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

Abstract

The present invention addresses the problem of providing a photoelectric conversion element having a low electric field strength dependence on response speed when blue-green light is received. A 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, said 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 dye compound with a specific structure as an active material for an organic image sensor.

[0003] Special table 2018-510845 publication

[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 response speed does not change significantly when the electric field strength is changed; in other words, its response speed 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. They found that the response speed when receiving blue-green light had a large dependence on electric field strength, indicating room for improvement. The blue-green light referred to above is light with a wavelength of 400 to 530 nm.

[0005] Therefore, the present invention aims to provide a photoelectric conversion element in which the response speed when receiving blue-green light has little dependence on the electric field strength. Furthermore, the present invention also aims to provide an image sensor, a light sensor, a method for manufacturing an 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] X １ However, -NR １ -, -CR ２ R ３ -, or -SiR ４ R ５- is the photoelectric conversion element according to [1]. [3] X ２ is a sulfur atom or an oxygen atom, the photoelectric conversion element according to [1] or [2]. [4] D is a group represented by the above formula (D-1), the photoelectric conversion element according to any one of [1] to [3]. [5] A １ and A ２ are each independently a group represented by the above formula (A-1), the photoelectric conversion element according to any one of [1] to [4]. [6] The above photoelectric conversion film further contains an n-type organic semiconductor, and the above photoelectric conversion film has a bulk heterostructure formed in a state where the compound represented by the above formula (1) and the above n-type organic semiconductor are mixed, according to any one of [1] to [5]. The photoelectric conversion element described. [7] The above n-type organic semiconductor contains fullerenes selected from the group consisting of fullerene and its derivatives, the photoelectric conversion element according to [6]. [8] The above photoelectric conversion film further contains a p-type organic semiconductor, the photoelectric conversion element according to any one of [1] to [7]. [9] The above photoelectric conversion film further contains a dye, the photoelectric conversion element according to any one of [1] to [8].

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

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

[10] .

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

[10] .

[13] A method for manufacturing an imaging device, which includes a step of manufacturing the photoelectric conversion element according to any one of [1] to

[10] .

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

[15] X １ is -NR １ -, -CR ２ R ３ -, or -SiR ４ R ５ -, is the compound according to

[14] .

[16] X ２ is a sulfur atom or an oxygen atom, the compound according to

[14] or

[15] .

[17] D is a group represented by the above formula (D-1), the compound according to any one of

[14] to

[16] .

[18] A １ and A ２However, each is independently a group represented by the above formula (A-1), which is one of the compounds described in any one of

[14] to

[17] .

[0008] According to the present invention, a photoelectric conversion element can be provided in which the response speed when receiving blue-green light has little dependence on the electric field strength. 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 groups and aliphatic heterocyclic groups), 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. Furthermore, the specific compounds described later offer superior effects of the present invention, and as substituents, they include carboxyl groups, salts of carboxyl groups, phosphate groups, salts of phosphate groups, sulfonic acid groups, salts of sulfonic acid groups, hydroxyl groups, thiol groups, acylamino groups, carbamoyl groups, ureido groups, and boronic acid groups (-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 has a fused ring structure containing multiple monocyclic aromatic rings (e.g., 2 to 6). The monocyclic aromatic ring is preferably a 5-membered or 6-membered ring. Furthermore, the polycyclic aromatic ring is preferably a fused ring structure containing multiple monocyclic aromatic rings selected from 5-membered and 6-membered rings (e.g., 2 to 6). It is also preferable that the polycyclic aromatic ring consists of a fused ring of monocyclic aromatic rings. Unless otherwise specified, the number of ring member atoms in the above aromatic ring is preferably 5 to 20. In this specification, the "number of ring member atoms" in a ring (aromatic rings, alicyclic rings, etc.) refers to the number of atoms constituting the ring structure, and in the case of polycyclic rings, it refers to the number of atoms constituting the polycyclic ring. In this specification, unless otherwise specified, an aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. When the aromatic ring is an aromatic heterocyclic ring, the number of heteroatoms it has as ring member atoms is, for example, 1 to 10. Examples of the heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron. Examples of the aromatic hydrocarbon rings include benzene, naphthalene, anthracene, pyrene, phenanthrene, 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 corresponding 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 corresponding 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 in only one form, either the cis or trans isomer. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans isomer, and the compound may be in either the cis or trans form. Furthermore, in this specification, with respect to compounds having a chiral atom, the general formula or structural formula representing the compound may, for convenience, be described without distinguishing between stereoisomers. Even in such cases, unless otherwise specified, the form of the compound is not limited to either form, and may be either one form or a mixture thereof. For example, a compound having a chiral carbon atom may, unless otherwise specified, be either the S or R isomer, or a mixture thereof.

[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 a 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 still 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). Such dye compounds tend to have high aggregation due to their conjugated structure. The specific compound has a predetermined fused ring structure as the donor structure and absorbs in the wavelength region of blue-green light. Furthermore, the combination of a specific compact donor portion and acceptor portion suppresses excessive aggregation in the photoelectric conversion film and carrier trapping by local dipoles, enabling efficient charge separation even at low electric field strengths. As a result, charge can move efficiently even at low electric field strengths; that is, the electric field strength dependence of the response speed when the photoelectric conversion element receives blue-green light is considered to be small. Hereinafter, a smaller dependence of the response speed of the photoelectric conversion element on the electric field strength will also be 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 Compounds> The photoelectric conversion film contains specific compounds, which are compounds represented by formula (1).

[0032]

[0033] In formula (1), D represents the group represented by formula (D-1) or the group represented by formula (D-2). １１ and R １２ Each of these independently represents a hydrogen atom or a substituent. １ and A ２ Each of these independently represents either the group represented by formula (A-1) or the group represented by formula (A-2). In formulas (D-1) and (D-2), X １ These are, independently, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, and -NR １ -, -CR ２ R ３ -, -SiR４ R ５ -, or -GeR ６ R ７ Represents -. R １ ~R ７ 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. ２ and R ３ These may be bonded to each other to form a ring which may have substituents, R ４ and R ５ These may be bonded to each other to form a ring which may have substituents, R ６ and R ７ These may be bonded to each other to form a ring which may have substituents. ２ and X ３ Each of these is independently a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or -NR １ This represents -. Y is independently -CR ｙ１ = or represents a nitrogen atom. R ｙ１ Z represents a hydrogen atom or substituent. １ ~Z ３ Of these, one represents -C(*) = and the other two independently represent -CR ｙ１ = represents a nitrogen atom. * represents a bond position. In formula (A-1), C １ This represents a ring containing two or more carbon atoms, which may have substituents. １ This consists of an oxygen atom, a sulfur atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ R represents a hydrogen atom or substituent. Ｗ２ and R Ｗ３ These are, independently, a cyano group and a -COOR group. Ｗ４ , -COR Ｗ５ , or -SO ２ R Ｗ６ Represents R Ｗ４ ~R Ｗ６each 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. * represents the bonding position. In formula (A-2), R Ａ１ and R Ａ２ each independently represents a cyano group, -COOR ｂ１ , -COR ｂ２ , -SOR ｂ３ , or -SO ２ R ｂ４ . R ｂ１ to R ｂ４ 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. * represents the bonding position.

[0034] In formula (1), D represents a group represented by formula (D-1) or a group represented by formula (D-2). From the viewpoint of more excellent quantum efficiency, the group represented by formula (D-1) is preferable.

[0035] In formula (D-1) and formula (D-2), X １ each independently represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, -NR １ -, -CR ２ R ３ -, -SiR ４ R ５ -, or -GeR ６ R ７ -. From the viewpoints of more excellent quantum efficiency and the effects of the present invention, -NR １ -, -CR ２ R ３ -, or -SiR ４ R ５ - is preferable.

[0036] In X １ , R １ to R ７Each 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, with the optionally substituted aliphatic hydrocarbon group or the optionally substituted aromatic ring group being preferred. Examples of substituents that the above aliphatic hydrocarbon group, aromatic ring group, and aliphatic heterocyclic group may have include the substituents exemplified by substituent W described above, and substituents selected from the substituent group S described later are preferred.

[0037] R １ ~R ７ The aliphatic hydrocarbon group represented above may be linear, branched, or cyclic. Examples of the 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.

[0038] R １ ~R ７The above aromatic ring group represented by may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The above aromatic ring group may be either monocyclic or polycyclic, with monocyclic being preferred. The number of ring atoms in the above aromatic ring group is preferably 5 to 18, more preferably 5 to 10, and even more preferably 5 to 8. The definition and specific examples of the 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 the heteroatom in the above aromatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom, an oxygen atom, or a nitrogen atom being preferred. The definition and specific examples of the aromatic heterocyclic group are as described above, with a thiophene ring group, a furan ring group, or a pyridine ring group being preferred. As described above, the above aromatic ring group may have a substituent. When the above aromatic ring group has a substituent, the number thereof is not particularly limited, but 1 to 3 are preferred.

[0039] R １ ~R ７ The above aliphatic heterocyclic group represented by may be either monocyclic or polycyclic, with monocyclic being preferred. The number of ring atoms in the above aliphatic heterocyclic group is preferably 3 to 18, more preferably 5 to 10, and even more preferably 5 to 8. Examples of the heteroatom in the above aliphatic heterocyclic group include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, with a sulfur atom or an oxygen atom and a nitrogen atom being preferred. The definition and specific examples of the aliphatic heterocyclic group are as described above, with a thiolane ring group, a piperidine ring group, a tetrahydrofuran ring group, or a tetrahydropyran ring group being preferred. As described above, the above aliphatic heterocyclic group may have a substituent. When the above aliphatic heterocyclic group has a substituent, the number thereof is not particularly limited, but 1 to 3 are preferred.

[0040] R ２ and R ３ may combine with each other to form a ring which may have a substituent, and R ４ and R ５ may combine with each other to form a ring which may have a substituent, and R ６ and R ７These may bond to each other to form a ring which may have substituents. The ring may be either an aromatic ring or an aliphatic ring, with an aliphatic ring being preferred. The ring may be either a monocyclic or polycyclic ring. The number of ring member atoms of the ring is preferably 3 to 20, more preferably 5 to 12, and even more preferably 5 to 10. The ring may have heteroatoms. The heteroatoms are preferably sulfur atoms, nitrogen atoms, or oxygen atoms. The substituents that the ring may have include the substituent W mentioned above, and alkyl groups, aryl groups, or halogen atoms are preferred.

[0041] In equations (D-1) and (D-2), X ２ and X ３ Each of these is independently a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or -NR １ Represents -. R １ is, X １ As stated above. X ２ Sulfur atoms or oxygen atoms are preferred in terms of quantum efficiency and the effects of the present invention. ３ A sulfur atom or an oxygen atom is preferred in that it provides superior effects compared to the present invention.

[0042] In equations (D-1) and (D-2), Y is independently -CR ｙ１ = or represents a nitrogen atom, and in terms of having superior effects in the present invention, -CR ｙ１ = is preferable. R ｙ１ R represents a hydrogen atom or substituent. ｙ１Examples of substituents represented by the above-mentioned substituent W include the substituents W described above, which are preferably an aliphatic hydrocarbon group which may have substituents, an aromatic ring group which may have substituents, an aliphatic heterocyclic group which may have substituents, an alkoxy group which may have substituents, an aryloxy group which may have substituents, an acyl group which may have substituents, a silyl group which may have substituents, a halogen atom which is more preferably an aliphatic hydrocarbon group which may have substituents, an aromatic ring group which may have substituents, an aliphatic heterocyclic group which may have substituents, a silyl group which may have substituents, an alkoxy group which may have substituents, or a halogen atom which is even more preferably a halogen atom which is even more preferably a substituent. Examples of substituents which each of the above-mentioned substituents may have include the substituents W described above, and substituents selected from the substituent group S described later are preferred.

[0043] R ｙ１ The definitions and preferred embodiments of the substituents represented by the following are: an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, and an optionally substituted aliphatic heterocyclic group, respectively. １ ~R ７ 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 .

[0044] 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.

[0045] The aryl group in the above aryloxy group may be monocyclic or polycyclic, with monocyclic being preferred. 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.

[0046] The hydrocarbon group of the above acyl group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred. Preferred embodiments of the aliphatic hydrocarbon group and aromatic hydrocarbon group of the above acyl group are R １ ~R７ The substituents represented are the same as those exemplified. The number of carbon atoms in the above acyl group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0047] The above silyl group is -SiR Ｓｉ ３ It is a group represented by R. Ｓｉ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. Ｓｉ The definitions and preferred embodiments of an optionally substituted aliphatic hydrocarbon group, optionally substituted aromatic ring group, and optionally substituted aliphatic heterocyclic group are as follows: Ａ These are the same groups as the substituents exemplified by the formulas.

[0048] 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.

[0049] In formula (D-2), Z １ ~Z ３ Of these, one represents -C(*) = and the other two independently represent -CR ｙ１ = or represents a nitrogen atom. R ｙ１ As stated above, the present invention has superior effects, Z １ ~Z ３ One of them represents -C(*) = and the other two represent -CR ｙ１ It is preferable to represent it as an equals sign (=).

[0050] In equations (D-1) and (D-2), * indicates a bonding position.

[0051] The substituent group S is described in detail below. Substituent group S: 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 5 to 12 ring member atoms which may have substituents, alkoxy groups having 1 to 5 carbon atoms, acyl groups having 2 to 6 carbon atoms, silyl groups, and halogen atoms.

[0052] The number of carbon atoms in the linear aliphatic hydrocarbon group in the substituent group S is 1 to 3, more preferably 1 or 2. The number of carbon atoms in the branched aliphatic hydrocarbon group in the substituent group S is 3 to 7, more preferably 3 or 4. The cyclic aliphatic hydrocarbon group in the substituent group S is preferably monocyclic.

[0053] The aromatic ring group in the substituent group S may be monocyclic or polycyclic, with monocyclic being preferred. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with aromatic hydrocarbon groups being preferred. The heteroatoms of the aromatic heterocyclic group are preferably oxygen atoms, nitrogen atoms, or sulfur atoms. The number of ring member atoms of the aromatic ring group is 5 to 12, preferably 5 to 10, and more preferably 5 or 6. Examples of substituents that the aromatic ring group may have are the substituents exemplified by substituent W described above, with substituents selected from substituent group S being preferred, and more preferably linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 7 carbon atoms, silyl groups, alkoxy groups having 1 to 5 carbon atoms, or halogen atoms. If the aromatic ring group has substituents, the number of substituents is preferably 1 to 3.

[0054] The number of carbon atoms in the alkoxy group in the above substituent group S is 1 to 5, more preferably 1 to 4, and even more preferably 1 or 2. The number of carbon atoms in the acyl group in the above substituent group S is 2 to 6, more preferably 2 to 5, and even more preferably 2 or 3.

[0055] The definition and preferred embodiment of the silyl group in the above substituent group S is as described above in R ｙ１ The substituent represented by is the same as the silyl group exemplified. In particular, R Ｓｉ However, each is independently a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 7 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group having 5 to 12 ring member atoms, which may have substituents, -SiR Ｓｉ ３ A base represented by is preferred.

[0056] Examples of halogen atoms in the above substituent group S include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or chlorine atoms being preferred.

[0057] In formula (1), R １１ and R １２ Each of these independently represents a hydrogen atom or a substituent. Examples of substituents include those exemplified by substituent W above. １１ and R １２ A hydrogen atom is preferred as the element.

[0058] In formula (1), A １ and A ２ Each of these independently represents either a group represented by formula (A-1) or a group represented by formula (A-2), and the group represented by formula (A-1) is preferred in that it provides superior effects of the present invention.

[0059]

[0060] In formula (A-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 (A-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 an aliphatic 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, 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. １ Among the carbon atoms constituting the ring represented by formula (A-1), the carbon atoms at the bond positions marked with * and W １Carbon atoms other than those bonded to may be substituted with carbonyl carbons (>C=O) or thiocarbonyl carbons (>C=S).

[0061] Examples of substituents that the above ring may have include the group exemplified by substituent W, and preferably a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic ring group, or a silyl group, 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. Preferred substituents that the alkyl group may have include halogen atoms, aromatic ring groups, or silyl groups. Preferred substituents that the aromatic ring group may have include halogen atoms, alkyl groups, or silyl groups.

[0062] The ring represented by formula (A-1) is preferably a ring used as an acidic nucleus (for example, an acidic nucleus made of merocyanine dye), and examples of such nuclei include the following: (a) 1,3-dicarbonyl nuclei: for example, 1,3-indanedione nuclei, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-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 nuclei: 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 core (2-thio-2,4-(3H,5H)-oxazoledione core): For example, 3-ethyl-2-thio-2,4-oxazolidinedione. (h) thianaphthenone core: For example, 3(2H)-thianaphthenone-1,1-dioxide. (i) 2-thio-2,5-thiazolidinedione core: For example, 3-ethyl-2-thio-2,5-thiazolidinedione.(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) nuclei: 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. (o) 3,5-pyrazolidinedione core: e.g., 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione. (p) Benzothiophen-3(2H)-one core: e.g., benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, and dioxobenzothiophen-3(2H)-one. (q) Indanone core: e.g., 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, and 3,3-dimethyl-1-indanone. (r) Benzofuran-3-(2H)-one nucleus: e.g., benzofuran-3-(2H)-one. (s) 2,2-dihydrophenalen-1,3-dione nucleus, etc.

[0063] In formula (A-1), W １ This consists of an oxygen atom, a sulfur atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ In terms of exhibiting superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ R represents a hydrogen atom or a substituent. Examples of substituents include the substituent W mentioned above. Ｗ２ and R Ｗ３ These are, independently, a cyano group and a -COOR group. Ｗ４ , -COR Ｗ５ , or -SO ２ R Ｗ６ Represents RＷ４ ~R Ｗ６ 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 4 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. Ｗ４ ~R Ｗ６ Examples of substituents that each group represented by the above substituent W may have include the substituents exemplified by substituent W.

[0064] In equation (A-1), * indicates a bonding position.

[0065] As the group represented by formula (A-1), the group represented by formula (A-3) is preferred in that it exhibits superior effects of the present invention.

[0066]

[0067] 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 an aliphatic 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, 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. The above CC 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.

[0068] In formula (A-3), W ２ and W ３ These are, independently, a sulfur atom, an oxygen atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ In terms of exhibiting superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ ~R Ｗ３ As stated above.

[0069] The group represented by formula (A-3) is preferably the group represented by formula (C-1) or the group represented by formula (C-2).

[0070]

[0071] In formula (C-1), X ｃ１ and X ｃ２ These are, independently, a sulfur atom, an oxygen atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ In terms of exhibiting superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ ~R Ｗ３ As stated above, the present invention has superior effects, X ｃ１ and X ｃ２ Preferably, one of them is an oxygen atom, X ｃ１ and X ｃ２ It is more preferable that it be an oxygen atom.

[0072] In formula (C-1), C ３ represents an aromatic ring which may have substituents. The aromatic ring may be monocyclic or polycyclic. The number of member atoms of the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 5 to 8. The number of member atoms of the aromatic ring is the number including the two carbon atoms explicitly shown in the formula. The aromatic ring may also be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. Specific examples of the aromatic ring are as described above, and are preferably a benzene ring, naphthalene ring, anthracene ring, pyrene ring, thiophene ring, furan ring, thiazole ring, oxazole ring, pyridine ring, thienothiophene cyclic 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 which the aromatic ring may have include the group exemplified by substituent W, and alkyl groups or halogen atoms are preferred. The number of substituents that the above aromatic ring may have is not particularly limited, but is preferably 0 to 8, and more preferably 0 to 4.

[0073] In formula (C-2), X ｃ３ ~X ｃ５ These are, independently, a sulfur atom, an oxygen atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３In terms of exhibiting superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ ~R Ｗ３ As stated above, the present invention has superior effects, X ｃ３ and X ｃ４ It is preferable that X is an oxygen atom. ｃ３ ~X ｃ５ It is more preferable that it be an oxygen atom.

[0074] Z ａ１ and Z ａ２ Each of these is independently -NR ｃ１ - or -CR ｃ２ R ｃ３ - indicates that the effects of the present invention are superior, and -NR ｃ１ - is preferable. R ｃ１ ~R ｃ３ Each of these independently represents a hydrogen atom or a substituent. Examples of the substituent include the group exemplified by substituent W, and alkyl groups or aryl groups are preferred, with alkyl groups being more preferred. The alkyl group may be linear, branched, or cyclic, with linear being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. The aryl group may be monocyclic or polycyclic, with phenyl groups being preferred. The aryl group may have further substituents, and examples of substituents include the group exemplified by substituent W.

[0075] In formula (A-2), R Ａ１ and R Ａ２ These are, independently, a cyano group and a -COOR group. ｂ１ , -COR ｂ２ , -SOR ｂ３ , or -SO ２ R ｂ４ Represents R ｂ１ ~R ｂ４ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. ｂ１ ~R ｂ４ The definitions and preferred embodiments of each group represented by RＷ４ ~R Ｗ６ It is the same as the group represented by R. ｂ１ ~R ｂ４ Among these, aliphatic hydrocarbon groups or phenyl groups having 1 to 4 carbon atoms are preferred.

[0076] In equation (A-2), * indicates the bonding position.

[0077] The following are specific examples of particular compounds, but the present invention is not limited to these.

[0078]

[0079]

[0080]

[0081]

[0082]

[0083] In the compounds exemplified above, A independently represents one of the following groups. Note that the two A's may be identical or different.

[0084]

[0085]

[0086]

[0087]

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] <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.

[0095] 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.

[0096] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.

[0097] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less, or in the range of 500 to 600 nm.

[0098] 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.

[0099] The difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or greater.

[0100] 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%.

[0101] 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.

[0102] 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 volume 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.

[0103] <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.

[0104] 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.

[0105]

[0106]

[0107]

[0108]

[0109] The difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or greater.

[0110] 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%.

[0111] 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.

[0112] <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 acryl Examples of dyes include lysinone 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. 2023-010305, and Japanese Patent Publication No. 2023-010299, 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.

[0113] 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.

[0114] 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%.

[0115] <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.

[0116] 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.

[0117] [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. Being transparent to the light to be detected means that the average transmittance of light in the wavelength range to be detected is 50% or more, preferably 60% or more, and more preferably 70% or more. Specifically, it is preferable that it be transparent to light with a wavelength of 400 to 800 nm. The above transmittance can be measured using a spectrophotometer. 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.

[0118] 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.

[0119] The lower electrode 11 may be made transparent or opaque to reflect light, depending on the application. The definition of transparency in the lower electrode 11 is the same as that for the upper electrode 15 described above. Examples of materials that make up the lower electrode 11 include conductive metal oxides such as antimony or fluorine-doped tin oxide (ATO, FTO), 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.

[0120] 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.

[0121] [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.

[0122] <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.

[0123] 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.

[0124] <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.

[0125] 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.

[0126] 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.

[0127] [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.

[0128] [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 the sealing layers described in paragraphs

[0210] to

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

[0129] [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.

[0130] [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.

[0131] [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 in which they are arranged in a plane.

[0132] [Compounds] This invention also includes inventions of specific compounds.

[0133] 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.

[0134] [Compounds used in photoelectric conversion films] The following lists the materials used in the photoelectric conversion films.

[0135] [Synthesis of Compound (A-1)] Compound (A-1) was synthesized according to the following scheme.

[0136]

[0137] <Synthesis of compound (A-1-A)> 2-bromothiophene-3-carboxylate methyl (5.0 g), 2-thiopheneboronic acid (3.47 g), potassium carbonate (K ２ CO ３9.70 g), tetrahydrofuran (THF, 90 mL), and water (18 mL) were placed in a round-bottom flask, and after nitrogen purging (3 times), dichlorobis(triphenylphosphine)palladium(II) (Pd(PPh) ３ ) ２ Cl ２ 794 mg of the compound was added, and nitrogen purging (twice) was performed. Under a nitrogen atmosphere, the reaction mixture was heated and stirred at 70°C for 3 hours, cooled to room temperature, and then filtered by Celite. The filtrate was separated into an aqueous phase and an organic phase. The aqueous phase was extracted with ethyl acetate, and the combined 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 / 5-85 / 15) to obtain 3.92 g of compound (A-1-A) (yield 77%). １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ (ppm) = 7.63 (1H, dd), 7.48 (1H, d), 7.34-7.33 (2H, m), 7.18 (1H, d), 3.80 (3H, s).

[0138] <Synthesis of Compound (A-1-B)> Compound (A-1-A) (3.81 g), THF (59 mL), and lanthanum(III) bis(lithium chloride) complex (THF solution (0.6 M), 32 mL) were placed in a round-bottom flask. The mixture was cooled on ice under a nitrogen atmosphere, and methylmagnesium bromide (THF solution (12%), 52 mL) was added dropwise, followed by aqueous ammonium chloride (50 mL) and 2 M hydrochloric acid (50 mL). 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 under reduced pressure to obtain 3.81 g of compound (A-1-B) (yield 97%). １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ (ppm) = 7.40 (1H, dd), 7.34 (1H, dd), 7.23 (1H, dd), 7.19 (1H, d), 7.10 (1H, d), 1.92 (1H, brs), 1.52 (6H, s).

[0139] <Synthesis of Compound (A-1-C)> Methylene chloride (90 mL) and trifluoromethanesulfonic acid (7.2 mL) were placed in a round-bottom flask, and a methylene chloride solution (270 mL) containing intermediate (A-1-B) (3.60 g) was added dropwise. After stirring at room temperature for 5 minutes, water (10 mL) and 1 M aqueous sodium hydroxide solution (80 mL) were added. The resulting reaction mixture was extracted with methylene chloride, 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 = 99:1-95:5) and gel permeation chromatography (eluent: chloroform) to obtain 1.0 g of compound (A-1-C) (yield 30%). １ The H-NMR data is shown below. １ H-NMR (CDCl ３ ): δ (ppm) = 7.27 (1H, d), 7.14 (1H, d), 7.05 (1H, d), 6.97 (1H, d), 6.99 (1H, d), 1.51 (6H, s).

[0140] <Synthesis of Compound (A-1-D)> Compound (A-1-C) (936 mg) and THF (45 mL) were placed in a round-bottom flask, and the reaction mixture was cooled to -78°C under a nitrogen atmosphere. After adding n-butyllithium (hexane solution (1.6 M), 17 mL) dropwise, the temperature was raised to room temperature and then cooled again to -78°C. N,N-dimethylformamide (DMF, 3.2 mL) was added, the temperature was raised to room temperature, and then aqueous ammonium chloride solution (20 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: hexane / ethyl acetate = 8 / 2-2 / 8) and recrystallized with methylene chloride / ethyl acetate to obtain 534 mg of compound (A-1-D) (yield 44%). １ The H-NMR data is shown below. １ H-NMR (CDCl ３): δ (ppm) = 9.93 (1H, s), 9.88 (1H, s), 7.80 (1H, s), 7.67 (1H, s), 1.60 (6H, s).

[0141] <Synthesis of Compound (A-1)> Compound (A-1-D) (524 mg), 1-ethyl-3-methylbarbituric acid (747 mg), toluene (26 mL), and piperidine (40 μL) were placed in a round-bottom flask and reacted at 100°C for 3 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 chloroform / toluene / methanol. The obtained solid was purified by sublimation to obtain compound (A-1) (242 mg, yield 70%). １ The H-NMR data is shown below. １ H-NMR (CD) ２ Cl ２ ): δ (ppm) = 8.78 (1H, s), 8.74 (1H, s), 7.98 (1H, s), 7.83 (1H, s), 4.10-4.05 (4H, m), 3.43-3.40 (6H, m), 1.70 (6H, s), 1.32-1.25 (6H, m).

[0142] The compounds used in each example and comparative example for photoelectric conversion films other than compound (A-1) are synthesized in accordance with the synthesis method of compound (A-1).

[0143] [Specific Compounds] The specific compounds used in the photoelectric conversion film and comparative compounds for the comparative examples are shown below. Compounds (A-1) to (A-18) are specific compounds, and compound (C-1) is a comparative compound.

[0144]

[0145]

[0146] [n-type organic semiconductor] ・C60: Fullerene (C ６０ )

[0147] [p-type organic semiconductor]

[0148]

[0149] [Pigment]

[0150]

[0151] [Evaluation] The dependence of the quantum efficiency and response speed of the photoelectric conversion element on electric field strength when it receives blue-green light (wavelength 460 nm) will be evaluated using the following method.

[0152] [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 the table below is deposited on the electron blocking film 16A on a single-layer basis: n-type organic semiconductor (fullerene (C) ６０ )): A p-type organic semiconductor (P-1) is co-deposited by vacuum deposition so that the ratio is 1:1:1 (in terms of film thickness). This forms a photoelectric conversion film 12 having a bulk heterostructure of 400 nm. At this time, the deposition rate of the photoelectric conversion film 12 is set to 1.0 Å / sec. Furthermore, a compound (EB-2) is 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 it by ALCVD (Atomic Layer Chemical Vapor Deposition). ２ O ３ A layer is formed. The resulting laminate is heated in a glove box at 150°C for 30 minutes to fabricate a photoelectric conversion element.

[0153]

[0154] [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. ５A voltage is applied to achieve an electric field strength of V / cm, and the current value in the dark (dark current) is measured. In all photoelectric conversion elements, the dark current is 50 nA / cm. ２ The following results are observed, indicating a sufficiently low dark current.

[0155] [Quantum Efficiency] For each photoelectric conversion element, the quantum efficiency when receiving blue-green light is measured using the following method. 2.0 × 10⁻¹⁰ for each photoelectric conversion element. ５ After applying a voltage to achieve an electric field strength of V / cm, light is irradiated from the upper electrode (transparent conductive film) side to evaluate the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 460 nm, and the quantum efficiency (relative ratio) is calculated according to equation (S1). From the obtained value, the quantum efficiency is evaluated according to the evaluation criteria below. For practical purposes, an evaluation of C or higher is preferable for the quantum efficiency. Equation (S1): Quantum efficiency (relative ratio) = (Photoelectric conversion efficiency of each photoelectric conversion element) / (Photoelectric conversion efficiency of the photoelectric conversion elements in Examples 1-8)

[0156] A: Quantum efficiency (relative ratio) of 1.2 or higher B: Quantum efficiency (relative ratio) of 1.0 or higher and less than 1.2 C: Quantum efficiency (relative ratio) of 0.8 or higher and less than 1.0 D: Quantum efficiency (relative ratio) less than 0.8

[0157] [Dependence of response speed 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. 7.0 × 10⁻¹⁰ ４ A voltage is applied to achieve an electric field strength 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, and the rise time from 0% signal strength to 97% signal strength is measured. Next, the voltage applied to each photoelectric conversion element is set to achieve an electric field strength of 2.0 × 10⁻⁶. ５ Except for changing it to V / cm, the same procedure is used to obtain an electric field strength of 2.0 × 10⁻⁶. ５The rise time at V / cm is measured. The electric field strength dependence of the response speed is calculated according to equation (S2), and the electric field strength dependence of the response speed is evaluated from the obtained value according to the evaluation criteria below. In equation (S2), the numerator and denominator are the values ​​measured for the same photoelectric conversion element. For practical purposes, an evaluation of C or higher for the electric field strength dependence of the response speed is preferable. Equation (S2): Electric field strength dependence of response speed = (Electric field strength of each photoelectric conversion element 7.0 × 10⁻⁶) ４ (Rise time at V / cm) / (Electric field strength of each photoelectric conversion element 2.0 × 10) ５ (Rise time at V / cm)

[0158] A: The electric field strength dependence of the response speed is less than 2.0. B: The electric field strength dependence of the response speed is 2.0 or more and less than 3.0. C: The electric field strength dependence of the response speed is 3.0 or more and less than 4.0. D: The electric field strength dependence of the response speed is 4.0 or more.

[0159] [result]

[0160] The evaluation results are shown in Table 1 below. In the table, the "Formula (1)" column is "A" if the photoelectric conversion element contains a specific compound, and "B" otherwise. １ The column indicates X for a specific compound. １ However, -NR １ -, -CR ２ R ３ -, or -SiR ４ R ５ If the condition is -, it is designated as "A", and if it is otherwise, it is designated as "B". In the table, "X ２ The column indicates X for a specific compound. ２ However, if it is a sulfur atom or an oxygen atom, it is designated as "A", and otherwise it is designated as "B". In the table, for specific compounds, the "D" column is designated as "A" if D is a group represented by formula (D-1), and otherwise it is designated as "B". In the table, "A １ , A ２ The column indicates that for specific compounds, A １ and A ２ However, if the base is represented by formula (A-1), it is designated as "A," and in all other cases, it is designated as "B."

[0161]

[0162] As shown in Table 1, the photoelectric conversion element of the present invention exhibits low dependence of the electric field strength on the response speed when receiving blue-green light. Furthermore, the photoelectric conversion element of the present invention is also confirmed to have excellent quantum efficiency when receiving blue-green light.

[0163] From a comparison between Example 1-8 and Example 1-7, and between Example 1-15 and Examples 1-10, 1-12 to 1-14, 1-16, and 1-18, X １ However, -NR １ -, -CR ２ R ３ -, or -SiR ４ R ５ - In this case, it is confirmed that the electric field strength dependence of the response speed is smaller and the quantum efficiency is better. From a comparison of Example 1-17 with Examples 1-10, 1-12 to 1-14, 1-16, and 1-18, X ２ However, when it is a sulfur atom or an oxygen atom, it is confirmed that the electric field strength dependence of the response speed is smaller and the quantum efficiency is better. From a comparison between Examples 1-11 to 1-18 and Examples 1-1 to 1-10, it is confirmed that when D is a group represented by formula (D-1), the quantum efficiency is better. From a comparison between Example 1-7 and Examples 1-1 to 1-6, and between Example 1-11 and Examples 1-10, 1-12 to 1-14, 1-16, and 1-18, A １ and A ２ However, when the group is represented by equation (A-1), it is confirmed that the electric field strength dependence of the response speed is smaller.

[0164] When a photoelectric conversion element is fabricated using a dye other than the specified compound in addition to the specified compound or comparative compound, the quantum efficiency (sensitivity) of the photoelectric conversion element when it receives blue-green light (wavelength 460 nm), and the electric field strength dependence of the quantum efficiency can be evaluated by the following method.

[0165] Each specific compound or each comparative compound, n-type organic semiconductor (fullerene (C) ６０The 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 specific compound:dye:p-type organic semiconductor:n-type organic semiconductor by vacuum deposition, with a p-type organic semiconductor (P-1) and one of the dyes selected from (R-1) to (R-10) in a single-layer ratio of 1:1:2:2. Each photoelectric conversion element is evaluated using the same procedure as described above. Even when a dye is used in combination, results equivalent to those shown in Table 1 above can be obtained. Specifically, for example, a photoelectric conversion element fabricated using compound (A-1) according to the above method shows evaluation results equivalent to Example 1-1 in Table 1. Photoelectric conversion elements are fabricated and each evaluation is performed for all combinations of each specific compound and each dye.

[0166] 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), D represents a group represented by formula (D-1) or a group represented by formula (D-2). R ２ , ２ , １ and R １２ each independently represents a hydrogen atom or a substituent. A １ and A ２ each independently represents a group represented by formula (A-1) or a group represented by formula (A-2). In formula (D-1) and formula (D-2), X １ each independently represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, -NR １ -, -CR ２ R ３ -, -SiR ４ R ５ -, or -GeR ６ R ７ -. R １ to R ７ each independently represents a hydrogen atom, an aliphatic hydrocarbon group that may have a substituent, an aromatic ring group that may have a substituent, or an aliphatic heterocyclic group that may have a substituent. R ２ and R ３ may combine with each other to form a ring that may have a substituent, and R ４ and R ５ may combine with each other to form a ring that may have a substituent, and R ６ and R ７ may combine with each other to form a ring that may have a substituent. X ２ and X ３ each independently represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or -NR １ -. Y each independently represents -CR ｙ１ = or a nitrogen atom. R ｙ１ represents a hydrogen atom or a substituent. Among Z １ to Z ３ , one represents -C(*)=, and two each independently represent -CR ｙ１ = or a nitrogen atom. * represents the bonding position. In formula (A-1), C １ This represents a ring containing two or more carbon atoms, which may have substituents. １ This consists of an oxygen atom, a sulfur atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ R represents a hydrogen atom or substituent. Ｗ２ and R Ｗ３ These are, independently, a cyano group and a -COOR group. Ｗ４ , -COR Ｗ５ , or -SO ２ R Ｗ６ Represents R Ｗ４ ~R Ｗ６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position. In formula (A-2), R Ａ１ and R Ａ２ These are, independently, a cyano group and a -COOR group. ｂ１ , -COR ｂ２ , -SOR ｂ３ , or -SO ２ R ｂ４ Represents R ｂ１ ~R ｂ４ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position.

2. X １ However, -NR １ -, -CR ２ R ３ -, or -SiR ４ R ５ - The photoelectric conversion element according to claim 1.

3. X ２ The photoelectric conversion element according to claim 1, wherein the atom is a sulfur atom or an oxygen atom.

4. The photoelectric conversion element according to claim 1, wherein D is a group represented by formula (D-1).

5. A １ and A ２ The photoelectric conversion element according to any one of claims 1 to 4, wherein each of the members is independently represented by the formula (A-1).

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

10. A photoelectric conversion element according to any one of claims 1 to 4, 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 4.

12. A light sensor having a photoelectric conversion element according to any one of claims 1 to 4.

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 4.

14. A compound represented by formula (1). In formula (1), D represents a group represented by formula (D-1) or a group represented by formula (D-2). R １１ and R １２ each independently represent a hydrogen atom or a substituent. A １ and A ２ each independently represent a group represented by formula (A-1) or a group represented by formula (A-2). In formula (D-1) and formula (D-2), X １ each independently represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, -NR １ -, -CR ２ R ３ -, -SiR ４ R ５ -, or -GeR ６ R ７ -. R １ to R ７ 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 ２ and R ３ may combine with each other to form a ring which may have a substituent, and R ４ and R ５ may combine with each other to form a ring which may have a substituent, and R ６ and R ７ may combine with each other to form a ring which may have a substituent. X ２ and X ３ each independently represent a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or -NR １ -. Y each independently represents -CR ｙ１ = or a nitrogen atom. R ｙ１ represents a hydrogen atom or a substituent. Among Z １ to Z ３ , one represents -C(*)=, and two each independently represent -CR ｙ１ = or a nitrogen atom. * represents the bonding position. In formula (A-1), C １ contains two or more carbon atoms and represents a ring which may have a substituent. W １ represents an oxygen atom, a sulfur atom, =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ . R Ｗ１ represents a hydrogen atom or a substituent. R Ｗ２ and R Ｗ３ each independently represent a cyano group, -COOR Ｗ４ , -COR Ｗ５ , or -SO ２ R Ｗ６ . R Ｗ４ to R Ｗ６ each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. * represents the bonding position. In formula (A-2), R Ａ１ and R Ａ２ [[ID=​​​​​​​​​​​​​​ 15. X １ However, -NR １ -, -CR ２ R ３ -, or -SiR ４ R ５ - The compound according to claim 14.

16. X ２ The compound according to claim 14, wherein the atom is a sulfur atom or an oxygen atom.

17. The compound according to claim 14, wherein D is a group represented by formula (D-1).

18. A １ and A ２ The compound according to any one of claims 14 to 17, wherein each of the groups is independently represented by formula (A-1).

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