, compounds obtained by adding substituents to the above fullerene. Preferred substituents are alkyl groups, aryl groups, or heterocyclic groups. As fullerene derivatives, compounds described in Japanese Patent Application Publication No. 2007-123707 are preferred.

[0083] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.

[0084] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less, or in the range of 400 to 600 nm.

[0085] The photoelectric conversion film preferably has a bulk heterostructure formed in a state in which a specific compound and an n-type organic semiconductor are mixed. The bulk heterostructure is a layer in the photoelectric conversion film in which the specific compound and the n-type organic semiconductor are mixed and dispersed. The photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. The bulk heterostructure is described in detail in paragraphs

[0013] to

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

[0086] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or greater.

[0087] The n-type organic semiconductor may be used alone or in combination of two or more types. When the photoelectric conversion film contains an n-type organic semiconductor, the content of the n-type organic semiconductor in the photoelectric conversion film (film thickness of the n-type organic semiconductor on a single-layer basis / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75 volume%, more preferably 20 to 60 volume%, and even more preferably 20 to 50 volume%.

[0088] When the n-type organic semiconductor contains fullerenes, the content of fullerenes relative to the total content of the n-type organic semiconductor (film thickness of fullerenes on a single-layer basis / total film thickness of each n-type organic semiconductor on a single-layer basis × 100) is preferably 50 to 100 volume%, and more preferably 80 to 100 volume%. Fullerenes may be used individually or in combination of two or more types.

[0089] In terms of the response speed of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (film thickness of the specific compound on a single-layer basis / (film thickness of the specific compound on a single-layer basis + film thickness of the n-type organic semiconductor on a single-layer basis) × 100) is preferably 20 to 80 volume%, and more preferably 40 to 80 volume%. When the photoelectric conversion film contains an n-type organic semiconductor and a p-type organic semiconductor, the content of the specific compound (film thickness of the specific compound on a single-layer basis / (film thickness of the specific compound on a single-layer basis + film thickness of the n-type organic semiconductor on a single-layer basis + film thickness of the p-type organic semiconductor on a single-layer basis) × 100) is preferably 10 to 75 volume%, and more preferably 15 to 50 volume%. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, an n-type organic semiconductor, and a p-type organic semiconductor included as desired. "Substantial" means that the total content of the specific compound, n-type organic semiconductor, and p-type organic semiconductor relative to the total mass of the photoelectric conversion film is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume.

[0090] <p-type organic semiconductor> The photoelectric conversion film preferably contains a p-type organic semiconductor in addition to the specified compounds mentioned above. The p-type organic semiconductor is a compound different from the specified compounds mentioned above. A p-type organic semiconductor is a donor organic semiconductor material (compound), which is an organic compound that readily donates electrons. In other words, a p-type organic semiconductor is the organic compound with the smaller ionization potential when two organic compounds are brought into contact. A single p-type organic semiconductor may be used, or two or more may be used.

[0091] Examples of p-type organic semiconductors include triarylamine compounds (for example, 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, and compounds described in paragraphs

[0119] to

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

[0044] to

[0051] of Japanese Patent Publication No. 2015-153910, and compounds described in paragraphs

[0086] to

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

[0031] to

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

[0043] to

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

[0025] to

[0037] and

[0099] to

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

[0029] to

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

[0015] to

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

[00] of JP 2019-054228. Compounds described in paragraphs

[45] to

[0053] , compounds described in paragraphs

[0045] to

[0055] of WO2019 / 058995, compounds described in paragraphs

[0063] to

[0089] of WO2019 / 081416, compounds described in paragraphs

[0033] to

[0036] of JP 2019-80052, compounds described in paragraphs

[0044] to

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

[0041] to

[0046] of WO2019 / 093188, compounds described in paragraphs

[0034] to

[0037] of JP 2019-050398,The compounds described in paragraphs

[0033] to

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

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

[0019] to

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

[0031] to

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

[0036] to

[0041] of Japanese Patent Publication No. 2018-078270, and Japanese Patent Publication No. 2018-166200 The compounds described in paragraphs

[0055] to

[0082] of the Patent Publication No. 2018-113425, the compounds described in paragraphs

[0041] to

[0050] of the Patent Publication No. 2018-085430, the compounds described in paragraphs

[0044] to

[0048] of the Patent Publication No. 2018-056546, the compounds described in paragraphs

[0041] to

[0045] of the Patent Publication No. 2018-046267, and paragraphs

[0042] to

[0049] of the Patent Publication No. 2018-014474 Examples include compounds described in

[0031] to

[0036] , 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.), cyanine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives, etc.), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, aminosubstituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having nitrogen-containing heterocyclic compounds as ligands. Furthermore, as p-type organic semiconductors, benzoxazole compounds (for example, the compounds described in Figures 3 to 7 of Japanese Patent Publication No. 2022-123944), dicarbazole compounds (for example, the compounds described in Figures 2 to 5 of Japanese Patent Publication No. 2022-122839), benzoquinazoline compounds (for example, the compounds described in paragraphs

[0053] to

[0056] of Japanese Patent Publication No. 2022-120323),Azine compounds (for example, compounds described in paragraphs

[0041] to

[0042] of Japanese Patent Publication No. 2022-120273), compounds described in Figures 2 to 10 of Japanese Patent Publication No. 2022-115832, indrotriphenylene compounds (for example, compounds described in paragraphs

[0065] to

[0072] of Japanese Patent Publication No. 2022-108268), indrocarbazole compounds (for example, paragraphs

[0052] to [00 Examples include compounds described in paragraph

[0028] of Japanese Patent Publication No. 2022-100258, triscarbazolylphenyl compounds (for example, compounds described in paragraphs

[0038] to

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

[0070] to

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

[0051] to

[0064] of Japanese Patent Publication No. 2021-163968. As p-type organic semiconductors, for example, compounds with a smaller ionization potential than n-type organic semiconductors can be used, and if this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductor compounds are given below.

[0092]

[0093]

[0094]

[0095]

[0096] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or greater.

[0097] The p-type organic semiconductor material may be used alone or in combination of two or more types. When the photoelectric conversion film contains a p-type organic semiconductor, the p-type organic semiconductor content in the photoelectric conversion film (film thickness of the p-type organic semiconductor on a single-layer basis / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75 volume%, more preferably 20 to 60 volume%, and even more preferably 25 to 50 volume%.

[0098] Photoelectric conversion films containing specific compounds are non-luminescent films and have characteristics different from organic light-emitting diodes (OLEDs). A non-luminescent film is defined as a film with a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less. The lower limit is often 0% or more.

[0099] <Dyes> The photoelectric conversion film preferably contains a dye in addition to the specified compounds mentioned above. The dye is a compound different from the specified compounds mentioned above. Organic dyes are preferred as dyes. Examples of organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azametine dyes, coumarin dyes, allylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, and Examples of organic dyes include cridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, imidazoquinoxaline dyes described in WO2020 / 013246, WO2022 / 168856, Japanese Patent Publication No. 2023-10305, and Japanese Patent Publication No. 2023-10299, as well as acceptor-donor-acceptor type dyes in which two acidic nuclei are bound to a donor, and donor-acceptor-donor type dyes in which two donors are bound to an acceptor. Among the organic dyes, cyanine dyes, imidazoquinoxaline dyes, or acceptor-donor-acceptor type dyes are preferred.

[0100] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably in the range of 400 to 650 nm, and even more preferably in the range of 450 to 650 nm.

[0101] The dye may be used alone or in combination of two or more types. The amount of dye in the photoelectric conversion film relative to the total amount of the specific compound and the dye (= (film thickness of the dye on a single-layer basis / (film thickness of the specific compound on a single-layer basis + film thickness of the dye on a single-layer basis) × 100)) is preferably 5 to 75 volume%, more preferably 5 to 60 volume%, and even more preferably 5 to 50 volume%.

[0102] The photoelectric conversion film may contain optional components in addition to the components described above. Examples of optional components include antioxidants, dispersants, and ultraviolet absorbers. Furthermore, the optional components may be specific compounds, n-type organic semiconductors, p-type organic semiconductors, or impurities derived from dyes. When the photoelectric conversion film contains optional components, the content of the optional components in the photoelectric conversion film (film thickness of the optional component on a single-layer basis / film thickness of the photoelectric conversion film × 100) is preferably 0.01 to 10 volume%, and more preferably 0.01 to 1 volume%.

[0103] <Method of Film Formation> As a method for forming the above-mentioned photoelectric conversion film, for example, a dry film formation method can be used. Examples of dry film formation methods include vapor deposition (especially vacuum deposition), sputtering, ion plating, and physical vapor deposition methods such as MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization, with vacuum deposition being preferred. When forming a photoelectric conversion film by vacuum deposition, manufacturing conditions such as the degree of vacuum and deposition temperature can be set according to conventional methods.

[0104] The film thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and even more preferably 50 to 500 nm.

[0105] [Electrodes] The photoelectric conversion element preferably has electrodes. The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of conductive materials include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as antimony tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); thin metal films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, as well as nanocarbon materials such as carbon nanotubes and graphene. Conductive metal oxides are preferred in terms of high conductivity and transparency.

[0106] Typically, when a conductive film is made thinner than a certain range, its resistance often increases sharply. In the solid-state image sensor incorporating the photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10000 Ω / □, and there is a great degree of freedom in the range of film thickness that can be thinned. Also, the thinner the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the light transmittance increases. An increase in light transmittance is desirable because it increases light absorption in the photoelectric conversion film and increases the photoelectric conversion ability. Considering the suppression of leakage current, the increase in the resistance of the thin film, and the increase in transmittance associated with thinning, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0107] The lower electrode 11 may be made transparent or opaque to reflect light, depending on the application. Examples of materials that make up the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and zinc indium oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and graphene.

[0108] 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 deposition, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD. When the electrode material is ITO, examples include electron beam methods, sputtering, resistance heating deposition, chemical reaction methods (sol-gel method, etc.), and coating of indium tin oxide dispersions.

[0109] [Charge-blocking films: electron-blocking films, hole-blocking films] It is preferable that the photoelectric conversion element has one or more intermediate layers between the conductive film and the transparent conductive film, in addition to the photoelectric conversion film. An example of the above intermediate layer is a charge-blocking film. When the photoelectric conversion element has this film, the characteristics of the resulting photoelectric conversion element (quantum efficiency, response speed, etc.) are better. Examples of charge-blocking films include electron-blocking films and hole-blocking films.

[0110] <Electron Blocking Film> The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. Polymer materials can also be used as electron blocking films. Examples of polymer materials include polymers such as phenylenevinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, as well as their derivatives.

[0111] Furthermore, the electron blocking film may be composed of multiple films. The electron blocking film may also be composed of inorganic materials. Generally, inorganic materials have a higher dielectric constant than organic materials, so when inorganic materials are used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher quantum efficiency. Examples of inorganic materials that can be used as electron blocking films include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

[0112] <Hole Blocking Film> The hole blocking film is an acceptor-type organic semiconductor material (compound), and the above-mentioned n-type organic semiconductor can be used. The hole blocking film may also be composed of multiple films.

[0113] Examples of methods for manufacturing charge-blocking films include dry deposition and wet deposition. Examples of dry 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 deposition being preferred. Examples of wet deposition methods include inkjet, spray, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with inkjet being preferred in terms of high-precision patterning.

[0114] The thickness of the charge blocking film (electron blocking film and hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm, respectively.

[0115] [Substrate] The photoelectric conversion element may further have a substrate. Examples of substrates include semiconductor substrates, glass substrates, and plastic substrates. Typically, the substrates are layered on the substrate in the following order: conductive film, photoelectric conversion film, and transparent conductive film.

[0116] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. Photoelectric conversion materials can be significantly degraded in performance due to the presence of degradation factors such as water molecules. Therefore, the entire photoelectric conversion film can be sealed by covering it with a sealing layer made of a dense metal oxide, metal nitride or metal nitride oxide ceramic, or diamond-like carbon (DLC), which does not allow water molecules to penetrate, thereby preventing the above-mentioned degradation. Examples of sealing layers include those described in paragraphs

[0210] to

[0215] of Japanese Patent Application Publication No. 2011-082508, and these contents are incorporated herein by reference.

[0117] [Method for Manufacturing a Photoelectric Conversion Element] Known manufacturing methods can be used to manufacture a photoelectric conversion element. Specifically, for example, a method for manufacturing a photoelectric conversion element can be used that includes the steps of forming a conductive film on a substrate, forming a photoelectric conversion film, and forming a transparent conductive film. The method for manufacturing a photoelectric conversion element may also include other steps (for example, a step of forming a charge blocking film and a step of forming a sealing layer). The method for forming each layer is as described above.

[0118] [Image Sensor] One example of an application of photoelectric conversion elements is an image sensor. An image sensor is an element that converts the optical information of an image into an electrical signal. Typically, multiple photoelectric conversion elements are arranged in a matrix on the same plane, and each photoelectric conversion element (pixel) converts the optical signal into an electrical signal, and these electrical signals can be output sequentially to the outside of the image sensor for each pixel. For this purpose, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. The method of manufacturing an image sensor is not particularly limited, but one example is a method that includes the process of manufacturing the photoelectric conversion elements described above.

[0119] [Optical Sensor] Other applications of the photoelectric conversion element include, for example, photocells and optical sensors, and the photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element may be used alone, or it may be used as a line sensor in which the photoelectric conversion elements are arranged in a straight line or as a two-dimensional sensor arranged on a plane.

[0120] [Compounds] This invention also includes inventions of specific compounds.

[0121] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0122] [Compounds used in photoelectric conversion films] The following lists the materials used in the photoelectric conversion films.

[0123] [Synthesis of Compound (B-2)] Compound (B-2) was synthesized according to the following scheme.

[0124]

[0125] <Synthesis of Intermediate (B-2A)> Intermediate (B-2A) was synthesized according to the method described in Journal of Physical Chemistry C, 2011, 115, 22640-22646.

[0126] <Synthesis of Intermediate (B-2B)> Intermediate (B-2A) (9.5 g) and tetrahydrofuran (THF, 340 mL) were placed in a round-bottom flask, and the reaction mixture was cooled to -78°C under a nitrogen atmosphere. Lithium diisopropylamide (LDA, n-hexane-THF solution (1.0 M), 100 mL) was added dropwise, and the mixture was stirred at -78°C for 1 hour. Then tert-butyldimethylchlorosilane (TMDMSCl, 19 g) was added, and the mixture was heated to room temperature before adding water (100 mL). The resulting reaction mixture was extracted with ethyl acetate, and the recovered organic phase was washed with saturated brine, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The resulting crude product was purified by silica gel column chromatography (eluent: n-hexane) to obtain 3.42 g of intermediate (B-2B) (yield 26%). １ The H-NMR (Nuclear Magnetic Resonance) data is shown below. １ H-NMR (CD) ２ Cl ２ ): δ (ppm) = 7.32 (s, 1H), 7.21 (d, 1H), 7.11 (d, 1H), 6.98 (s, 1H), 1.27 (s, 6H), 0.77 (s, 9H), 0.15 (s, 6H).

[0127] <Synthesis of Intermediate (B-2C)> 5.22 g of intermediate (B-2B) and 133 mL of tetrahydrofuran (THF) were placed in a round-bottom flask. The reaction mixture was cooled to -78°C under a nitrogen atmosphere. 12 mL of n-butyllithium (hexane solution (1.6 M), 12 mL) was added dropwise, and the mixture was stirred at -78°C for 15 minutes. Then, 2.1 mL of N,N-dimethylformamide (DMF) was added, and the mixture was heated to room temperature before adding 53 mL of water. The resulting reaction mixture was extracted with ethyl acetate, the recovered organic phase was washed with saturated brine, dried over sodium sulfate, and the solvent was removed by vacuum distillation to obtain 4.03 g of intermediate (B-3C) (89% yield). １ The H-NMR data is shown below. １ H-NMR (CDCl ３): δ (ppm) = 10.00 (s, 1H), 7.89 (s, 1H), 7.79 (d, 1H), 7.53 (d, 1H), 7.16 (s, 1H), 1.51 (s, 6H), 0.97 (s, 9H), 0.35 (s, 6H).

[0128] <Synthesis of Intermediate (B-2D)> Intermediate (B-2C) (4.03 g) and tetrahydrofuran (THF, 40 mL) were placed in a round-bottom flask, and tetrabutylammonium fluoride (TBAF, THF solution (1.0 M), 13 mL) was added dropwise. After stirring at room temperature for 1 hour, 5% sodium bicarbonate aqueous solution (40 mL) was added. The resulting reaction mixture was extracted with ethyl acetate, the recovered organic phase was washed with saturated brine, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The resulting crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 95 / 5-90 / 10) to obtain 1.72 g of intermediate (B-2D) (yield 64%). １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ (ppm) = 10.00 (s, 1H), 7.90 (s, 1H), 7.80 (d, 1H), 7.54 (d, 1H), 7.46 (d, 1H), 7.08 (d, 1H), 1.51 (s, 6H).

[0129] <Synthesis of Intermediate (B-2E)> Intermediate (B-2D) (1.7 g), ethanol (34 mL), triethyl orthoformate (3.3 g), and ammonium chloride (200 mg) were placed in a round-bottom flask and stirred at 80°C for 2 hours, after which 5% sodium bicarbonate aqueous solution (40 mL) was added. The resulting reaction mixture was extracted with ethyl acetate, the recovered organic phase was washed with saturated brine, dried with sodium sulfate, and the solvent was removed by vacuum distillation to obtain 2.08 g of intermediate (B-2E) (yield 92%). １ The H-NMR data is shown below. １ H-NMR (CD) ２ Cl ２): δ (ppm) = 7.50 (s, 1H), 7.43 (d, 1H), 7.38 (d, 1H), 7.36 (d, 1H), 7.10 (d, 1H), 5.53 (s, 1H), 3.71-3.54 (m, 4H), 1.50 (s, 6H), 1.27 (t, 6H).

[0130] <Synthesis of Intermediate (B-2F)> Intermediate (B-2E) (2.08 g) and tetrahydrofuran (THF, 69 mL) were placed in a round-bottom flask, and the reaction mixture was cooled to -78°C under a nitrogen atmosphere. Lithium diisopropylamide (LDA, n-hexane-THF solution (1.0 M), 21 mL) was added dropwise, and the mixture was stirred at -78°C for 2 hours. Then, N,N-dimethylformamide (DMF, 2.7 mL) was added, and the mixture was heated to room temperature before adding water (20 mL). The resulting reaction mixture was extracted with ethyl acetate, and the recovered organic phase was washed with saturated brine, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The resulting crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 95 / 5-70 / 30) to obtain 2.17 g of intermediate (B-2F) (yield 96%). １ The H-NMR data is shown below. １ H-NMR (CD) ２ Cl ２ ): δ (ppm) = 9.91 (s, 1H), 7.76 (s, 1H), 7.59 (d, 1H), 7.58 (s, 1H), 7.47 (d, 1H), 5.55 (s, 1H), 3.71-3.55 (m, 4H), 1.55 (s, 6H), 1.27 (t, 6H).

[0131] <Synthesis of Compound (B-2G)> Intermediate (B-2F) (2.1 g), 4,5-dimethyl-4-cyclopentene-1,3-dione (0.95 g), n-butanol (21 mL), and piperidine (128 μL) were placed in a round-bottom flask and reacted at 80°C for 4 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, and the precipitated solid was filtered off to obtain compound (B-2G) (2.05 g, yield 73%). １ The H-NMR data is shown below. １ H-NMR (CD) ２ Cl ２): δ (ppm) = 7.96 (1H, s), 7.61 (1H, d), 7.60 (1H, s), 7.56 (1H, s), 7.47 (1H, d), 5.5 5 (1H, s), 3.72-3.55 (m, 4H), 2.11 (3H, s), 2.09 (3H, s), 1.55 (6H, s), 1.27 (6H, t).

[0132] <Synthesis of Compound (B-2H)> Intermediate (B-2G) (2.0 g), tetrahydrofuran (THF, 40 mL), and aqueous hydrochloric acid (1.0 M, 9.2 mL) were placed in a round-bottom flask and stirred at room temperature under a nitrogen atmosphere for 30 minutes. Then, water (40 mL) was added, and the precipitated solid was filtered off to obtain compound (B-2H) (1.51 g, yield 91%). １ The H-NMR data is shown below. １ H-NMR (CD) ２ Cl ２ ): δ (ppm) = 10.07 (1H, s), 7.98 (1H, s), 7.97 (1H, s), 7.90 (1H, d), 7.76 (1H, d), 7.61 (1H, s), 2.13 (3H, s), 2.10 (3H, s), 1.58 (6H, s).

[0133] <Synthesis of Compound (B-2)> Intermediate (B-2H) (1.50 g), 1-ethyl-3-methylbarbituric acid (1.29 g), n-butanol (30 mL), and piperidine (82 μL) were placed in a round-bottom flask and reacted at 80°C for 8 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, the precipitated solid was filtered off, and the resulting crude product was recrystallized with methylene chloride / methanol. The obtained solid was purified by sublimation to obtain compound (B-2) (991 mg, yield 46%). １ The H-NMR data is shown below. １ H-NMR (CD) ２ Cl ２ ): δ (ppm) = 8.61 (1H, s), 8.31 (1H, d), 8.21 (1H, dd), 7.98 (1H, d), 7.70 (1H, d), 7.62 (1H, s), 4.10-4.04 (m, 2H), 3.41 (3H, d), 2.13 (3H, s), 2.10 (3H, s), 1.60 (6H, s), 1.28 (3H, t).

[0134] The compounds used in each example and comparative example for photoelectric conversion films other than compound (B-2) are synthesized in accordance with the synthesis method of compound (B-2).

[0135] [Specific Compounds] The specific compounds used in the photoelectric conversion film and comparative compounds for the comparative examples are shown below. Compounds (B-1) to (B-16) are specific compounds, and compounds (C1) to (C2) are comparative compounds.

[0136]

[0137]

[0138] [n-type organic semiconductors] ・Fullerene (C ６０ )

[0139] [p-type organic semiconductor]

[0140]

[0141] [Pigment]

[0142]

[0143] [Evaluation] The dependence of the response speed of the photoelectric conversion element on electric field strength when receiving blue-green light (wavelength 460 nm) will be evaluated using the following method.

[0144] [Fabrication of Photoelectric Conversion Element] A photoelectric conversion element in the form shown in Figure 2 is fabricated using the various components shown above. Here, the photoelectric conversion element consists 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. Specifically, amorphous ITO is deposited on a glass substrate by sputtering to form the lower electrode 11 (thickness: 30 nm), and then a compound (EB-1) is deposited on the lower electrode 11 by vacuum heating deposition to form the electron blocking film 16A (thickness: 30 nm). Subsequently, with the glass substrate at room temperature, each specific compound or each comparative compound shown in Table 1 and an n-type organic semiconductor (fullerene (C)) are deposited on the electron blocking film 16A. ６０A p-type organic semiconductor (D-1) and a photoelectric conversion film (AL) are co-deposited by vacuum deposition to form a film with a single-layer equivalent thickness of 133 nm. This forms a photoelectric conversion film 12 having a bulk heterostructure of 400 nm. The deposition rate of the photoelectric conversion film 12 is set to 1.0 Å / sec. A compound (EB-2) is then deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO is deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). An SiO film is formed on the upper electrode 15 as a sealing layer by vacuum deposition, and then aluminum oxide (Al) is deposited on top of it by ALCVD (Atomic Layer Chemical Vapor Deposition). ２ O ３ A layer is formed, and the resulting laminate is heated in a glove box at 150°C for 30 minutes to obtain a photoelectric conversion element.

[0145]

[0146] [Dark Current] The dark current of each obtained photoelectric conversion element is measured using the following method. 2.5 × 10⁻¹⁰ ions are applied to the lower and upper electrodes of each photoelectric conversion element. ５ A voltage is applied to achieve an electric field strength of V / cm, and the current value in the dark (dark current) is measured. As a result, the dark current for all photoelectric conversion elements was 50 nA / cm. ２ The following is observed, and it is confirmed that a sufficiently low dark current is present.

[0147] [Dependence of response speed (responsiveness) on electric field strength] For each photoelectric conversion element, the dependence of the response speed on electric field strength when blue-green light is received is evaluated using the following method. 2.0 × 10⁻¹⁰ ５ A voltage is applied to achieve an intensity of V / cm. Then, the LED (light emitting diode) is momentarily lit to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 460 nm is measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity. Subsequently, the voltage applied to each photoelectric conversion element is set to 7.0 × 10⁻¹⁰. ４Except for changing to V / cm, the procedure was the same: 7.0 × 10 ４ The response speed at V / cm is measured. The obtained value is 2.0 × 10⁻⁶. ５ Response speed at V / cm, and 7.0 × 10 ４ From the response speed value at V / cm, the electric field strength dependence of the response speed is calculated according to equation (S1), and the electric field strength dependence of the quantum efficiency is evaluated according to the evaluation criteria below. Note that in equation (S1), each photoelectric conversion element in the numerator and denominator is the same. For example, for Example 1-1, the photoelectric conversion efficiency of Example 1-1 at a wavelength of 460 nm is 7.0 × 10⁻⁶. ４ The rise time at V / cm and the photoelectric conversion efficiency of Example 1-1 at a wavelength of 460 nm was 2.0 × 10⁻⁶. ５ Compare with the rise time at V / cm. Equation (S1): Dependence of response speed on electric field strength = (7.0 × 10⁻¹⁰ at a wavelength of 460 nm for each example or comparative example) ４ (Rise time at V / cm) / (2.0 × 10⁻¹⁰ at a wavelength of 460 nm for each example or comparative example) ５ (Rise time at V / cm)

[0148] (Evaluation Criteria) A: Response speed dependence on electric field strength is less than 2.0 B: Response speed dependence on electric field strength is 2.0 or more, but less than 3.0 C: Response speed dependence on electric field strength is 3.0 or more, but less than 4.0 D: Response speed dependence on electric field strength is 4.0 or more, but less than 5.0 E: Response speed dependence on electric field strength is 5.0 or more

[0149] [Results] The evaluation results are shown in the table below. In the table, the "Formula (1)" column is marked "A" if the compound is represented by formula (1), and "B" otherwise. In the table, the "Formula (A2-1)" column is marked A for the specific compound. １ and A ２ If one of the groups is represented by formula (A2-1), it is designated as "A," and in all other cases, it is designated as "B." In the table, the "Formula (A2-3), Formula (A2-4)" column indicates that in a specific compound, A １ and A ２If the other is a group represented by formula (A2-3) or formula (A2-4), it is designated as "A", and in all other cases, it is designated as "B". In the table, the "Formula (A1-1), (A1-2)" column indicates that in a specific compound, A １ and A ２ If at least one of the groups is represented by either formula (A1-1) or formula (A1-2), it is designated as "A", and otherwise it is designated as "B". In the table, the column "Formula (A2-3) × Formula (A1-1), (A1-2)" indicates that in a specific compound, A １ and A ２ If one of the groups is a group represented by formula (A2-3) and the other is a group represented by either formula (A1-1) or formula (A1-2), it is designated as "A"; otherwise, it is designated as "B".

[0150]

[0151] The table shows that the photoelectric conversion element of the present invention exhibits low dependence of the electric field strength on the response speed to blue-green light.

[0152] Furthermore, from a comparison between Examples 1-3 and 1-5 and Example 1-11, it was found that in a specific compound, A １ and A ２ When one of the groups is represented by formula (A2-1), it is shown that the electric field strength dependence of the response speed to blue-green light is smaller. Comparison of Examples 1-4 and 1-10 shows that in a specific compound, A １ and A ２ When at least one of the groups is represented by either formula (A1-1) or formula (A1-2), it is shown that the electric field strength dependence of the response speed to blue-green light is smaller. Comparison of Examples 1-10 and 1-11 shows that in a specific compound, A １ and A ２ When the other is a group represented by formula (A2-3) or formula (A2-4), it is shown that the electric field strength dependence of the response speed to blue-green light is smaller. From a comparison of Examples 1-7 to 1-10, it is shown that in a specific compound, A １ and A ２When one of the groups is represented by formula (A2-3) and the other is represented by either formula (A1-1) or formula (A1-2), it is shown that the electric field strength dependence of the response speed to blue-green light is smaller.

[0153] Next, in addition to the specific compound or comparative compound, a photoelectric conversion element is fabricated using a dye other than the specific compound, and the electric field strength dependence of the response speed of the photoelectric conversion element when it receives blue-green light (wavelength 460 nm) is evaluated using the following method.

[0154] Each specific compound or each comparative compound, n-type organic semiconductor (fullerene (C) ６０ A photoelectric conversion element is fabricated using the same procedure as described above, except that a photoelectric conversion film (thickness 320 nm) is formed by co-depositing a p-type organic semiconductor (compound (D-1)) and one of the dyes selected from (R-1) to (R-10) by vacuum deposition in a single-layer ratio of specific compound:dye:p-type organic semiconductor:n-type organic semiconductor = 1:1:2:2. As a result, even when a dye is used in combination, the results are similar to those of the electric field strength dependence of the response speed shown in the table. Specifically, for example, a photoelectric conversion element fabricated using compound B-1 according to the above method shows evaluation results equivalent to Example 1-1 in Table 1. Photoelectric conversion elements are fabricated and evaluations are performed for all combinations of each specific compound and each dye.

[0155] 10a, 10b Photoelectric conversion element 11 Conductive film (lower electrode) 12 Photoelectric conversion film 15 Transparent conductive film (upper electrode) 16A Electron blocking film 16B Hole blocking film

Claims

1. A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1). In formula (1), R ｘ１ and R ｘ２ each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. R ｘ１ and R ｘ２ may be linked to each other to form a ring. The ring may have a substituent. R １ and R ２ each independently represent a hydrogen atom or a substituent. A １ and A ２ one of them represents a group represented by any one of formula (A1-1) to formula (A1-3), and the other represents a group represented by either formula (A2-1) or formula (A2-2). However, A １ and A ２ represent different groups from each other. In formula (A1-1) and formula (A1-2), R Ｗ１ and R Ｗ２ each independently represent an aliphatic hydrocarbon group which may have a substituent. In formula (A1-3), Y １ to Y ４ each independently represent -CR Ｙ１ = or a nitrogen atom. R Ｙ１ represents a hydrogen atom or a substituent. When two of Y １ to Y ４ are -CR Ｙ１ where R Ｙ１ is a substituent, the substituents represented by R Ｙ１ may be bonded to each other to form a ring which may have a substituent. In formula (A2-1), C １ contains two or more carbon atoms and represents a ring which may have a substituent. W １ represents a sulfur atom, an oxygen atom, =NR Ｗ３ , or =CR Ｗ４ R Ｗ５ represents a hydrogen atom or a substituent. R Ｗ３ represents a hydrogen atom or a substituent. R Ｗ４ and R Ｗ５ These are, independently, a cyano group and -SO ２ R Ｗ６ , -COOR Ｗ７ , or -COR Ｗ８ Represents R Ｗ６ ~R Ｗ８ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. In formula (A2-2), R Ａ１ The cyano group, -COR Ａ２ , or -COOR Ａ３ Represents R Ａ２ and R Ａ３ Each of these independently represents an optionally substituted aromatic ring group or an optionally substituted aliphatic hydrocarbon group. In formulas (A1-1) to (A1-3), (A2-1), and (A2-2), * represents a bond position.

2. The photoelectric conversion element according to claim 1, wherein the other is a base represented by formula (A2-1).

3. The photoelectric conversion element according to claim 1, wherein the other is a base represented by formula (A2-3) or formula (A2-4). In formula (A2-3), W ２ and W ３ Each of these independently represents either an oxygen atom or a sulfur atom. ５ and Y ６ Each of these is independently -CR Ｙ２ = or represents a nitrogen atom. R Ｙ２ represents a hydrogen atom or substituent. Y ５ and Y ６ However, R Ｙ１ -CR is a substituent Ｙ１ If =, R Ｙ１ The substituents represented by may bond to each other to form a ring which may have substituents. In formula (A2-4), W ４ ~W ６ Each of these independently represents either an oxygen atom or a sulfur atom. Ｗ３ and R Ｗ４ Each of these independently represents an aliphatic hydrocarbon group which may have substituents. In formulas (A2-3) and (A2-4), * represents a bond position.

4. The photoelectric conversion element according to claim 1, wherein one of the members is a base represented by either formula (A1-1) or formula (A1-2).

5. The photoelectric conversion element according to claim 3, wherein one of the members is a group represented by either formula (A1-1) or formula (A1-2), and the other member is a group represented by formula (A2-3).

6. The photoelectric conversion element according to any one of claims 1 to 5, wherein the photoelectric conversion film further comprises an n-type organic semiconductor, and the photoelectric conversion film has a bulk heterostructure formed by mixing the compound represented by formula (1) and the n-type organic semiconductor.

7. The photoelectric conversion element according to claim 6, wherein the n-type organic semiconductor comprises fullerenes selected from the group consisting of fullerenes and their derivatives.

8. The photoelectric conversion element according to any one of claims 1 to 5, wherein the photoelectric conversion film further comprises a p-type organic semiconductor.

9. The photoelectric conversion element according to any one of claims 1 to 5, wherein the photoelectric conversion film further comprises a dye.

10. A photoelectric conversion element according to any one of claims 1 to 5, wherein the conductive film and the transparent conductive film are interposed between them, and one or more intermediate layers in addition to the photoelectric conversion film.

11. An image sensor having a photoelectric conversion element according to any one of claims 1 to 5.

12. A light sensor having a photoelectric conversion element according to any one of claims 1 to 5.

13. A method for manufacturing an image sensor, comprising the step of manufacturing a photoelectric conversion element according to any one of claims 1 to 5.

14. A compound represented by formula (1). In formula (1), R ｘ１ and R ｘ２ Each of these independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ｘ１ and R ｘ２ These may be linked together to form a ring. The ring may have substituents. R １ and R ２ Each of these independently represents a hydrogen atom or a substituent. １ and A ２ One of them represents a group represented by any of formulas (A1-1) to (A1-3), and the other represents a group represented by either formula (A2-1) or formula (A2-2). However, A １ and A ２ R represents a different group from each other. In formulas (A1-1) and (A1-2), R Ｗ１ and R Ｗ２ Each of these independently represents an aliphatic hydrocarbon group which may have substituents. In formula (A1-3), Y １ ~Y ４ Each of these is independently -CR Ｙ１ = or represents a nitrogen atom. R Ｙ１ represents a hydrogen atom or substituent. Y １ ~Y ４ Two of them are R Ｙ１ -CR is a substituent Ｙ１ If =, R Ｙ１ The substituents represented by may bond to each other to form a ring which may have substituents. In formula (A2-1), C １ W represents a ring containing two or more carbon atoms, which may have substituents. １ This consists of a sulfur atom, an oxygen atom, and =NR Ｗ３ , or =CR Ｗ４ R Ｗ５ Represents R Ｗ３ R represents a hydrogen atom or substituent. Ｗ４ and R Ｗ５ These are, independently, a cyano group and -SO ２ R Ｗ６ , -COOR Ｗ７ , or -COR Ｗ８ represents. R Ｗ６ ~R Ｗ８ each independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. In formula (A2-2), R Ａ１ represents a cyano group, -COR Ａ２ , or -COOR Ａ３ represents. R Ａ２ and R Ａ３ each independently represents an aromatic ring group which may have a substituent or an aliphatic hydrocarbon group which may have a substituent. In formulas (A1-1) to (A1-3), formula (A2-1) and formula (A2-2), * represents a bonding position.

15. The compound according to claim 14, wherein the other is a group represented by formula (A2-1).

16. The compound according to claim 14, wherein the other party is a group represented by formula (A2-3) or formula (A2-4). In formula (A2-3), W ２ and W ３ each independently represents an oxygen atom or a sulfur atom. Y ５ and Y ６ each independently represents -CR Ｙ２ = or a nitrogen atom. R Ｙ２ represents a hydrogen atom or a substituent. Y ５ and Y ６ when is -CR Ｙ１ = where R Ｙ１ is a substituent, the substituents represented by R Ｙ１ may be bonded to each other to form a ring which may have a substituent. In formula (A2-4), W ４ to W ６ each independently represents an oxygen atom or a sulfur atom. R Ｗ３ and R Ｗ４ each independently represents an aliphatic hydrocarbon group which may have a substituent. In formula (A2-3) and formula (A2-4), * represents the bonding position.

17. The compound according to claim 14 or 15, wherein one of the members is a group represented by either formula (A1-1) or formula (A1-2).

18. The compound according to claim 16, wherein one of the members is a group represented by either formula (A1-1) or formula (A1-2), and the other member is a group represented by formula (A2-3).

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