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

Abstract

The present invention provides a photoelectric conversion element having excellent electric-field-strength-dependent responsiveness, and provides an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound relating to the above photoelectric conversion element. 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, wherein the photoelectric conversion film includes 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 an organic photoelectric conversion device that contains a predetermined p-type molecule in the photoelectric conversion layer.

[0003] International Publication No. 2018 / 207722

[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 example of a required characteristic for a photoelectric conversion element is excellent electric field strength dependence of response speed (responsiveness). In this specification, "excellent electric field strength dependence of responsiveness" means that the response speed of the photoelectric conversion element does not change significantly even when the electric field strength is changed. Under these requirements, the present inventors fabricated and investigated a photoelectric conversion element containing a p-type molecule disclosed in Patent Document 1, and found that there is room for further improvement in the electric field strength dependence of responsiveness.

[0005] Therefore, the present invention aims to provide a photoelectric conversion element that exhibits excellent responsiveness dependent on 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] Y is -CR Ｙ１ [1] The photoelectric conversion element described in [1], where = [2]. [3] The photoelectric conversion element described in [1] or [2], where n11, n12, n21 and n22 are all 0. [4] Z １ This is the base represented by the formula (Z1) described later, and Z３ is a group represented by the following formula (Z2), and Z ２ and Z ４ are each independently, -CR Ｙ１ = or a nitrogen atom, the photoelectric conversion element according to any one of [1] to [3]. [5] Ar １ｂ and Ar ２ｂ are each independently, a monovalent aromatic ring group represented by any one of the following formulas (Ar-1) to (Ar-11), 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, the photoelectric conversion element according to any one of [1] to [5]. [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 at least one kind of dye, the photoelectric conversion element according to any one of [1] to [7]. [9] The photoelectric conversion element according to any one of [1] to [8], 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.

[10] An imaging device having the photoelectric conversion element according to any one of [1] to [9].

[11] An optical sensor having the photoelectric conversion element according to any one of [1] to [9].

[12] A method for manufacturing an imaging device, which has a step of manufacturing the photoelectric conversion element according to any one of [1] to [9].

[13] A compound represented by the following formula (1).

[14] Y are all -CR Ｙ１ =, the compound according to

[13] .

[15] n11, n12, n21 and n22 are all 0, the compound according to

[13] or

[14] .

[16] Z １ is a group represented by the following formula (Z1), and Z ３ is a group represented by the following formula (Z2), and Z ２ and Z ４ are each independently, -CR Ｙ１ = or a nitrogen atom, the compound according to any one of

[13] to

[15] .

[17] Ar １ｂ and Ar２ｂ However, each is independently a monovalent aromatic ring group represented by one of the formulas (Ar-1) to (Ar-11) described later, and is one of the compounds described in any one of

[13] to

[16] .

[0008] According to the present invention, a photoelectric conversion element exhibiting excellent responsiveness dependent on electric field strength can be provided. 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. The specific compounds described later may have substituents such as carboxyl group, carboxyl group salt, phosphate group, phosphate group salt, sulfonic acid group, sulfonic acid group salt, hydroxyl group, thiol group, acylamino group, carbamoyl group, ureido group, or boronic acid group (-B(OH)). ２ ) and / or the absence of a primary amino group is also preferable.

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

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

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

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

[0019] In this specification, unless otherwise specified, the aromatic ring or aromatic ring group may be monocyclic or polycyclic (e.g., 2 to 6 rings). A monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as its ring structure. A polycyclic (e.g., 2 to 6 rings) aromatic ring 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, for example, 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 rings 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 rings is included. In the optionally substituted aromatic ring group, optionally substituted aryl group, and optionally substituted heteroaryl 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 (e.g., 1 to 4).

[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 the photoelectric conversion element having the above configuration can solve the problems of the present invention is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than those described below, it is still within the scope of the present invention. The specific compound has a rigid central skeleton in which the six rings explicitly shown in formula (1) are fused, and furthermore, it has a group containing at least one of a heterocyclic structure and a fused ring structure, thus promoting intermolecular interactions and improving crystallinity in the photoelectric conversion film. As a result, it is speculated that the photoelectric conversion element having a photoelectric conversion film containing the specific compound exhibits superior electric field strength dependence of responsiveness. Hereinafter, superior electric field strength dependence of responsiveness is also referred to as "the effect of the present invention is superior."

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

[0029] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15. Furthermore, when using the photoelectric conversion element 10a (or 10b), a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and between this pair of electrodes, 1 × 10⁻¹⁰ －５ ~1 x 10 ７ It is preferable to apply a voltage of V / cm. In terms of performance and power consumption, the applied voltage should be 1 × 10⁻⁶. －４ ~1 x 10 ７ V / cm is more preferable, 1 × 10 －３ ~5 x 10 ６ A voltage of V / cm is even more preferable. Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side becomes the cathode and the photoelectric conversion film 12 side becomes the anode, as shown in Figures 1 and 2. The same method can be used to apply the voltage when the photoelectric conversion element 10a (or 10b) is used as a light sensor or when it is incorporated into an image sensor. As will be described in detail later, the photoelectric conversion element 10a (or 10b) is suitably applicable to image sensor applications. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

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

[0031] <Specific Compounds> The photoelectric conversion film contains specific compounds, which are compounds represented by formula (1).

[0032]

[0033] In formula (1), X represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and the two Xs in the formula are the same atom. A sulfur atom or an oxygen atom is preferred for X, and a sulfur atom is more preferred. Y is independently -CR Ｙ１ = or represents a nitrogen atom. R Ｙ１ represents a hydrogen atom or substituent. In terms of the superior effects of the present invention, Y is always -CR Ｙ１ It is preferable that R is equal to R. Ｙ１ A hydrogen atom is preferred as the component. Ｙ１When is a substituent, examples of substituents include each of the groups exemplified as substituent W above, and among these, a methyl group, a fluorine atom, or a chlorine atom are preferred.

[0034] In the above formula (1), Z １ and Z ２ One side represents the base represented by formula (Z1), and the other side represents -CR Ｙ１ = represents a nitrogen atom. Also, Z ３ and Z ４ One side represents the base represented by formula (Z2), and the other side represents -CR Ｙ１ = represents a nitrogen atom. In formulas (Z1) and (Z2), the dashed line represents the bond position. The present invention has superior effects, Z １ The group is represented by the above formula (Z1), and Z ３ The group is represented by the above formula (Z2), and Z ２ and Z ４ However, each independently, -CR Ｙ１ = Preferably a nitrogen atom. Z １ and Z ３ It is more preferable that they be the same group, Z ２ and Z ４ is, -CR Ｙ１ It is more preferable that it is equal to R Ｙ１ The definition and preferred embodiment are as described above.

[0035] In the above formulas (Z1) and (Z2), n11, n12, n21, and n22 each independently represent 0 or 1. For the effects of the present invention to be superior, it is preferable that at least two of n11, n12, n21, and n22 are 0, more preferably that at least n11 and n21 are 0, and even more preferably that all of n11, n12, n21, and n22 are 0. m1 and m2 each independently represent integers from 0 to 2. m1 and m2 are preferably 0 or 1, and more preferably both are 0.

[0036] In the above formulas (Z1) and (Z2), Ar １ａ and Ar ２ａ Each of these independently represents a divalent aromatic ring group, which may have substituents. １ｂ and Ar ２ｂEach independently represents a monovalent aromatic ring group which may have substituents. However, if both m1 and m2 are 0, Ar １ｂ and Ar ２ｂ If at least one of the structures includes a fused ring structure and at least one of m1 and m2 is 1 or 2, then m1 contains Ar １ａ m2 Ar ２ａ Ar １ｂ and Ar ２ｂ At least one of these includes at least one of a heterocyclic structure and a fused ring structure.

[0037] Ar １ａ and Ar ２ａ The divalent aromatic ring group, which may have substituents represented by Ar, may be monocyclic or fused. That is, Ar １ａ and Ar ２ａ This may be either a divalent monocyclic aromatic ring group or a divalent fused aromatic ring group. Note that a divalent fused aromatic ring group corresponds to an aromatic ring group containing a fused ring structure. In other words, Ar １ａ and Ar ２ａ It may include a fused ring structure. In particular, Ar １ａ and Ar ２ａ As such, a divalent fused aromatic ring group is preferred. The number of monocyclic aromatic rings contained in the fused aromatic ring group is two or more, may be three or more, and is often five or less. Therefore, the fused aromatic ring group may contain a fused ring structure of two or more rings, or a fused ring structure of three or more rings. Among these, in terms of the superior effects of the present invention, it is preferable that the number of monocyclic aromatic rings contained in the fused aromatic ring group is two or three. In other words, Ar １ａ and Ar ２ａ The divalent fused aromatic ring group represented by preferably includes a two-ring fused ring structure or a three-ring fused ring structure. The number of ring member atoms of the monoring constituting the divalent monoring aromatic ring group and the number of ring member atoms of the monoring constituting the divalent fused aromatic ring group is preferably 5 to 10, and more preferably 5 or 6.

[0038] Ar １ａ and Ar ２ａA divalent aromatic ring group which may have substituents represented by Ar may be either a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. Note that a divalent aromatic heterocyclic group corresponds to an aromatic ring group which contains a heterocyclic structure. In other words, Ar １ａ and Ar ２ａ The heterocyclic structure may also be included. The number of heteroatoms in the aromatic heterocyclic group and the heterocyclic structure is preferably 1 to 8, more preferably 1 to 3, and even more preferably 1 or 2. Examples of the heteroatoms are as described above, with sulfur atoms, oxygen atoms, selenium atoms, tellurium atoms, or nitrogen atoms being preferred, and sulfur atoms or oxygen atoms being more preferred.

[0039] Ar １ａ and Ar ２ａ When the divalent aromatic ring group represented by is a divalent monocyclic aromatic ring group, the aromatic ring constituting the divalent monocyclic aromatic ring group is preferably a benzene ring, thiophene ring, furan ring, selenofen ring, pyridine ring, pyrimidine ring, or thiazole ring, and more preferably a benzene ring, thiophene ring, or furan ring. １ａ and Ar ２ａ When the divalent aromatic ring group represented by is a divalent fused aromatic ring group, the aromatic ring constituting the divalent fused aromatic ring group is preferably a benzene ring, thiophene ring, furan ring, selenofen ring, pyridine ring, pyrimidine ring, or thiazole ring, and more preferably a benzene ring, thiophene ring, or furan ring.

[0040] Ar １ａ and Ar ２ａ The divalent aromatic ring group represented by may include a heterocyclic structure or a condensed structure, as described above. That is, Ar １ａ and Ar ２ａ The divalent aromatic ring group represented by may be a divalent fused aromatic ring group that may contain a heterocycle. That is, Ar １ａ and Ar ２ａ This may include a heterocycle or a fused ring structure of two or more rings. The divalent fused aromatic ring group, which may include a heterocycle, is preferably composed of two or three rings.

[0041] Ar １ａ and Ar ２ａThe divalent aromatic ring group represented by is preferably unsubstituted, although it may have a substituent. Ar １ａ and Ar ２ａ When the divalent aromatic ring group represented by has a substituent, examples of the substituent include each group exemplified as the above substituent W. Among them, a methyl group, a fluorine atom, or a chlorine atom is preferable.

[0042] In terms of more excellent effects of the present invention, at least one (more preferably both) of Ar １ａ and Ar ２ａ is preferably a divalent aromatic ring group represented by any one of the following formulas (L-1) to (L-5).

[0043]

[0044] In formulas (L-1) to (L-5), Y ａ each independently represents -CR Ｙ２ = or a nitrogen atom. R Ｙ２ represents a hydrogen atom or a substituent. As Y ａ , -CR Ｙ２ = is preferable. R Ｙ２ is preferably a hydrogen atom. When R Ｙ２ is a substituent, examples of the substituent include each group exemplified as the above substituent W. Among them, a methyl group, a fluorine atom, or a chlorine atom is preferable. In formulas (L-2) to (L-4), X ２ to X ４ each independently represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or >NR Ｎ . R Ｎ represents a hydrogen atom or a substituent. As X ２ to X ４ , each independently, a sulfur atom or an oxygen atom is preferable, and a sulfur atom is more preferable.

[0045] As R Ｎ , a substituent is preferable. Examples of the substituent represented by R Ｎ include, for example, the substituents exemplified by the above substituent W, and 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 is preferable.

[0046] In the above formula (L-2), Z １１ and Z １２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ２ = or represents a nitrogen atom. Z １１ and Z １２ For example, one atom may be a sulfur atom or an oxygen atom, and the other may be -CR Ｙ２ It is preferable that it is equal to R. Ｎ and R Ｙ２ The definition and preferred embodiment of are as described above. In the above formula (L-3), Z １３ and Z １４ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ２ = or represents a nitrogen atom. Z １３ and Z １４ For example, one atom may be a sulfur atom or an oxygen atom, and the other may be -CR Ｙ２ It is preferable that it is equal to R. Ｎ and R Ｙ２ The definition and preferred embodiment are as described above.

[0047] Ar １ｂ and Ar ２ｂ The monovalent aromatic ring group, which may have substituents represented by Ar, may be a monocyclic or fused ring. １ｂ and Ar ２ｂ This may be either a monovalent monocyclic aromatic ring group or a monovalent fused aromatic ring group. Note that a monovalent fused aromatic ring group corresponds to an aromatic ring group containing a fused ring structure. In other words, Ar １ｂ and Ar ２ｂ It may include a fused ring structure. In particular, Ar １ｂ and Ar ２ｂAs such, a monovalent fused aromatic ring group is preferred. The number of monocyclic aromatic rings contained in the fused aromatic ring group is two or more, may be three or more, and is often five or less. Therefore, the fused aromatic ring group may contain a fused ring structure of two or more rings, or a fused ring structure of three or more rings. Among these, in terms of the superior effects of the present invention, it is preferable that the number of monocyclic aromatic rings contained in the fused aromatic ring group is two or three. In other words, Ar １ｂ and Ar ２ｂ The monovalent fused aromatic ring group represented by preferably includes a two-ring fused ring structure or a three-ring fused ring structure. The number of ring member atoms in the monoring constituting the monovalent monoring aromatic ring group and the number of ring member atoms in the monovalent fused aromatic ring group are preferably 5 to 10, and more preferably 5 or 6.

[0048] Ar １ｂ and Ar ２ｂ A monovalent aromatic ring group which may have substituents represented by Ar may be either a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group. Note that a monovalent aromatic heterocyclic group corresponds to an aromatic ring group which contains a heterocyclic structure. In other words, Ar １ｂ and Ar ２ｂ This may include a complex algebra. １ｂ and Ar ２ｂ It is also preferable that both are monovalent aromatic heterocyclic groups which may have substituents. That is, Ar １ｂ and Ar ２ｂ It is preferable that both include a heterocyclic structure. The number of heteroatoms in the aromatic heterocyclic group and the heterocyclic structure is preferably 1 to 8, more preferably 1 to 3, and even more preferably 1 or 2. Examples of the heteroatoms are as described above, with sulfur atoms, oxygen atoms, selenium atoms, tellurium atoms, or nitrogen atoms being preferred, and sulfur atoms or oxygen atoms being more preferred.

[0049] Ar １ｂ and Ar ２ｂ When the monovalent aromatic ring group represented by is a monovalent monocyclic aromatic ring group, the aromatic ring constituting the monovalent monocyclic aromatic ring group is preferably a benzene ring, thiophene ring, furan ring, selenofen ring, pyridine ring, pyrimidine ring, or thiazole ring, and more preferably a benzene ring, thiophene ring, or furan ring.１ｂ and Ar ２ｂ When the monovalent aromatic ring group represented by is a monovalent fused aromatic ring group, the aromatic ring constituting the monovalent fused aromatic ring group is preferably a benzene ring, thiophene ring, furan ring, selenofene ring, pyridine ring, pyrimidine ring, or thiazole ring, and more preferably a benzene ring, thiophene ring, or furan ring.

[0050] Ar １ｂ and Ar ２ｂ The monovalent aromatic ring group represented by may contain a heterocyclic structure or a condensed structure, as described above. That is, Ar １ｂ and Ar ２ｂ The monovalent aromatic ring group represented by may be a monovalent fused aromatic ring group that may contain a heterocycle. That is, Ar １ｂ and Ar ２ｂ It may contain a heterocycle or a fused ring structure of two or more rings. The monovalent fused aromatic ring group which may contain a heterocycle is preferably composed of two or three rings. In terms of the superior effects of the present invention, Ar １ｂ and Ar ２ｂ Preferably, at least one of them includes a bimodal structure containing a heterocycle, or a fused structure of three or more rings, and more preferably, both include a bimodal structure containing a heterocycle, or a fused structure of three or more rings.

[0051] Ar １ｂ and Ar ２ｂ The monovalent aromatic ring group represented by Ar may have substituents, but it is preferable that it does not. １ｂ and Ar ２ｂ When the monovalent aromatic ring group represented by has substituents, examples of substituents include each of the groups exemplified as substituent W above, and among these, a methyl group, a fluorine atom, or a chlorine atom are preferred.

[0052] In terms of having superior effects, Ar １ｂ and Ar ２ｂPreferably, at least one (more preferably both) of these is a monovalent aromatic ring group represented by any of the following formulas (Ar-1) to (Ar-12), and more preferably a monovalent aromatic ring group represented by any of the following formulas (Ar-1) to (Ar-11).

[0053]

[0054] In formulas (Ar-1) to (Ar-12), Y ｂ Each of these is independently -CR Ｙ１ = or represents a nitrogen atom. R Ｙ１ Y represents a hydrogen atom or substituent. ｂ As for -CR Ｙ１ = is preferable. R Ｙ１ A hydrogen atom is preferred. Ｙ１ When is a substituent, examples of substituents include each of the groups exemplified as substituent W above, and among them, a methyl group, a fluorine atom, or a chlorine atom are preferred. In formulas (Ar-1) to (Ar-4) and (Ar-9) to (Ar-11), X １ ~X ４ and X ９ ~X １１ These are, independently, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or >NR Ｎ Represents R Ｎ X represents a hydrogen atom or substituent. １ ~X ４ and X ９ ~X １１ As for each, a sulfur atom or an oxygen atom is preferred, and a sulfur atom is more preferred. Ｎ Specific examples and preferred embodiments are as described above.

[0055] In the above formula (Ar-1), Z １１ and Z １２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = or represents a nitrogen atom. Z １１ and Z １２ For example, one atom may be a sulfur atom or an oxygen atom, and the other may be -CR Ｙ１ It is preferable that =. In the above formula (Ar-2), Z２１ and Z ２２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = or represents a nitrogen atom. Z ２１ and Z ２２ For example, one atom may be a sulfur atom or an oxygen atom, and the other may be -CR Ｙ１ It is preferable that =. In the above formula (Ar-5), Z ５１ and Z ５２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = or represents a nitrogen atom. Z ５１ and Z ５２ For example, one atom may be a sulfur atom or an oxygen atom, and the other may be -CR Ｙ１ It is preferable that =. In the above formula (Ar-7), Z ７１ and Z ７２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = or represents a nitrogen atom. Z ７１ and Z ７２ For example, one atom may be a sulfur atom or an oxygen atom, and the other may be -CR Ｙ１ It is preferable that =. In the above formula (Ar-9), Z ９１ and Z ９２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = or represents a nitrogen atom. Z ９１ and Z ９２ For example, one atom may be a sulfur atom or an oxygen atom, and the other may be -CR Ｙ１ It is preferable that it is equal to R. Ｎ and R Ｙ１ The definition and preferred embodiment are as described above.

[0056] In the above formula (Ar-10), Z １０１ and Z １０２ One side represents -C(*) = and the other side represents -CR Ｙ１ = or represents a nitrogen atom. Z １０２ga -C(*) = Z １０１ ga-CR Ｙ１ It is preferable that =. In the above formula (Ar-11), Z １１３ and Z １１４ One side represents -C(*) = and the other side represents -CR Ｙ１ = or represents a nitrogen atom. Z １１４ ga -C(*) = Z １１３ ga-CR Ｙ１ It is preferable that it is equal to Z. １１１ and Z １１２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = or represents a nitrogen atom. Z １１１ and Z １１２ For example, one atom may be a sulfur atom or an oxygen atom, and the other may be -CR Ｙ１ It is preferable that it is equal to R. Ｎ and R Ｙ１ The definition and preferred embodiment are as described above.

[0057] As mentioned above, if both m1 and m2 are 0, Ar １ｂ and Ar ２ｂ At least one of them includes a fused ring structure. If both m1 and m2 are 0, Ar １ｂ and Ar ２ｂ As one preferred embodiment, Ar １ｂ and Ar ２ｂ Examples include embodiments in which both include a fused ring structure, １ｂ and Ar ２ｂ Examples include a two-ring fused structure containing a heterocycle, or a three-ring or more-ring fused structure. Also, when both m1 and m2 are 0, Ar １ｂ and Ar ２ｂ As another preferred embodiment, Ar １ｂ and Ar ２ｂ Embodiments in which at least one of the embodiments includes a bimodal structure containing a heterocycle, or a fused structure of three or more rings. The number of aromatic rings included in the fused structure of three or more rings may be three or more, preferably three to five, and more preferably three.

[0058] Furthermore, as mentioned above, if at least one of m1 and m2 is 1 or 2, then m1 has Ar １ａ m2 Ar ２ａ Ar １ｂ and Ar ２ｂ At least one of the structures includes at least one of a heterocyclic structure and a fused ring structure. When at least one of m1 and m2 is 1 or 2, one preferred embodiment is m1 containing Ar １ａ m2 Ar ２ａ Ar １ｂ and Ar ２ｂ One embodiment includes at least one of which has a fused ring structure. Also, when at least one of m1 and m2 is 1 or 2, another preferred embodiment is when at least one of m1 and m2 is 1 or 2, and m1 has Ar １ａ m2 Ar ２ａ Ar １ｂ and Ar ２ｂ Examples include embodiments in which at least two of the above include a heterocyclic structure and at least one of a fused ring structure. In particular, in this embodiment, m1 Ar １ａ m2 Ar ２ａ Ar １ｂ and Ar ２ｂ Preferably, at least two of these include a fused ring structure of two or more rings, including a heterocycle. In particular, if at least one of m1 and m2 is 1 or 2, Ar １ｂ and Ar ２ｂ Preferably, at least one of the structures includes at least one of a heterocyclic structure and a fused ring structure; more preferably, both include at least one of a heterocyclic structure and a fused ring structure; and even more preferably, both include a fused ring structure of two or more rings including a heterocyclic structure. The number of aromatic rings included in the fused ring structure of two or more rings including a heterocyclic structure may be two or more, preferably 2 to 5, and more preferably 2 or 3.

[0059] The following are specific examples of particular compounds, but the present invention is not limited to these.

[0060]

[0061]

[0062] For the effects of the present invention to be more pronounced, the molecular weight of the specific compound is preferably 900 or less, more preferably 800 or less, and even more preferably 750 or less. The lower limit is preferably 400 or more, more preferably 450 or more, and even more preferably 500 or more. When the molecular weight is as described above, the sublimation temperature of the specific compound becomes appropriate, and it is presumed that the manufacturing suitability is excellent.

[0063] The specific compound can be suitably used as a p-type organic semiconductor. A p-type organic semiconductor is a donor organic semiconductor material (compound) that is an organic compound that readily donates electrons. The ionization potential of the specific compound is preferably 5.0 to 6.0 eV.

[0064] The maximum absorption wavelength of the specific compound is not particularly limited, but is preferably in the range of 300 to 600 nm, and more preferably in the range of 350 to 500 nm. The 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 measured using the specific compound in the form of a film obtained by vapor deposition.

[0065] The specific compound is particularly useful as a material for photoelectric conversion films used in image sensors, photosensitive devices, or photocells. The specific compound often functions as a p-type organic semiconductor within the photoelectric conversion film. However, the photoelectric conversion film only needs to contain the specific compound; the function and mechanism of action of the specific compound in the photoelectric conversion film are not particularly limited. 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 material.

[0066] 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.

[0067] 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 15 to 75 volume%, more preferably 20 to 60 volume%, and even more preferably 25 to 50 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.

[0068] 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.

[0069] <n-type organic semiconductor> The photoelectric conversion film preferably further contains an n-type organic semiconductor in addition to the specified compound mentioned above. The n-type organic semiconductor is a compound different from the specified compound 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 the acceptor organic semiconductor. The electron affinity of the n-type organic semiconductor is preferably 3.0 to 5.0 eV. 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.

[0070] The n-type organic semiconductor (compound) preferably includes fullerenes selected from the group consisting of fullerenes and their derivatives. 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.

[0071] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.

[0072] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less, or in the range of 400 to 600 nm.

[0073] The photoelectric conversion film preferably has a bulk heterostructure formed by mixing a specific compound with an n-type organic semiconductor. The bulk heterostructure is a layer in the photoelectric conversion film in which 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.

[0074] 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%.

[0075] 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.

[0076] 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 dye described later, 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 dye 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 dye included as desired. "Substantial" means that the total content of the specific compound, n-type organic semiconductor, and dye relative to the total mass of the photoelectric conversion film is 90 to 100% by volume, preferably 95 to 100% by volume, and more preferably 99 to 100% by volume.

[0077] <p-type organic semiconductor> The photoelectric conversion film may contain a p-type organic semiconductor. A p-type organic semiconductor is a donor organic semiconductor material (compound) that has a property of readily donating electrons. In other words, a p-type organic semiconductor is the organic compound with the lower 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.

[0078] Examples of p-type organic semiconductors other than the specified compounds 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), the compounds described in paragraphs

[0128] to

[0148] of JP 2011-228614, the compounds described in paragraphs

[0052] to

[0063] of JP 2011-176259, the compounds described in paragraph

[0052] to

[0063] of JP 2011-225544) Compounds described in paragraphs

[0119] to

[0158] , 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) The compound, thieno[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivative, the compound described in paragraphs

[0031] to

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

[0043] to

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

[0025] to

[0037] and

[0099] to

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

[0029] to

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

[0015] to

[002] of WO2018 / 207722 Compounds described in [5], compounds described in paragraphs

[0045] to

[0053] of Japanese Patent Publication No. 2019-054228, 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 Japanese Patent Publication No. 2019-80052, compounds described in paragraphs

[0044] to

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

[0041] to

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

[0034] to

[0037] of Japanese Patent Publication No. 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 paragraph

[003] of Japanese Patent Publication No. 2018-078270 Compounds described in paragraphs [6] to

[0041] , compounds described in paragraphs

[0055] to

[0082] of Japanese Patent Publication No. 2018-166200, compounds described in paragraphs

[0041] to

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

[0044] to

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

[0041] to

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

[0042] to

[0049] of Japanese Patent Publication No. 2018-046267 Compounds described in paragraphs

[0031] to

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

[0036] to

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

[0045] to

[0048] of Japanese Patent 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, ammonium compounds, etc.) Examples of p-type organic semiconductors include metal complexes having ligands such as tracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, aminosubstituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and nitrogen-containing heterocyclic compounds. Furthermore, examples of p-type organic semiconductors include benzoxazole compounds (for example, compounds described in Figures 3-7 of Japanese Patent Publication No. 2022-123944), dicarbazole compounds (for example, compounds described in Figures 2-5 of Japanese Patent Publication No. 2022-122839), benzoquinazoline compounds (for example,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, Japanese Patent Publication No. 2023-00 Examples include compounds described in paragraphs

[0052] to

[0073] of Japanese Patent Publication No. 5703 and paragraph

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

[0038] to

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

[0070] to

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

[0051] to

[0064] of Japanese Patent Application Publication No. 2021-163968. 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 semiconductors are given below.

[0079]

[0080]

[0081]

[0082]

[0083] The p-type organic semiconductor may be used alone or in combination of two or more types. When the photoelectric conversion film contains a p-type organic semiconductor other than the specified compound, 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 0 to 75 volume%, more preferably 15 to 75 volume%, even more preferably 20 to 60 volume%, and particularly preferably 25 to 50 volume%.

[0084] 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.

[0085] <Dyes> In addition to the above-mentioned specific compounds, the photoelectric conversion film preferably contains at least one more dye. The dye is a compound different from the above-mentioned specific compounds. Organic dyes are preferred as dyes. Examples of organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azametine dyes, coumarin dyes, allylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, and Examples of organic dyes include cridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, imidazoquinoxaline dyes described in WO2020 / 013246, WO2022 / 168856, Japanese Patent Publication No. 2023-10305, and Japanese Patent Publication No. 2023-10299, as well as acceptor-donor-acceptor type dyes in which two acidic nuclei are bound to a donor, and donor-acceptor-donor type dyes in which two donors are bound to an acceptor. Among the organic dyes, triphenylmethane dyes, imidazoquinoxaline dyes, and acceptor-donor-acceptor type dyes are preferred.

[0086] 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.

[0087] The dye may be used alone or in combination of two or more types. The dye content in the photoelectric conversion film (= film thickness of the dye on a single-layer basis / film thickness of the photoelectric conversion film × 100) is preferably 15 to 85 volume%, more preferably 20 to 60 volume%, and even more preferably 25 to 40 volume%. The dye content in the photoelectric conversion film relative to the total content 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 15 to 75 volume%, more preferably 20 to 65 volume%, and even more preferably 25 to 60 volume%.

[0088] The dye is preferably of -5.0 to -6.0 eV as a single film, in terms of energy level matching with the n-type organic semiconductor.

[0089] The difference in ionization potential between the dye and the specific compound is preferably 0.1 eV or greater. Furthermore, the difference in ionization potential between the dye and the n-type organic semiconductor is also preferably 0.1 eV or greater.

[0090] <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.

[0091] 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.

[0092] [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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] [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.

[0097] <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.

[0098] 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.

[0099] <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.

[0100] 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.

[0101] 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.

[0102] [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.

[0103] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. Photoelectric conversion materials can be significantly degraded in performance due to the presence of degradation factors such as water molecules. Therefore, the entire photoelectric conversion film can be sealed by covering it with a sealing layer made of a dense metal oxide, metal nitride or metal nitride oxide ceramic, or diamond-like carbon (DLC), which does not allow water molecules to penetrate, thereby preventing the above-mentioned degradation. Examples of sealing layers include those described in paragraphs

[0210] to

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

[0104] [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.

[0105] [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.

[0106] [Optical Sensor] Other applications of the photoelectric conversion element include, for example, photocells and optical sensors, and the photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element may be used alone, or it may be used as a line sensor in which the photoelectric conversion elements are arranged in a straight line or as a two-dimensional sensor arranged on a plane.

[0107] [Compounds] The following preferred embodiments of the compound represented by formula (1) are also mentioned.

[0108]

[0109] In formula (1), X, Y, Z １ ~Z ４ , n11, n12, n21, n22, m1, m2, Ar １ａ Ar ２ａ Ar １ｂ and Ar ２ｂ The definition and preferred embodiment of are as described above. However, if both m1 and m2 are 0, Ar １ｂ and Ar ２ｂ If at least one of them includes a two-ring fused structure containing a heterocycle, or a three-ring or more-ring fused structure, and at least one of m1 and m2 is 1 or 2, then m1 has Ar １ａ m2 Ar ２ａ Ar １ｂ and Ar ２ｂ At least one of them includes a fused ring structure.

[0110] A more advantageous aspect of the present invention is that when both m1 and m2 are 0, Ar １ｂand Ar ２ｂ It is preferable that both include a two-ring fused structure containing a heterocycle, or a three-ring or more-ring fused structure, and it is more preferable that both include a two-ring or more-ring fused structure containing a heterocycle. Also, if at least one of m1 and m2 is 1 or 2, then m1 has Ar １ａ m2 Ar ２ａ Ar １ｂ and Ar ２ｂ It is preferable that at least two of them include a fused ring structure, and it is more preferable that at least two of them include a fused ring structure of two or more rings including a heterocycle. In particular, when at least one of m1 and m2 is 1 or 2, Ar １ｂ and Ar ２ｂ It is preferable that at least one of the rings contains a fused ring structure, more preferably both contain a fused ring structure, and even more preferably both contain a fused ring structure of two or more rings including a heterocycle. Examples of heteroatoms included in the heterocycle include sulfur, oxygen, nitrogen, selenium, and tellurium atoms, of which sulfur or oxygen atoms are preferred, and sulfur atoms are more preferred. Furthermore, in the heterocycle, the number of heteroatoms among the ring member atoms is preferably 1 to 3, and more preferably 1 or 2.

[0111] 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.

[0112] [Compounds used in photoelectric conversion films] The following lists the materials used in the photoelectric conversion films.

[0113] [Synthesis of Compound (P-3)] Compound (P-3) can be synthesized, for example, according to the following scheme.

[0114]

[0115] (Synthesis of Compound (P-3-3)) Compound (P-3-3) can be synthesized, for example, by the Suzuki-Miyaura coupling reaction as shown in the scheme above. The reaction conditions can be carried out according to the conventional method, but the following scheme shows, as one example of synthesis, a reaction in which Compound (P-3-1) and Compound (P-3-2) are reacted at 60°C in a tetrahydrofuran (THF)-water mixed solvent in the presence of (2-dicyclohexylphosphin-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate (XPhos Pd G3) as a metal catalyst and tripotassium phosphate as a base.

[0116] (Synthesis of compound (P-3)) ​​Compound (P-3) can be synthesized, for example, by reacting compound (P-3-3) obtained by the above procedure in NMP (N-methylpyrrolidone) in the presence of sodium tert-butoxide at 160-170°C.

[0117] The compounds used in each example and comparative example for photoelectric conversion films other than compound (P-3) are synthesized in accordance with the synthesis method of compound (P-3).

[0118] [Specific Compounds] The specific compounds used in the photoelectric conversion film and comparative compounds for the comparative examples are shown below. Compounds (C-1) to (C-7) are comparative compounds, while the other compounds are specific compounds.

[0119]

[0120]

[0121] [n-type organic semiconductor] ・C60: Fullerene (C ６０ )

[0122] [Pigment]

[0123]

[0124] [Evaluation] A photoelectric conversion element will be fabricated using the above materials, and the following tests X and Y will be performed.

[0125] [Test X] A photoelectric conversion element will be fabricated using the above materials as described below, and the quantum efficiency, response speed, and the electric field strength dependence of the response speed will be evaluated when blue-green light (wavelength 500 nm) is received.

[0126] <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 and an n-type organic semiconductor (fullerene (C)) are deposited on the electron blocking film 16A. ６０ The )) and the dye (B-1) are co-deposited by vacuum deposition to form films with single-layer thicknesses of 130 nm, 130 nm, and 140 nm, respectively. This forms a photoelectric conversion film 12 having a bulk heterostructure of 400 nm. Further, 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, and the resulting laminate is heated in a glove box at 150°C for 30 minutes to obtain a photoelectric conversion element.

[0127]

[0128] <Dark Current> The dark current of each obtained photoelectric conversion element is measured using the following method. 2.5 × 10⁻¹⁰ ₀ ５A voltage is applied to achieve an electric field strength of V / cm, and the current value in the dark (dark current) is measured. As a result, the dark current for all photoelectric conversion elements was 50 nA / cm. ２ The following confirms that it exhibits a sufficiently low dark current.

[0129] <Quantum Efficiency> For each photoelectric conversion element, the quantum efficiency when receiving blue-green light is measured using the following method. 2.0 × 10⁻¹⁶ 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, and the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 500 nm is evaluated. The photoelectric conversion efficiency of each photoelectric conversion element (= (photoelectric conversion efficiency of each photoelectric conversion element) / (photoelectric conversion efficiency of the photoelectric conversion element of Example 1-1)) is calculated with the photoelectric conversion efficiency of Example 1-1 set to 1, and the quantum efficiency is evaluated from the obtained value according to the evaluation criteria below.

[0130] A: 0.90 or higher B: 0.80 or higher, less than 0.90 C: 0.70 or higher, less than 0.80 D: Less than 0.70

[0131] <Response Speed ​​(Responsiveness)> The response speed (responsiveness) of each photoelectric conversion element when exposed to blue-green light will be evaluated using the following method. 2.0 × 10⁻¹⁰ ５ A voltage is applied to achieve an intensity of V / cm. Then, the LED (light emitting diode) is momentarily lit to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 500 nm at that time is measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity. The rise time of each photoelectric conversion element (= (rise time of each photoelectric conversion element) / (rise time of the photoelectric conversion element in Example 1-1)) is determined, with the rise time of the above photoelectric conversion element of Example 1-1 set to 1, and the response speed is evaluated according to the evaluation criteria below. A response speed of B or higher is preferable.

[0132] A: Less than 1.1 B: 1.1 or more, less than 1.5 C: 1.5 or more, less than 2.0 D: 2.0 or more

[0133] <Dependence of response speed (responsiveness) on electric field strength> For each photoelectric conversion element, the dependence of the response speed (responsiveness) on electric field strength when receiving blue-green light is evaluated using the following method. In the evaluation of the above <responsiveness (responsiveness)>, the voltage applied to each photoelectric conversion element is 7.5 × 10 ４ Except for changing to V / cm, the procedure was the same: 7.5 × 10 ４ The response speed at V / cm is measured. The electric field strength dependence of the response speed is calculated according to equation (S1), and the electric field strength dependence of the response speed is evaluated according to the evaluation criteria below. In equation (S1), the numerator and denominator are the values ​​measured for the photoelectric conversion element of the same example or comparative example. For example, for Example 1-1, the electric field strength at a wavelength of 500 nm of the photoelectric conversion element of Example 1-1 is 7.5 × 10⁻¹⁰. ４ Photoelectric conversion efficiency at V / cm and electric field strength of 2.0 × 10⁻¹⁰ at a wavelength of 500 nm for the photoelectric conversion element of Example 1-1. ５ This is compared with the photoelectric conversion efficiency at V / cm. A rating of B or higher is preferable for the electric field strength dependence of the response speed. Equation (S1): Electric field strength dependence of response speed = (Applied voltage to each photoelectric conversion element 7.5 × 10⁻⁶) ４ (Response speed at V / cm) / (Applied voltage to each photoelectric conversion element 2.0 × 10) ５ (Response speed in V / cm)

[0134] A: The electric field strength dependence of the response speed is less than 1.5. B: The electric field strength dependence of the response speed is 1.5 or more and less than 2.0. C: The electric field strength dependence of the response speed is 2.0 or more and less than 2.5. D: The electric field strength dependence of the response speed is 2.5 or more.

[0135] [Results (Test X)] The evaluation results are shown in Table 1 below. In the table, "Y = CR Ｙ１ The column indicates that for specific compounds, in formula (1), Y is always -CR Ｙ１ If the values ​​are equal, it is designated as "A," and otherwise it is designated as "B." In the table, the column "n11, n12, n21 and n22 = 0" indicates that for a specific compound, if n11, n12, n21 and n22 in formula (1) are all 0, it is designated as "A," and otherwise it is designated as "B." In the table, "Z ２ and Z ４ =CR Ｙ１The column indicates that for a specific compound, in formula (1), Z １ The group is represented by the above formula (Z1), and Z ３ The group is represented by the above formula (Z2), and Z ２ and Z ４ However, each independently, -CR Ｙ１ = If it is a nitrogen atom, it is designated as "A", and in all other cases, it is designated as "B". In the table, the "(Ar-1) to (Ar-11)" column indicates that for specific compounds, in formula (1), Ar １ｂ and Ar ２ｂ However, if each is independently a monovalent aromatic ring group represented by any of the formulas (Ar-1) to (Ar-11), it is designated as "A," and if it is otherwise designated as "B."

[0136]

[0137] The results shown in the table demonstrate that the photoelectric conversion element of the present invention exhibits excellent responsiveness (response speed) and electric field strength dependence of responsiveness, as well as excellent quantum efficiency. Comparison of Examples 1-1 to 1-12 and 1-18 shows that for the specific compound, Y in formula (1) is all -CR Ｙ１ When this is the case, it is shown that the quantum efficiency is superior. Comparisons between Examples 1-1 to 1-12 and 1-14 and 1-15 show that for a specific compound, when n11, n12, n21, and n22 in formula (1) are all 0, the responsiveness (response speed) and the electric field strength dependence of the responsiveness are superior. Comparisons between Examples 1-1 to 1-13 show that for a specific compound, in formula (1), Z １ The group is represented by the above formula (Z1), and Z ３ The group is represented by the above formula (Z2), and Z ２ and Z ４ However, each independently, -CR Ｙ１ = Or, if it is a nitrogen atom, it is shown that the quantum efficiency is better. Comparison of Examples 1-1 to 1-12 with 1-16 and 1-17, etc., shows that Ar １ｂ and Ar ２ｂ However, it is shown that when each is independently a monovalent aromatic ring group represented by any of the formulas (Ar-1) to (Ar-11), the responsiveness (response rate) and the electric field strength dependence of the responsiveness are superior.

[0138] Although the above evaluation uses dye (B-1), if any of the dyes (B-2) to (B-9) shown in the upper section are used instead of dye (B-1) and the evaluations described in [Test X] above are performed, the same results as those shown in Table 1 will be obtained.

[0139] [Test Y] Next, a photoelectric conversion element is fabricated using one of the dyes (B-1) to (B-9) in addition to dyes (D-1) to (D-5), and the quantum efficiency, response speed, and electric field strength dependence of the response speed when the photoelectric conversion element receives blue-green light (wavelength 500 nm) are evaluated by the following method.

[0140] <Fabrication of photoelectric conversion elements> A specific compound selected from compounds (P-1) to (P-20), an n-type organic semiconductor (fullerene (C) ６０ A photoelectric conversion film 12 is formed by co-depositing a dye B selected from dyes (B-1) to (B-9) and a dye D selected from dyes (D-1) to (D-5) shown below using vacuum deposition, such that the ratio of the specific compound:n-type organic semiconductor:dye B:dye D = 2:2:1:1 on a single-film basis. The photoelectric conversion elements for each example and comparative example are then fabricated using the same procedure as in Test X. As a result, even when dyes other than the specific compound are used in combination, results similar to those for quantum efficiency, response speed, and electric field strength dependence of response speed shown in Table 1 are obtained.

[0141]

[0142] 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), X represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and the two Xs in the formula are the same atom. Y is each independently -CR Ｙ１ =, or represents a nitrogen atom. R Ｙ１ represents a hydrogen atom or a substituent. Z １ and Z ２ One represents a group represented by formula (Z1), and the other represents -CR Ｙ１ =, or represents a nitrogen atom. Z ３ and Z ４ One represents a group represented by formula (Z2), and the other represents -CR Ｙ１ =, or represents a nitrogen atom. In formula (Z1) and formula (Z2), the wavy line represents the bonding position. n11, n12, n21, and n22 each independently represent 0 or 1. m1 and m2 each independently represent an integer from 0 to 2. Ar １ａ and Ar ２ａ each independently represent a divalent aromatic ring group which may have a substituent. Ar １ｂ and Ar ２ｂ each independently represent a monovalent aromatic ring group which may have a substituent. However, when both m1 and m2 are 0, at least one of Ar １ｂ and Ar ２ｂ contains a condensed ring structure, and when at least one of m1 and m2 is 1 or ②, m1 Ar １ａ , m2 Ar ２ａ , Ar １ｂ and Ar ２ｂ at least one of them contains at least one of a heterocyclic structure and a condensed ring structure.

2. Y is -CR in all cases Ｙ１ The photoelectric conversion element according to claim 1, wherein the value is equal to the value of the photoelectric conversion element according to claim 1.

3. The photoelectric conversion element according to claim 1, wherein n11, n12, n21, and n22 are all 0.

4. Z １ The group is represented by the above formula (Z1), and Z ３ The group is represented by the above formula (Z2), and Z ２ and Z ４ However, each independently, -CR Ｙ１ The photoelectric conversion element according to claim 1, wherein the element is either a nitrogen atom or a nitrogen atom.

5. Ar １ｂ and Ar ２ｂ The photoelectric conversion element according to claim 1, wherein each is independently a monovalent aromatic ring group represented by any of the following formulas (Ar-1) to (Ar-11). In formulas (Ar-1) to (Ar-11), Y ｂ Each of these is independently -CR Ｙ１ = or represents a nitrogen atom. R Ｙ１ X represents a hydrogen atom or substituent. In formulas (Ar-1) to (Ar-4), and (Ar-9) to (Ar-11), X １ ~X ４ and X ９ ~X １１ These are, independently, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or >NR Ｎ Represents R Ｎ represents a hydrogen atom or substituent. In formula (Ar-1), Z １１ and Z １２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = represents a nitrogen atom. In formula (Ar-2), Z ２１ and Z ２２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = represents a nitrogen atom. In formula (Ar-5), Z ５１ and Z ５２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = represents a nitrogen atom. In formula (Ar-7), Z ７１ and Z ７２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = represents a nitrogen atom. In formula (Ar-9), Z ９１ and Z ９２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = represents a nitrogen atom. In formula (Ar-10), Z １０１ and Z １０２ One side represents -C(*) = and the other side represents -CR Ｙ１ = represents a nitrogen atom. In formula (Ar-11), Z １１１ and Z １１２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = or represents a nitrogen atom. Z １１３ and Z １１４ One side represents -C(*) = and the other side represents -CR Ｙ１ = represents a nitrogen atom. * represents a bond position.

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

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

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

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

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

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

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

13. A compound represented by formula (1). In formula (1), X represents a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom, and the two Xs in the formula are the same atom. Y is independently -CR Ｙ１ = or represents a nitrogen atom. R Ｙ１ Z represents a hydrogen atom or substituent. １ and Z ２ One side represents the base represented by formula (Z1), and the other side represents -CR Ｙ１ = or represents a nitrogen atom. Z ３ and Z ４ One side represents the base represented by formula (Z2), and the other side represents -CR Ｙ１ = represents a nitrogen atom. In equations (Z1) and (Z2), the dashed line represents the bond position. n11, n12, n21, and n22 each independently represent 0 or 1. m1 and m2 each independently represent an integer from 0 to 2. Ar １ａ and Ar ２ａ Each of these independently represents a divalent aromatic ring group, which may have substituents. １ｂ and Ar ２ｂ Each independently represents a monovalent aromatic ring group which may have substituents. However, if both m1 and m2 are 0, Ar １ｂ and Ar ２ｂ If at least one of them includes a two-ring fused structure containing a heterocycle, or a three-ring or more-ring fused structure, and at least one of m1 and m2 is 1 or 2, then m1 has Ar １ａ m2 Ar ２ａ Ar １ｂ and Ar ２ｂ At least one of them includes a fused ring structure.

14. Y is -CR in all cases. Ｙ１ The compound according to claim 13, which is equal to =.

15. The compound according to claim 13, wherein n11, n12, n21, and n22 are all 0.

16. Z １ The group is represented by the above formula (Z1), and Z ３ The group is represented by the above formula (Z2), and Z ２ and Z ４ However, each independently, -CR Ｙ１ The compound according to claim 13, wherein the atom is either a nitrogen atom or a nitrogen atom.

17. Ar １ｂ and Ar ２ｂ each independently represents a monovalent aromatic ring group represented by any one of the following formulas (Ar-1) to (Ar-11), the compound according to any one of claims 13 to 16. In the formulas (Ar-1) to (Ar-11), Y ｂ each independently represents -CR Ｙ１ =, or a nitrogen atom. R Ｙ１ represents a hydrogen atom or a substituent. In the formulas (Ar-1) to (Ar-4), and the formulas (Ar-9) to (Ar-11), X １ to X ４ and X ９ to X １１ each independently represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or >NR Ｎ represents a hydrogen atom or a substituent. In the formula (Ar-1), Z Ｎ and Z １１ and Z １２ one represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or >NR Ｎ and the other represents -CR Ｙ１ =, or a nitrogen atom. In the formula (Ar-2), Z ２１ and Z ２２ one represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or >NR Ｎ and the other represents -CR Ｙ１ =, or a nitrogen atom. In the formula (Ar-5), Z ５１ and Z ５２ one represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or >NR Ｎ and the other represents -CR Ｙ１ =, or a nitrogen atom. In the formula (Ar-7), Z ７１ and Z ７２ one represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or >NR Ｎ and the other represents -CR Ｙ１ =, or a nitrogen atom. In the formula (Ar-9), Z ９１ and Z ９２ one represents a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = represents a nitrogen atom. In formula (Ar-10), Z １０１ and Z １０２ One side represents -C(*) = and the other side represents -CR Ｙ１ = represents a nitrogen atom. In formula (Ar-11), Z １１１ and Z １１２ One of them is a sulfur atom, oxygen atom, selenium atom, tellurium atom, or >NR Ｎ This represents one, and the other is -CR Ｙ１ = or represents a nitrogen atom. Z １１３ and Z １１４ One side represents -C(*) = and the other side represents -CR Ｙ１ = represents a nitrogen atom. * represents a bond position.

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