Composition, photoelectric conversion element, imaging element, optical sensor, and production method for imaging element

Abstract

The present invention addresses the problem of providing a composition that makes it possible to form a photoelectric conversion element for which response speed has little dependence on electric field strength. This composition includes a compound represented by formula (1) and a compound represented by formula (2), the compound represented by formula (2) content relative to the total mass of the compound represented by formula (1) being 0.2–7.5 mass%.

Description

Composition, photoelectric conversion element, imaging element, optical sensor, and method for manufacturing imaging element

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

[0002] In recent years, development of devices having photoelectric conversion films (e.g., image pickup devices) has progressed. For example, Patent Document 1 discloses a specific polycyclic fused ring compound as a compound applicable to organic semiconductor materials such as organic transistors.

[0003] Japanese Patent Application Laid-Open No. 2015-199716

[0004]

[0003] With the demand for improved performance of image sensors, optical sensors, and the like, there is a demand for photoelectric conversion elements that exhibit excellent characteristics. For example, the characteristics required for a photoelectric conversion element include a response speed that is not easily changed even when the electric field strength is changed, i.e., a small dependency of the response speed on the electric field strength. In response to such demands, the present inventors fabricated and investigated a photoelectric conversion element containing the compound disclosed in Patent Document 1, and found that the dependency of the response speed on the electric field strength did not satisfy the desired level and there was room for improvement.

[0005] Therefore, an object of the present invention is to provide a composition that can form a photoelectric conversion element having a response speed that is less dependent on electric field strength. Another object of the present invention is to provide a photoelectric conversion element, an imaging element, an optical sensor, and a method for manufacturing an imaging element, which relate to the composition.

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0007] [1] A composition containing a compound represented by the formula (1) described below and a compound represented by the formula (2) described below, wherein the content of the compound represented by the formula (2) is 0.2 to 7.5 mass % relative to the total mass of the compound represented by the formula (1). [2] In the formula (2), Ar １ｂ and Ar ２ｂ In the group represented by the formula (3), the total number of groups represented by the formula (3) contained as the substituents is 1, and Ar ３ｂ and Ar４ｂ [3] The composition according to [1], wherein the total number of groups represented by formula (3) contained as the substituents in the group represented by formula (3) is 0. １ ~R ３ is a branched alkyl group having 3 carbon atoms. [4] In the formula (1), the number of aromatic rings represented by A to D and Ar １ａ ~Ar ４ａ and the total number of aromatic rings in the group represented by Ar is 9 or 10, and in the formula (2), the total number of aromatic rings represented by A to D and Ar １ｂ ~Ar ４ｂ [5] The composition according to any one of [1] to [3], wherein the total number of aromatic rings in the group represented by Ar is 9 or 10. １ａ , Ar ２ａ , Ar ３ａ , and Ar ４ａ Each of them satisfies the requirement 1 described later, and Ar １ｂ , Ar ２ｂ , Ar ３ｂ , and Ar ４ｂ wherein each of them satisfies Requirement 2 described below. [6] 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 the composition described in any one of [1] to [5] and an n-type organic semiconductor. [7] The photoelectric conversion element according to [6], wherein the n-type organic semiconductor contains a fullerene selected from the group consisting of fullerenes and derivatives thereof. [8] The photoelectric conversion element according to [6] or [7], wherein the photoelectric conversion film further contains a dye. [9] The photoelectric conversion element according to any one of [6] to [8], wherein one or more intermediate layers are provided between the conductive film and the transparent conductive film in addition to the photoelectric conversion film.

[10] An imaging element comprising the photoelectric conversion element according to any one of [6] to [9].

[11] A photosensor comprising the photoelectric conversion element according to any one of [6] to [9].

[12] A method for manufacturing an imaging element, comprising a step of manufacturing the photoelectric conversion element according to any one of [6] to [9].

[0008] According to the present invention, a composition can be provided that can form a photoelectric conversion element having a response speed that is less dependent on electric field strength. Furthermore, according to the present invention, a photoelectric conversion element, an imaging element, an optical sensor, and a method for manufacturing an imaging element, which are related to the composition, can also be provided.

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

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

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] In this specification, a hydrogen atom may be either a protist atom (a normal hydrogen atom) or a deuterium atom (for example, a deuterium atom). In this specification, when there are multiple substituents, linking groups, etc. (hereinafter also referred to as "substituents, etc.") represented by a specific symbol, or when multiple substituents, etc. are specified at the same time, this means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc.

[0013] In this specification, unless otherwise specified, examples of the "substituent" include the groups exemplified as the substituent W below.

[0014] (Substituent W) The substituent W in this specification will be described. Examples of the substituent W include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (a heteroaryl group or an aliphatic heterocyclic group), a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryl ... Examples of substituents include an alkyloxy group, a primary, secondary, or tertiary amino group (including an anilino group), an alkylthio group, an arylthio group, a heterocyclic thio group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a carboxy group, a phosphate group, a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, and a boronic acid group. Each of the above groups may further have a substituent (e.g., one or more of the above groups) if possible. For example, an alkyl group which may have a substituent is also included as one form of the substituent W. When the substituent W has a carbon atom, the number of carbon atoms contained in the substituent W is, for example, 1 to 20. The number of atoms other than hydrogen atoms contained in the substituent W is, for example, 1 to 30. The specific compounds described below may have, as substituents, a carboxy group, a salt of a carboxy group, a phosphate group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH) ２ ) and / or does not have a primary amino group.

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

[0017] In this specification, unless otherwise specified, the alkyl group moiety in the alkoxy group and alkylthio group is preferably the above-mentioned alkyl group. In the alkoxy group which may have a substituent, examples of the substituent that the alkoxy group may have include the same as the substituent in the alkyl group which may have a substituent. In the alkylthio group which may have a substituent, examples of the substituent that the alkylthio group may have include the same as the substituent in the alkyl group which may have a substituent.

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

[0019] In this specification, unless otherwise specified, an aromatic ring or an aromatic ring constituting an aromatic ring group may be either monocyclic or polycyclic (e.g., 2 to 6 rings, etc.). A monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as a ring structure. A polycyclic (e.g., 2 to 6 rings, etc.) aromatic ring is an aromatic ring having multiple (e.g., 2 to 6) condensed aromatic ring structures as a ring structure. The number of ring members in the aromatic ring is preferably 5 to 15. In this specification, unless otherwise specified, an aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle. When the aromatic ring is an aromatic heterocycle, the number of heteroatoms contained as ring member atoms is, for example, 1 to 10. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a phenanthrene ring, and a fluorene ring.Examples of the aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (e.g., a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring), a tetrazine ring (e.g., a 1,2,4,5-tetrazine ring), a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a naphthopyrrole ring, a naphthofuran ring, a naphthothiophene ring, a naphthoimidazole ring, a naphthoxazole ring, a pyrroloimidazole ring (e.g., a 5H-pyrrolo[1,2-a]imidazole ring), an imidazooxazole ring (e.g., an imidazo[2,1-b]oxazole ring), Thienothiazole rings (for example, thieno[2,3-d]thiazole rings, etc.), benzothiadiazole rings, benzodithiophene rings (for example, benzo[1,2-b:4,5-b']dithiophene rings, etc.), thienothiophene rings (for example, thieno[3,2-b]thiophene rings, etc.), thiazolothiazole rings (for example, thiazolo[5,4-d]thiazole rings, etc.), naphthodithiophene rings (for example, naphtho[2,3- 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, the term "aromatic ring group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic ring. In this specification, the term "aromatic hydrocarbon group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic hydrocarbon ring, and the term "aromatic heterocyclic group" includes, for example, a group obtained by removing one or more (e.g., 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic heterocycle. In this specification, the term "aryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to the aromatic hydrocarbon ring of the above-mentioned aromatic ring. In this specification, the term "heteroaryl group" includes, for example, a group obtained by removing one hydrogen atom from a ring corresponding to the aromatic heterocycle of the above-mentioned aromatic ring. In this specification, the term "arylene group" includes, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to the aromatic hydrocarbon ring of the above-mentioned aromatic ring. In this specification, the term "heteroarylene group" refers to, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the above-mentioned aromatic rings. In the optionally substituted aromatic ring group, optionally substituted aryl group, optionally substituted heteroaryl group, optionally substituted arylene group, and optionally substituted heteroarylene group, the types of substituents that these groups may have include, for example, the groups exemplified for the substituent W. When these groups have substituents, the number of substituents may be 1 or more (for example, 1 to 4, etc.).

[0021] As used herein, the term "non-aromatic ring" refers to a ring structure that does not fall under the category of aromatic rings, and examples thereof include aliphatic hydrocarbon rings and aliphatic heterocycles. Examples of the aliphatic hydrocarbon ring include cycloalkanes, cycloalkenes, and cycloalkynes. Examples of the aliphatic heterocycle include a pyrrolidine ring, oxolane ring, thiolane ring, piperidine ring, tetrahydropyran ring, thiane ring, piperazine ring, morpholine ring, quinuclidine ring, azetidine ring, oxetane ring, aziridine ring, dioxane ring, and γ-butyrolactone ring. As used herein, the term "aliphatic hydrocarbon ring group" refers to, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5, etc.) from a ring that falls under the category of an aliphatic hydrocarbon ring. As used herein, the term "aliphatic heterocyclic group" refers to, for example, a group obtained by removing one or more hydrogen atoms (e.g., 1 to 5, etc.) from a ring that falls under the category of an aliphatic heterocycle.

[0022] In this specification, when a formula showing a chemical structure contains a plurality of identical symbols indicating the type or number of groups, the contents of the plurality of identical symbols are independent of each other, and the contents of the plurality of identical symbols may be the same or different, unless otherwise specified. In this specification, when a formula showing a chemical structure contains a plurality of groups of the same type (e.g., alkyl groups, etc.), the specific contents of the plurality of groups of the same type are independent of each other, and the specific contents of the plurality of groups of the same type may be the same or different, unless otherwise specified.

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

[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 be described in only one of the cis and trans forms for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form. Furthermore, in this specification, with respect to compounds having an asymmetric atom, the general formula or structural formula representing the compound may be described without distinguishing between stereoisomers for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either form, and may be any one form or a mixture. For example, a compound having an asymmetric carbon atom may be either the S-form or the R-form, or a mixture thereof, unless otherwise specified.

[0025] In this specification, unless otherwise specified, * in a formula indicates a bonding position.

[0026] [Composition] The composition of the present invention contains a compound represented by formula (1) (hereinafter also referred to as "Specific Compound 1") and a compound represented by formula (2) (hereinafter also referred to as "Specific Compound 2"), and the content of the compound represented by formula (2) is 0.2 to 7.5 mass% relative to the total mass of the compound represented by formula (1).

[0027]

[0028] In formula (1) and formula (2), A to D each independently represent a monocyclic aromatic ring selected from group X, which may have a substituent. Group X: a benzene ring, a furan ring, a thiophene ring, a selenophene ring, and a thiazole ring. q represents an integer of 1 to 4. Ar １ａ and Ar ４ａ each independently represents a monocyclic aromatic ring group selected from Group X, a bicyclic aromatic ring group composed of aromatic rings selected from Group X, or a tricyclic aromatic ring group composed of aromatic rings selected from Group X, which may have a substituent different from the group represented by Formula (3). ２ａ and Ar ３ａeach independently represents a monocyclic aromatic ring group selected from the above group X, or a bicyclic aromatic ring group composed of aromatic rings selected from the above group X, which may have a substituent different from the group represented by formula (3). １ｂ and Ar ４ｂ each independently represents a monocyclic aromatic ring group selected from Group X, a bicyclic aromatic ring group composed of aromatic rings selected from Group X, or a tricyclic aromatic ring group composed of aromatic rings selected from Group X, each of which may have a substituent. ２ｂ and Ar ３ｂ each independently represents a monocyclic aromatic ring group selected from the above group X, or a bicyclic aromatic ring group composed of aromatic rings selected from the above group X, which may have a substituent. １ｂ , Ar ２ｂ , Ar ３ｂ , and Ar ４ｂ In the group represented by the formula (3), the total number of groups represented by the formula (3) contained as the substituent is 1 or more. n and m each independently represent an integer of 0 to 2. １ａ has a substituent different from the group represented by formula (3), Ar １ｂ is Ar １ａ has the same substituents as those of Ar ２ａ has a substituent different from the group represented by formula (3), Ar ２ｂ is Ar ２ａ has the same substituents as those of Ar ３ａ has a substituent different from the group represented by formula (3), Ar ３ｂ is Ar ３ａ has the same substituents as those of Ar ４ａ has a substituent different from the group represented by formula (3), Ar ４ｂ is Ar ４ａ In addition, A to D, n, m, and q in the formula (2) are the same as A to D, n, m, and q in the formula (1), respectively. １ ~R ３each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.

[0029] While the reason why the composition having the above-described configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. Polycyclic compounds such as specific compound 1 generally have high crystallinity and therefore high sublimation temperatures. Therefore, when a vapor-deposited film is formed using a composition containing the polycyclic compound, decomposition of the polycyclic compound may occur. The composition of the present invention contains a specific compound 2 having a group represented by formula (3) (hereinafter also referred to as a "specific silyl group") in a predetermined amount or more relative to specific compound 1, thereby reducing the crystallinity and lowering the sublimation temperature of the composition. Furthermore, because the content of specific compound 2 is equal to or less than the predetermined amount, the charge transport efficiency when a photoelectric conversion film is formed is also maintained. Therefore, it is believed that a decrease in charge transport efficiency due to decomposition products generated during film formation can be suppressed in a film formed using the composition of the present invention, and as a result, a photoelectric conversion element with a response speed that is less dependent on electric field strength can be formed. Hereinafter, the fact that the response speed of a photoelectric conversion element formed using the composition of the present invention has a smaller electric field strength dependency will also be simply referred to as "the effect of the present invention is superior." Each component contained in the composition will be described in detail below.

[0030] [Compound Represented by Formula (1)] The composition of the present invention contains a specific compound 1 represented by formula (1).

[0031]

[0032] In formula (1), A to D each independently represent a monocyclic aromatic ring selected from Group X, which may have a substituent. Group X: a benzene ring, a furan ring, a thiophene ring, a selenophene ring, and a thiazole ring. Each of the rings represented by A to D is fused with an adjacent monocyclic aromatic ring. For example, the monocyclic aromatic ring represented by A is fused with the monocyclic aromatic ring represented by B.

[0033] Examples of the substituent that the monocyclic aromatic ring may have include the above-mentioned substituent W, and are preferably a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms, more preferably having 1 to 3 carbon atoms) that may have a halogen atom, and more preferably a halogen atom, a methyl group, or a trifluoromethyl group. In terms of achieving better effects of the present invention, it is preferable that the monocyclic aromatic ring has no substituent.

[0034] In formula (1), q represents an integer of 1 to 4. q is preferably an integer of 1 to 3. When q is 1, the compound represented by formula (1) is represented by formula (1-1), when q is 2, the compound represented by formula (1) is represented by formula (1-2), when q is 3, the compound represented by formula (1) is represented by formula (1-3), and when q is 4, the compound represented by formula (1) is represented by formula (1-4). In formulas (1-2) to (1-4), the rings represented by C that are present in plural may be the same or different from each other.

[0035]

[0036] In formula (1), Ar １ａ and Ar ４ａ each independently represents a monocyclic aromatic ring group selected from the above group X, a bicyclic aromatic ring group composed of aromatic rings selected from the above group X, or a tricyclic aromatic ring group composed of aromatic rings selected from the above group X, which may have a substituent different from the specific silyl group. In this specification, the monocyclic aromatic ring group selected from the above group X is more specifically a monocyclic aromatic ring group composed of aromatic rings selected from the above group X. Furthermore, the x-cyclic aromatic ring group (x is an integer of 2 or more) composed of aromatic rings selected from the above group X is more specifically an x-cyclic aromatic ring group composed of fused rings of x aromatic rings selected from the above group X. Ar １ａ and Ar ４ａ The aromatic ring group represented by the formula (I) is preferably a monocyclic or bicyclic group, since the effects of the present invention are more excellent. １ａ and Ar ４ａExamples of the aromatic ring constituting the group represented by the formula (I) include a benzene ring, a furan ring, a thiophene ring, a selenophene ring, a thiazole ring, a naphthalene ring, a benzothiophene ring, a benzofuran ring, a benzoselenophene ring, a benzothiazole ring, a thienothiophene ring, a thiazolothiazole ring, an anthracene ring, a phenanthrene ring, a naphthothiophene ring, a naphthofuran ring, a naphthoselenophene ring, a naphthothiazole ring, a dibenzothiophene ring, a dibenzofuran ring, and a dibenzoselenophene ring, and a benzene ring, a furan ring, a thiophene ring, a selenophene ring, a thiazole ring, a naphthalene ring, a benzothiophene ring, a benzofuran ring, a benzoselenophene ring, a benzothiazole ring, a thienothiophene ring, or a thiazolothiazole ring is preferred. １ａ and Ar ４ａ The group represented by the following formula (I) is preferably an aromatic ring group consisting of the above ring.

[0037] As mentioned above, the monocyclic aromatic ring group, the bicyclic aromatic ring group, and the tricyclic aromatic ring group may all have a substituent different from the specific silyl group.As the substituent different from the specific silyl group, the above-mentioned substituent W other than the specific silyl group can be mentioned, and a halogen atom, an aliphatic hydrocarbon group which may have a substituent, a cyano group, or an alkoxy group which may have a substituent is preferred, a halogen atom is more preferred, and a fluorine atom or a chlorine atom is even more preferred.The specific silyl group will be described later.

[0038] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or a chlorine atom being preferred.

[0039] The aliphatic hydrocarbon group may be linear, branched, or cyclic, with linear or branched being preferred. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. The branched aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 7, and even more preferably 3 to 5. The cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic. The cyclic aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 6. Examples of the substituent that the aliphatic hydrocarbon group may have include the substituent W described above, with a halogen atom or an alkoxy group that may have a substituent being preferred, and a halogen atom being more preferred.

[0040] The alkoxy group may be linear, branched, or cyclic, and is preferably linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 4. Examples of the substituent that the alkoxy group may have include the aforementioned substituent W, and a halogen atom is preferred, and a fluorine atom or a chlorine atom is more preferred.

[0041] The effect of the present invention is more excellent, １ａ and Ar ４ａ Each of the groups represented by the following formula (I) preferably has no substituent or has a fluorine atom or a chlorine atom as a substituent.

[0042] Ar １ａ and Ar ４ａ may be the same or different, and are preferably the same groups.

[0043] Ar １ａ and Ar ４ａ Examples of the group include the groups shown below.

[0044]

[0045]

[0046] In formula (1), Ar ２ａ and Ar ３ａ each independently represents a monocyclic aromatic ring group selected from Group X above, or a bicyclic aromatic ring group composed of aromatic rings selected from Group X above, which may have a substituent different from the specific silyl group. ２ａ and Ar ３ａ The aromatic ring group represented by Ar is preferably a monocyclic group. ２ａ and Ar ３ａ Examples of the aromatic ring constituting the group represented by the formula (I) include a benzene ring, a furan ring, a thiophene ring, a selenophene ring, a thiazole ring, a naphthalene ring, a benzothiophene ring, a benzofuran ring, a benzoselenophene ring, a benzothiazole ring, a thienothiophene ring, and a thiazolothiazole ring, and a benzene ring, a furan ring, a thiophene ring, a selenophene ring, or a thiazole ring is preferred. ２ａ and Ar ３ａ The group represented by the following formula (I) is preferably an aromatic ring group consisting of the above ring.

[0047] As described above, the monocyclic aromatic ring group and the bicyclic aromatic ring group may each have a substituent different from the specific silyl group. ２ａ and Ar ３ａ The definition and preferred embodiments of the substituents, which may be contained in the group represented by the formula (I), which are different from the specific silyl group, are as follows: １ａ and Ar ４ａ is the same as the substituent different from the specific silyl group that the group represented by the formula (I) may have.

[0048] The effect of the present invention is more excellent, ２ａ and Ar ３ａ Each of these groups preferably has no substituent, or if it has a substituent, it preferably has a fluorine atom or a chlorine atom as the substituent.

[0049] Ar ２ａ When there are multiple Ar ２ａ may be the same or different, and Ar ３ａ When there are multiple Ar ３ａ may be the same or different. ２ａand Ar ３ａ may be the same or different, and are preferably the same groups.

[0050] Ar ２ａ and Ar ３ａ Examples of the group include the groups shown below.

[0051]

[0052] The effect of the present invention is more excellent, １ａ , Ar ２ａ , Ar ３ａ , and Ar ４ａ It is preferable that each of the groups represented by the following formula (1) satisfies Requirement 1. Requirement 1: The group has no substituent, or has a fluorine atom or a chlorine atom as a substituent. That is, Ar １ａ has no substituent or has a fluorine atom or a chlorine atom as a substituent, and Ar ２ａ has no substituent or has a fluorine atom or a chlorine atom as a substituent, and Ar ３ａ has no substituent or has a fluorine atom or a chlorine atom as a substituent, and Ar ４ａ It is preferred that the group represented by the following formula (I) has no substituent or has a fluorine atom or a chlorine atom as a substituent.

[0053] In formula (1), n ​​and m each independently represent an integer of 0 to 2. n and m are preferably 0 or 1, and more preferably 1. n and m may be the same or different, and are preferably the same.

[0054] The effect of the present invention is more excellent, １ａ and Ar ２ａ The total number of aromatic rings in the group represented by Ar is preferably 1 to 4, and more preferably 2 or 3. ４ａ and Ar ３ａ The total number of aromatic rings in the group represented by the formula (I) is preferably 1 to 4, more preferably 2 or 3. For example, Ar １ａ is a monocyclic aromatic ring group, n is 2, and one of Ar ２ａis a monocyclic aromatic ring group, and the other Ar ２ａ is a bicyclic aromatic ring group, the total number of aromatic rings is calculated as 1+1+2=4.

[0055] In formula (1), the number of aromatic rings represented by A to D and Ar １ａ ~Ar ４ａ The total number of aromatic rings in the group represented by the formula (I) is preferably 6 to 10, and more preferably 9 or 10. For example, when q is 2 and Ar １ａ and Ar ４ａ is a monocyclic aromatic ring group, n and m are 2, and one of Ar ２ａ is a monocyclic aromatic ring group, and the other Ar ２ａ is a bicyclic aromatic ring group, and one Ar ３ａ is a monocyclic aromatic ring group, and the other Ar ３ａ When Ar is a bicyclic aromatic ring group, the number of aromatic rings represented by A to D is 5, １ａ ~Ar ４ａ The number of aromatic rings in the group represented by the formula (I) is 1+1+2+1+1+2=8, and the number of aromatic rings represented by the formula (I) and the number of aromatic rings represented by the formula (I) are the same as those of the formula (I). １ａ ~Ar ４ａ The sum of the number of aromatic rings in the group represented by q can be calculated as 5 + 8 = 13. When q is 2 as described above, the number of aromatic rings represented by A to D is the sum of the number of aromatic rings represented by one A, one aromatic ring represented by B, two aromatic rings represented by C, and one aromatic ring represented by D. In other words, the number of aromatic rings represented by A to D varies depending on the aromatic rings constituting C represented by q.

[0056] In the composition, Specific Compound 1 may be used singly or in combination of two or more. The content of Specific Compound 1 is preferably 80.0 mass% or more, more preferably 90.0 mass% or more, based on the total mass of the composition. The upper limit is preferably 99.8 mass% or less.

[0057] [Compound Represented by Formula (2)] The composition of the present invention contains a specific compound 2 represented by formula (2).

[0058]

[0059] In formula (2), A to D, n, m, and q have the same meanings as A to D, n, m, and q in formula (1). Note that A to D, n, m, and q in formula (2) are each the same as A to D, n, m, and q in formula (1).

[0060] In formula (2), Ar １ｂ and Ar ４ｂ each independently represents a monocyclic aromatic ring group selected from Group X, a bicyclic aromatic ring group composed of aromatic rings selected from Group X, or a tricyclic aromatic ring group composed of aromatic rings selected from Group X, each of which may have a substituent. １ｂ and Ar ４ｂ The aromatic ring group represented by the formula (I) is preferably a monocyclic or bicyclic group, since the effects of the present invention are more excellent. １ｂ and Ar ４ｂ Examples and preferred embodiments of the aromatic ring constituting the group represented by the formula １ａ and Ar ４ａ In terms of the effects of the present invention being more excellent, the aromatic ring is the same as that constituting the group represented by Ar １ｂ The aromatic ring constituting the group represented by Ar １ａ In addition, in order to improve the effects of the present invention, it is preferable that the aromatic ring is the same as the aromatic ring constituting the group represented by Ar ４ｂ The aromatic ring constituting the group represented by Ar ４ａ It is preferable that the aromatic ring is the same as the aromatic ring constituting the group represented by the formula:

[0061] As described above, the monocyclic aromatic ring group, the bicyclic aromatic ring group, and the tricyclic aromatic ring group may all have a substituent. １ｂ and Ar ４ｂ Examples of the substituent that the aromatic ring group represented by the formula (I) may have include the substituent W described above. Of these, a specific silyl group, a halogen atom, an aliphatic hydrocarbon group which may have a substituent, a cyano group, or an alkoxy group which may have a substituent is preferred, a specific silyl group or a halogen atom is more preferred, and a specific silyl group, a fluorine atom, or a chlorine atom is even more preferred.

[0062] The specific silyl group is a group represented by formula (3).

[0063]

[0064] In formula (3), R １ ~R ３ each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, with linear or branched being preferred, and branched being more preferred. The number of carbon atoms in a linear alkyl group is preferably 1 to 3, more preferably 1. The number of carbon atoms in a branched or cyclic alkyl group is 3 or 4, more preferably 3. R １ ~R ３ Among these, a branched alkyl group having 3 or 4 carbon atoms is preferred, and a branched alkyl group having 3 carbon atoms (isopropyl group) is more preferred.

[0065] Ar １ｂ and Ar ４ｂ The definitions and preferred embodiments of the halogen atom, the aliphatic hydrocarbon group which may have a substituent, and the alkoxy group which may have a substituent that may be contained in the aromatic ring group represented by the formula １ａ and Ar ４ａ The definitions and preferred embodiments are the same as those of the halogen atom, the aliphatic hydrocarbon group which may have a substituent, and the alkoxy group which may have a substituent, which may be contained in the aromatic ring group represented by the following formula:

[0066] The effect of the present invention is more excellent, １ｂ and Ar ４ｂ Each of these preferably has no substituent, or if it has a substituent, it preferably has a specific silyl group, a fluorine atom, or a chlorine atom as the substituent.

[0067] Ar １ｂ and Ar ４ｂ may be the same or different, and are preferably groups formed from the same aromatic ring.

[0068] In addition, Ar １ａ has a substituent different from the specific silyl group, Ar １ｂ is Ar １ａ has the same substituents as those of Ar ４ａhas a substituent different from the specific silyl group, Ar ４ｂ is Ar ４ａ For example, Ar １ａ When the group represented by the formula (I) has a fluorine atom as a substituent, Ar １ｂ It is preferable that the group represented by the following formula also has a fluorine atom as a substituent. １ｂ The group represented by the formula (I) may further have a specific silyl group as a substituent.

[0069] Ar １ｂ does not have a specific silyl group, Ar １ｂ and Ar １ａ and the groups represented by Ar １ｂ When Ar has a specific silyl group, １ｂ A group in which a specific silyl group in the group represented by the formula: １ａ It is preferable that Ar is the same as the group represented by ４ｂ does not have a specific silyl group, Ar ４ｂ and Ar ４ａ and the groups represented by Ar ４ｂ When Ar has a specific silyl group, ４ｂ A group in which a specific silyl group in the group represented by the formula: ４ａ It is preferable that the group is the same as the group represented by the following formula:

[0070] Ar １ｂ and Ar ４ｂ Examples of the aryl group include Ar. １ａ and Ar ４ａ In the following, R １ ~R ３ each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.

[0071]

[0072]

[0073]

[0074] In formula (2), Ar２ｂ and Ar ３ｂ each independently represents a monocyclic aromatic ring group selected from the above group X, or a bicyclic aromatic ring group composed of aromatic rings selected from the above group X, which may have a substituent. As described above, both the monocyclic aromatic ring group and the bicyclic aromatic ring group may have a substituent. ２ｂ and Ar ３ｂ The aromatic ring group represented by Ar is preferably a monocyclic group. ２ｂ and Ar ３ｂ Examples and preferred embodiments of the aromatic ring constituting the group represented by the formula ２ａ and Ar ３ａ In terms of the effects of the present invention being more excellent, the aromatic ring is the same as that constituting the group represented by Ar ２ｂ The aromatic ring constituting the group represented by Ar ２ａ In addition, in order to improve the effects of the present invention, it is preferable that the aromatic ring is the same as the aromatic ring constituting the group represented by Ar ３ｂ The aromatic ring constituting the group represented by Ar ３ａ It is preferable that the aromatic ring is the same as the aromatic ring constituting the group represented by the formula:

[0075] Ar ２ｂ and Ar ３ｂ The definition and preferred embodiments of the substituents that may be possessed by the aromatic ring group represented by Ar １ｂ and Ar ４ｂ These are the same as the substituents that may be possessed by the aromatic ring group represented by the following formula:

[0076] The effect of the present invention is more excellent, ２ｂ and Ar ３ｂ Each of these preferably has no substituent, or if it has a substituent, it preferably has a specific silyl group, a fluorine atom, or a chlorine atom as the substituent.

[0077] Ar ２ｂ When there are multiple Ar ２ｂ may be the same or different, and Ar ３ｂ When there are multiple Ar ３ｂ may be the same or different. ２ｂ and Ar ３ｂmay be the same or different, and are preferably aromatic ring groups each composed of the same aromatic ring.

[0078] In addition, Ar ２ａ has a substituent different from the specific silyl group, Ar ２ｂ is Ar ２ａ has the same substituents as those of Ar ３ａ has a substituent different from the specific silyl group, Ar ３ｂ is Ar ３ａ For example, Ar ２ａ When the group represented by the formula (I) has a fluorine atom as a substituent, Ar ２ｂ It is preferable that the group represented by the following formula also has a fluorine atom as a substituent. ２ｂ The group represented by the formula (I) may further have a specific silyl group as a substituent.

[0079] Ar ２ｂ does not have a specific silyl group, Ar ２ｂ and Ar ２ａ and the groups represented by Ar ２ｂ When Ar has a specific silyl group, ２ｂ A group in which a specific silyl group in the group represented by the formula: ２ａ It is preferable that Ar is the same as the group represented by ３ｂ does not have a specific silyl group, Ar ３ｂ and Ar ３ａ and the groups represented by Ar ３ｂ When Ar has a specific silyl group, ３ｂ A group in which a specific silyl group in the group represented by the formula: ３ａ It is preferable that the group is the same as the group represented by the following formula:

[0080] Ar ２ｂ and Ar ３ｂ Examples of the aryl group include Ar. ２ａ and Ar ３ａ In the following, R １ ~R ３each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.

[0081]

[0082] The effect of the present invention is more excellent, １ｂ , Ar ２ｂ , Ar ３ｂ , and Ar ４ｂ It is preferable that each of the groups represented by the following formula (1) satisfies Requirement 2. Requirement 2: The group has no substituent, or has a fluorine atom, a chlorine atom, or a specific silyl group as a substituent. That is, Ar １ｂ has no substituent or has a fluorine atom, a chlorine atom, or a specific silyl group as a substituent, and Ar ２ｂ has no substituent or has a fluorine atom, a chlorine atom, or a specific silyl group as a substituent, and Ar ３ｂ has no substituent or has a fluorine atom, a chlorine atom, or a specific silyl group as a substituent, and Ar ４ｂ It is preferred that the group represented by the formula (I) has no substituent or has a fluorine atom, a chlorine atom, or a specific silyl group as a substituent.

[0083] In formula (2), Ar １ｂ , Ar ２ｂ , Ar ３ｂ , and Ar ４ｂ In the group represented by the formula (I), the total number of the specific silyl groups contained as the substituent is 1 or more, and in terms of the effects of the present invention being more excellent, it is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1. １ｂ and Ar ２ｂ In the group represented by the formula (I), the total number of the specific silyl groups contained as the substituents is 1, and Ar ３ｂ and Ar ４ｂ In the group represented by the formula (I), it is preferable that the total number of the specific silyl groups contained as the substituents is 0 or 1, and １ｂ and Ar ２ｂ In the group represented by the formula (I), the total number of the specific silyl groups contained as the substituents is 1, and Ar ３ｂ and Ar ４ｂIn the group represented by the formula (I), it is more preferable that the total number of the specific silyl groups contained as the substituents is 0.

[0084] The effect of the present invention is more excellent, １ｂ and Ar ２ｂ The total number of aromatic rings in the group represented by Ar is preferably 1 to 4, and more preferably 2 or 3. ４ｂ and Ar ３ｂ The total number of aromatic rings in the group represented by the formula (I) is preferably 1 to 4, and more preferably 2 or 3.

[0085] In formula (2), the number of aromatic rings represented by A to D and Ar １ｂ ~Ar ４ｂ The total number of aromatic rings in the group represented by the formula (I) is preferably 6 to 10, and more preferably 9 or 10.

[0086] In terms of achieving better effects of the present invention, it is preferable that Specific Compound 2 is a compound having the same structure as Specific Compound 1 when the specific silyl group in Specific Compound 2 is substituted with a hydrogen atom.

[0087] The content of Specific Compound 2 is 0.2 to 7.5% by mass relative to the content of Specific Compound 1. If the content of Specific Compound 2 is less than 0.2% by mass relative to the content of Specific Compound 1, the sublimation temperature of the composition becomes too high, causing decomposition of Specific Compound 1 and Specific Compound 2, and deteriorating the electric field strength dependency of the response speed, which is undesirable. If the content of Specific Compound 2 exceeds 7.5% by mass, the excess Specific Compound 2 reduces the charge transport efficiency, which is undesirable, and deteriorating the electric field strength dependency of the response speed. In order to achieve better effects of the present invention, the content of Specific Compound 2 is preferably 0.3 to 5.0% by mass relative to the content of Specific Compound 1. The content of Specific Compound 2 relative to the content of Specific Compound 1 is determined by the following method. The composition is incinerated using 60% nitric acid, and Si is quantified by ICP-OES (Optima 7300, absolute calibration curve method). The content of Specific Compound 2 relative to the content of Specific Compound 1 is calculated from the measured amount of Si and the molecular weights of Specific Compound 1 and Specific Compound 2. The above measurement is carried out three times, and the arithmetic mean of the three values ​​obtained is used as the value of the content of specific compound 2 relative to the content of specific compound 1.

[0088] The total content of Specific Compound 1 and Specific Compound 2 is preferably 99.0% by mass or more, more preferably 99.5% by mass or more, and even more preferably 99.9% by mass or more, based on the total mass of the composition. The upper limit of the total content of Specific Compound 1 and Specific Compound 2 is not particularly limited, and is preferably 100% by mass.

[0089] Examples of specific compound 1 and specific compound 2 include the following compounds: In the following structural formula, one A in specific compound 1 is Ar １ａ -(Ar ２ａ ) ｎ -, and the other A is Ar ４ａ -(Ar ３ａ ) ｍ In specific compound 2, one A represents a group represented by Ar １ｂ -(Ar ２ｂ ) ｎ -, and the other A is Ar ４ｂ -(Ar ３ｂ ) ｍ represents a group represented by -.１ａ ~Ar ４ａ and Ar １ｂ ~Ar ４ｂ Details and specific examples of the group represented by the formula are as described above.

[0090]

[0091]

[0092]

[0093] [Other Components] The composition may contain other components in addition to Specific Compound 1 and Specific Compound 2. Examples of other components include an n-type organic semiconductor and a dye that may be contained in the photoelectric conversion film described below.

[0094] [Method for Producing Composition] The composition of the present invention can be produced by a known method. Suitable examples of the method for producing the composition of the present invention include a method of mixing Specific Compound 1 and Specific Compound 2, and a method including a step X of obtaining the composition of the present invention using a derivative of Specific Compound 1 having a specific silyl group.

[0095] As a method for preparing the composition of the present invention by mixing specific compound 1 and specific compound 2, a method in which a mixed sample of specific compound 1 and specific compound 2 is sublimated can be mentioned.

[0096] <Step X> Specifically, step X is a step of obtaining the composition of the present invention by using a derivative of specific compound 1 as a raw material and eliminating specific silyl groups so that the content ratio of specific compound 2 to specific compound 1 is a predetermined ratio. The derivative of specific compound 1 is a compound in which one or more specific silyl groups are substituted on specific compound 1. The derivative of specific compound 1 can be appropriately selected depending on the structures of specific compound 1 and specific compound 2, and may be specific compound 2 itself or a compound in which specific compound 2 is further substituted with a specific silyl group. The derivative of specific compound 1 can be synthesized by a known method (for example, a coupling reaction).

[0097] As a method for removing the specific silyl group, a known desilylation reaction can be used, for example, a method for removing the specific silyl group using a fluorine anion can be mentioned. By adjusting the reaction conditions (reaction concentration, reaction temperature, reaction time), etc., the contents of specific compound 1 and specific compound 2 in the product can be adjusted. The content ratio of specific compound 1 to specific compound 2 in the product obtained by the above method can be measured by the method described above.

[0098] The composition obtained by the above reaction is preferably further subjected to a purification treatment, such as sublimation purification or heated suspension washing.

[0099] It is also preferable that the derivative of Specific Compound 1 is purified before being subjected to the elimination reaction, for example, by recrystallization, silica gel column chromatography, or heated suspension washing.

[0100] [Uses] The composition of the present invention is particularly useful as a material for a photoelectric conversion film used in a photoelectric conversion element, an imaging element, a photosensor, or a photovoltaic cell. The composition of the present invention can function as a p-type organic semiconductor in the photoelectric conversion film. In particular, the effects of the present invention are significantly exhibited when the composition of the present invention is used as a material for a photoelectric conversion film formed by a dry film formation method.

[0101] [Photoelectric Conversion Element] The photoelectric conversion element of the present invention has a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film contains the composition of the present invention and an n-type organic semiconductor.

[0102] FIG. 1 shows a cross-sectional schematic diagram of one embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in FIG. 1 has a configuration in which a conductive film (hereinafter also referred to as "lower electrode") 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing the composition of the present invention, and a transparent conductive film (hereinafter also referred to as "upper electrode") 15 functioning as an upper electrode are stacked in this order. FIG. 2 shows an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in FIG. 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 and 2 may be changed as appropriate depending on the application and characteristics.

[0103] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 through the upper electrode 15. When the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1×10 is applied between the pair of electrodes. －５ ~1 x 10 ７ In terms of performance and power consumption, it is preferable to apply a voltage of 1×10 V / cm. －４ ~1 x 10 ７ V / cm is more preferable, and 1×10 －３ ~5 x 10 ６ V / cm is more preferable. Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode in FIGS. 1 and 2. When the photoelectric conversion element 10a (or 10b) is used as a photosensor or incorporated into an imaging element, a voltage can be applied in a similar manner. As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably used as an imaging element. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

[0104] [Photoelectric Conversion Film] The photoelectric conversion element has a photoelectric conversion film. The photoelectric conversion film contains the composition of the present invention and an n-type organic semiconductor. In other words, the photoelectric conversion film contains Specific Compound 1, Specific Compound 2, and an n-type organic semiconductor, and the content of Specific Compound 2 is 0.2 to 7.5 mass% relative to the content of Specific Compound 1.

[0105] Details of the composition of the present invention are as described above. It is also preferable that the composition of the present invention in the photoelectric conversion film comprises Specific Compound 1 and Specific Compound 2. The total content of Specific Compound 1 and Specific Compound 2 in the photoelectric conversion film ((film thickness of Specific Compound 1 in terms of a single layer + film thickness of Specific Compound 2 in terms of a single layer) / film thickness of photoelectric conversion film × 100) is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and even more preferably 25 to 50 vol%.

[0106] <n-Type Organic Semiconductor> The n-type organic semiconductor is a compound different from the above-mentioned Specific Compound 1 and Specific Compound 2. The n-type organic semiconductor is an acceptor organic semiconductor material (compound), and refers to an organic compound that has the property of easily accepting electrons. In other words, when two organic compounds are used in contact with each other, the n-type organic semiconductor refers to the organic compound that has a larger electron affinity. In other words, any organic compound can be used as the acceptor organic semiconductor as long as it has electron-accepting properties. Examples of n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and derivatives thereof; fused aromatic carbon ring compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole). ), polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic dianhydride; 1,4,5,8-naphthalenetetracarboxylic diimide derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and derivatives thereof; triazole compounds; distyrylarylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silole compounds; 3,4,9,10-perylenetetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic diimide derivatives; and the compounds described in paragraphs

[0056] to

[0057] of JP-A No. 2006-100767.

[0107] As the n-type organic semiconductor (compound), fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferred. For example, fullerene C ６０ , fullerene C ７０ , fullerene C ７６ , fullerene C７８ , fullerene C ８０ , fullerene C ８２ , fullerene C ８４ , fullerene C ９０ , fullerene C ９６ , fullerene C ２４０ , fullerene C ５４０ and mixed fullerenes. Examples of fullerene derivatives include compounds in which a substituent is added to the above-mentioned fullerenes. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. Preferred fullerene derivatives are the compounds described in JP-A-2007-123707.

[0108] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0109] The maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less or in the range of 500 to 600 nm.

[0110] The content of the n-type organic semiconductor in the photoelectric conversion film (thickness of the n-type organic semiconductor in terms of a single layer / thickness of the photoelectric conversion film × 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 20 to 50% by volume.

[0111] When the n-type organic semiconductor contains fullerenes, the content of the fullerenes relative to the total content of the n-type organic semiconductors (film thickness of fullerenes converted into a single layer / total film thickness of each n-type organic semiconductor converted into a single layer × 100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume. Fullerenes may be used singly or in combination of two or more types.

[0112] <Dye> The photoelectric conversion film preferably further contains a dye. The dye is preferably an organic dye. Examples of the organic dye include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, and the like. Examples of the dye include clidinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, imidazoquinoxaline dyes described in WO2020 / 013246, WO2022 / 168856, JP2023-10305A, and JP2023-10299A, as well as acceptor-donor-acceptor type dyes in which two acidic nuclei are bonded to a donor, and donor-acceptor-donor type dyes in which two donors are bonded to an acceptor.

[0113] The maximum absorption wavelength of the dye is preferably in the visible light region, more preferably in the wavelength range of 400 to 650 nm, and even more preferably in the wavelength range of 450 to 650 nm. The maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1.0. However, if the specific compound is insoluble in chloroform, the value measured using the specific compound vapor-deposited into a film state is used as the maximum absorption wavelength of the specific compound.

[0114] The dye preferably has an ionization potential of −5.0 to −6.0 eV in a single film in terms of stability when used as a p-type organic semiconductor and matching of the energy level with that of an n-type organic semiconductor.

[0115] When the photoelectric conversion film contains a dye, it preferably has a bulk heterostructure formed in a state in which the dye and an n-type organic semiconductor are mixed. The bulk heterostructure is a layer in the photoelectric conversion film in which the dye 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 JP 2005-303266 A.

[0116] The difference in electron affinity between the dye and the n-type organic semiconductor is preferably 0.1 eV or more.

[0117] The content of the dye (film thickness in monolayer equivalent of the dye / (film thickness in monolayer equivalent of the specific compound 1 + film thickness in monolayer equivalent of the specific compound 2 + film thickness in monolayer equivalent of the n-type organic semiconductor + film thickness in monolayer equivalent of the dye) × 100) is preferably 10 to 75 vol%, more preferably 15 to 50 vol%. The photoelectric conversion film is preferably substantially composed of specific compound 1, specific compound 2, an n-type organic semiconductor, and a dye that is contained as desired. "Substantially" means that the total content of specific compound 1, specific compound 2, the n-type organic semiconductor, and the dye is 90 to 100 vol%, preferably 95 to 100 vol%, more preferably 99 to 100 vol%, relative to the total mass of the photoelectric conversion film.

[0118] The photoelectric conversion film containing the specific compound is a non-luminescent film and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode). A non-luminescent film means a film having a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, more preferably 0.1% or less. The lower limit is often 0% or more.

[0119] <Film formation method> Examples of the film formation method for the photoelectric conversion film include dry film formation methods. Examples of dry film formation methods include physical vapor deposition methods such as vapor deposition (particularly vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization, and vacuum deposition methods are preferred. When forming the photoelectric conversion film by vacuum deposition, manufacturing conditions such as the degree of vacuum and deposition temperature can be set according to conventional methods.

[0120] The thickness of the photoelectric conversion film is preferably from 10 to 1,000 nm, more preferably from 50 to 800 nm, and even more preferably from 50 to 500 nm.

[0121] [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, the upper electrode 15 is preferably transparent to the light to be detected. "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 preferably transparent to light with a wavelength of 400 to 800 nm. The transmittance can be measured using a spectrophotometer. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO: Antimony Tin Oxide, FTO: Fluorine-doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO); metal thin films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and nanocarbon materials such as carbon nanotubes and graphene. Of these, conductive metal oxides are preferred in terms of high conductivity and transparency.

[0122] Typically, when the conductive film is made thinner than a certain range, the resistance value often increases rapidly. In a solid-state imaging device incorporating a photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10,000 Ω / □, and there is a wide degree of freedom in the range of film thickness that can be reduced. Furthermore, the thinner the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the higher the light transmittance. An increase in light transmittance is desirable because it increases light absorption in the photoelectric conversion film and enhances photoelectric conversion performance. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance that accompany a reduction in film thickness, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0123] Depending on the application, the lower electrode 11 may be made transparent or may be made non-transparent and reflect light. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and graphene.

[0124] The method for forming the electrodes can be appropriately selected depending on the electrode material. Specific examples include wet methods such as printing and coating; physical methods such as vacuum deposition, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD. When the electrode material is ITO, examples include electron beam methods, sputtering, resistance heating deposition, chemical reaction methods (such as the sol-gel method), and coating of a dispersion of indium tin oxide.

[0125] [Charge-blocking film: electron-blocking film, hole-blocking film] The photoelectric conversion element preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. Examples of the intermediate layer include a charge-blocking film. When the photoelectric conversion element has this film, the properties (quantum efficiency, response speed, etc.) of the resulting photoelectric conversion element are more excellent. Examples of the charge-blocking film include an electron-blocking film and a hole-blocking film.

[0126] <Electron Blocking Film> The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. Polymer materials can also be used as the electron blocking film. Examples of polymer materials include polymers of phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, as well as derivatives thereof.

[0127] The electron blocking film may be composed of multiple films. The electron blocking film may be composed of an inorganic material. In general, inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher quantum efficiency. Examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

[0128] <Hole-Blocking Film> The hole-blocking film is an acceptor organic semiconductor material (compound), and the n-type organic semiconductors described above can be used. The hole-blocking film may be composed of multiple films.

[0129] Examples of methods for producing a charge blocking film include dry film formation and wet film formation. Examples of dry film formation methods include vapor deposition and sputtering. Vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition such as vacuum deposition being preferred. Examples of wet film formation methods include inkjet printing, spray printing, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with the inkjet method being preferred in terms of high-precision patterning.

[0130] The thickness of each of the charge blocking films (electron blocking film and hole blocking film) is preferably from 3 to 200 nm, more preferably from 5 to 100 nm, and even more preferably from 5 to 30 nm.

[0131] [Substrate] The photoelectric conversion element may further include a substrate. Examples of the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate. The substrate is usually positioned such that a conductive film, a photoelectric conversion film, and a transparent conductive film are stacked in this order on the substrate.

[0132] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. The performance of photoelectric conversion materials may be significantly degraded in the presence of degrading factors such as water molecules. Therefore, the degradation can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer made of ceramics such as dense metal oxides, metal nitrides, or metal nitride oxides, or diamond-like carbon (DLC), which do not allow water molecules to penetrate. Examples of sealing layers include those described in paragraphs

[0210] to

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

[0133] [Method for manufacturing photoelectric conversion element] Examples of methods for manufacturing photoelectric conversion elements include known manufacturing methods. Specifically, for example, methods for manufacturing photoelectric conversion elements include a step of forming a conductive film on a substrate, a step of forming a photoelectric conversion film, and a step of forming a transparent conductive film. The method for manufacturing a photoelectric conversion element may include other steps (for example, a step of forming a charge blocking film and a step of forming a sealing layer) in addition to the above. The method for forming each layer is as described above.

[0134] [Imaging element] An example of an application of a photoelectric conversion element is an imaging element. An imaging element is an element that converts the optical information of an image into an electrical signal, and typically has multiple photoelectric conversion elements arranged in a matrix on the same plane, converting the optical signal into an electrical signal at each photoelectric conversion element (pixel), and outputting the electrical signal pixel by pixel sequentially to the outside of the imaging element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. A manufacturing method for an imaging element is not particularly limited, but examples include a method including the step of manufacturing the photoelectric conversion element described above.

[0135] [Optical Sensor] Other applications of the photoelectric conversion element include, for example, a photocell and an optical sensor, and the photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element may be used alone, or may be used as a line sensor in which the photoelectric conversion elements are arranged linearly or as a two-dimensional sensor in which the photoelectric conversion elements are arranged on a plane.

[0136] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0137] [Compounds used in photoelectric conversion film] The materials used in the photoelectric conversion film are shown below.

[0138] [Synthesis of Compound (2-1)] Compound (2-1) was synthesized according to the following scheme.

[0139]

[0140] Compound (2-1-a) (1.0 g, 2.5 mmol) and compound (2-1-b) (4.0 g, 6.0 mmol) were placed in a three-neck flask, and dehydrated N,N-dimethylformamide (60 mL) was added. Vacuum degassing and nitrogen substitution were repeated three times. Tris(dibenzylideneacetone)dipalladium(0) (0.07 g, 0.08 mmol) and tri(o-tolyl)phosphine (0.09 g, 0.3 mmol) were added to the mixture under a nitrogen atmosphere. Vacuum degassing and nitrogen substitution were repeated three times, and the mixture was allowed to react at 100°C for four hours. After allowing the mixture to cool to 50°C, methanol (60 mL) was added, and the precipitate was filtered off. The resulting crude product was dissolved in chlorobenzene (30 mL) by heating at 140°C and filtered on silica gel while hot. The silica gel was further washed with chlorobenzene (50 mL) heated at 140°C. The resulting filtrate was stirred, and methanol (80 mL) was added thereto, followed by stirring for another hour. The precipitate was filtered off and dried under reduced pressure to obtain compound (2-1). The structure of the product was confirmed by NMR (Nuclear Magnetic Resonance).

[0141] [Synthesis of Compound (1-1)] Compound (1-1) was synthesized according to the following scheme.

[0142]

[0143] Compound (2-1) (500 mg, 0.5 mmol) was placed in a three-neck flask, and anhydrous tetrahydrofuran (100 mL) was added under a nitrogen atmosphere. The mixture was heated to reflux for 1 hour. A solution of tetrabutylammonium fluoride in tetrahydrofuran (2.0 mL, 2.0 mmol) was then added dropwise, and the mixture was heated to reflux for 4 hours. The precipitate was then filtered off. The resulting crude product was washed by heating and suspending it in chlorobenzene (30 mL), N,N-dimethylformamide (30 mL), tetrahydrofuran (30 mL), and ethyl acetate (30 mL), in that order. The precipitate was filtered off and dried under reduced pressure to obtain compound (1-1). The structure of the product was confirmed by field desorption-mass spectrometry (FD-MS).

[0144] [Preparation of Composition of Example (A-1)] Compound (1-1) (400 mg, 0.6 mmol) and compound (2-1) (8 mg, 0.008 mmol) were purified by sublimation under reduced pressure to obtain a composition of Example (A-1) containing compound (1-1) and compound (2-2).

[0145] [Preparation of Composition of Example (A-2)] The composition of Example (A-2) was prepared by the following method.

[0146]

[0147] Compound (2-1) (500 mg, 0.5 mmol) was placed in a three-neck flask, and dehydrated tetrahydrofuran (30 mL) was added under a nitrogen atmosphere. A tetrahydrofuran solution of tetrabutylammonium fluoride (2.0 mL, 2.0 mmol) was then added dropwise. After the dropwise addition, the mixture was heated under reflux for 2 hours, and the precipitate was separated by filtration. The obtained crude product was washed by heating and suspending it in chlorobenzene (30 mL), N,N-dimethylformamide (30 mL), tetrahydrofuran (30 mL), and ethyl acetate (30 mL), in that order, and the precipitate was separated by filtration. The obtained precipitate was purified by sublimation under reduced pressure to obtain the composition of Example (A-2).

[0148] [Preparation of Compositions of Examples (A-8) to (A-39)] The compositions of Examples (A-3) to (A-6) were obtained in the same manner as in Example (A-2), except that the amount of dehydrated tetrahydrofuran was changed to 20 mL. The composition of Example (A-7) was obtained in the same manner as in Example (A-2), except that the amount of dehydrated tetrahydrofuran was changed to 20 mL and the amount of tetrabutylammonium fluoride in tetrahydrofuran was changed to 1.5 mL, 1.5 mmol. The compositions of Examples (A-8) to (A-39) were prepared in accordance with the preparation method of Example (A-2).

[0149] [Preparation of the composition of Comparative Example (B-1)]

[0150]

[0151] According to the above scheme, compound (1-1-1) obtained by synthesis in accordance with the procedure described in Chinese Patent CN201210591543A was used.

[0152] [Preparation of Compositions of Comparative Examples (B-2) to (B-3)] The composition of Comparative Example (B-2) was obtained in the same manner as in Example (A-2), except that the amount of dehydrated tetrahydrofuran was changed to 60 mL. The composition of Comparative Example (B-3) was obtained in the same manner as in Example (A-2), except that the amount of dehydrated tetrahydrofuran was changed to 20 mL, the amount of tetrabutylammonium fluoride in tetrahydrofuran was changed to 1.5 mL, 1.5 mmol, and the reaction conditions were changed to stirring at 40°C for 2 hours.

[0153] [Preparation of Compositions of Comparative Examples (B-4) to (B-8)] Each comparative compound obtained by synthesis using the following method was used as a composition. Comparative compound (3-1) was synthesized by the method described in JP 2010-018529 A. Comparative compound (3-2) was synthesized by the method described in JP 2015-048350 A. Comparative compound (3-3) was synthesized by the method described in JP 2015-199716 A. Comparative compound (3-4) was synthesized by the method described in JP 2015-199716 A. Comparative compound (3-5) was synthesized by the method described in JP 2017-508010 A.

[0154] The components used in forming the photoelectric conversion film are shown below.

[0155] [Specific compound 1]

[0156]

[0157]

[0158] [Specific compound 2]

[0159]

[0160]

[0161] In the compounds, TMS, TIPS, and TBDPS each represent the following structure.

[0162]

[0163] [Comparative composition compounds]

[0164]

[0165] [n-type organic semiconductor] C60: fullerene (C ６０ )

[0166] [Pigment]

[0167]

[0168] [Content Ratio of Specific Compounds] The ratio of specific compound 1 to specific compound 2 in each composition was calculated using the following method. Approximately 10 mg of the resulting composition was transferred to a Teflon (registered trademark) vial, and 60% nitric acid (4 mL) was added and incinerated (260°C). The volume was adjusted to 20 mL with ultrapure water, and then Si was quantified using ICP-OES (Optima 7300, absolute calibration curve method). From the measured amount of Si and the molecular weights of specific compound 1 and specific compound 2, the content of specific compound 2 relative to the content of specific compound 1 {(content of specific compound 2 / content of specific compound 1) × 100} was calculated. The above procedure was repeated three times, and the arithmetic average value of the three measurements was used.

[0169] [Evaluation] The response speed and the electric field strength dependency of the response speed of the photoelectric conversion element obtained using the composition were evaluated by the following method.

[0170] [Fabrication of Photoelectric Conversion Element] A photoelectric conversion element having the configuration shown in FIG. 2 was fabricated using the various components shown above. Here, the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15. Specifically, amorphous ITO was formed on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and compound (EB-1) was further formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm). Next, with the glass substrate at room temperature, a composition of each example or comparative example shown in the table below and an n-type organic semiconductor (fullerene (C ６０)) and the dyes (D-1 to D-4) shown in the table below were co-deposited by vacuum deposition so that the composition ratio was (composition of the example or comparative example / n-type organic semiconductor / dye = 1 / 1 / 1, volume ratio). This resulted in a photoelectric conversion film 12 having a bulk heterostructure of 350 nm. The deposition rate of the photoelectric conversion film 12 was 1.0 Å / sec. Furthermore, compound (EB-2) was deposited on the photoelectric conversion film 12 to form a hole-blocking film 16B (thickness: 10 nm). Amorphous ITO was deposited on the hole-blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming an SiO film as a sealing layer on the upper electrode 15 by vacuum deposition, aluminum oxide (Al ２ O ３ The resulting laminate was heated in a glove box at 150° C. for 30 minutes to obtain a photoelectric conversion element.

[0171]

[0172] [Dark Current] The dark current of each of the obtained photoelectric conversion elements was measured by the following method. ５ A voltage was applied to the photoelectric conversion element so as to obtain an electric field strength of 50 nA / cm. The current value in a dark place (dark current) was measured. As a result, the dark current was 50 nA / cm for all the photoelectric conversion elements. ２ It was confirmed that the dark current was sufficiently low.

[0173] [Quantum efficiency] The operation of each of the obtained photoelectric conversion elements was confirmed. ５ A voltage was applied to the device to achieve an electric field strength of 1000 V / cm. Light was then irradiated from the upper electrode (transparent conductive film) side to evaluate the photoelectric conversion efficiency (external quantum efficiency) at a wavelength of 550 nm. As a result, all devices showed an external quantum efficiency of 30% or more.

[0174] [Response Speed] The response speed of each photoelectric conversion element was evaluated by the following method. ５A voltage was applied so as to achieve an electric field strength of 1000 V / cm. Thereafter, an LED (light emitting diode) was momentarily turned on to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 550 nm at that time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity, and the relative response speed was calculated according to formula (S1). From the obtained value, the response speed was evaluated according to the following evaluation criteria. The response speed is preferably rated B or higher. Formula (S1): Relative response speed = (rise time of each photoelectric conversion element) / (rise time of the photoelectric conversion element of Comparative Example B-1)

[0175] A: Relative response speed is less than 0.8 B: Relative response speed is 0.8 or more and less than 1.2 C: Relative response speed is 1.2 or more

[0176] [Dependence of response speed on electric field strength] The dependence of response speed on electric field strength of each photoelectric conversion element was evaluated by the following method. In the evaluation of [Response speed], a voltage of 7.5×10 ４ The same procedure was followed except that the pressure was changed to 7.5 × 10 ４ The rise time at 7.5 V / cm was measured. The electric field strength dependency of the response speed was calculated according to formula (S2), and the electric field strength dependency of the response speed was evaluated according to the following evaluation criteria. In formula (S2), the numerator and denominator are values ​​measured for the photoelectric conversion element of the same Example or Comparative Example. The electric field strength dependency of the response speed is preferably rated B or higher. Formula (S2): Electric field strength dependency of response speed = (applied voltage of each photoelectric conversion element 7.5 × 10 ４ V / cm) / (applied voltage of each photoelectric conversion element 2.0×10 ５ rise time in V / cm)

[0177] A: The electric field strength dependency of the response speed is less than 2.0. B: The electric field strength dependency of the response speed is 2.0 or more and less than 3.0. C: The electric field strength dependency of the response speed is 3.0 or more and less than 4.0. D: The electric field strength dependency of the response speed is 4.0 or more.

[0178] [Results] The evaluation results are shown in Table 1 below. In the table, the column "Number of specific silyl groups" indicates the number of specific silyl groups that specific compound 2 has. １ ~R ３ " column, R １ ~R ３ is a branched alkyl group having 3 carbon atoms, the value is designated "A", and other cases are designated "B". In the tables, the "Number of aromatic rings" column indicates the number of aromatic rings contained in the specific compound. In the tables, the "Substituent" column indicates the substituents other than the specific silyl group that are possessed by the aromatic rings contained in the specific compound. "Me" means a methyl group. In the tables, "-" in the evaluation column indicates that the photoelectric conversion element could not be manufactured and the evaluation could not be performed.

[0179]

[0180]

[0181] The results shown in the table confirm that the use of the composition of the present invention enables the formation of a photoelectric conversion element whose response speed is less dependent on electric field strength. Furthermore, it was confirmed that the photoelectric conversion element formed using the composition of the present invention also has an excellent response speed.

[0182] From a comparison between Example A-1 and Examples A-7 to A-9, Ar １ｂ and Ar ２ｂ The total number of specific silyl groups contained in Ar is 1, ３ｂ and Ar ４ｂ It was confirmed that the effect of the present invention is more excellent when the total number of specific silyl groups in R is 0. From the comparison of Examples A-8 to A-9 with Examples A-10 to A-33, １ ~R ３ is a branched alkyl group having 3 carbon atoms. Comparison of Examples A-13 to A-14 and A-35 to A-36 with other Examples has shown that the number of aromatic rings represented by A to D in formula (1) and the number of Ar １ａ ~Ar ４ａ The total number of aromatic rings in the group represented by １ｂ ~Ar ４ｂIt was confirmed that the response speed was better when the total number of aromatic rings in the group represented by Ar １ａ , Ar ２ａ , Ar ３ａ , and Ar ４ａ Each of the groups represented by the following formula satisfies requirement 1, and Ar １ｂ , Ar ２ｂ , Ar ３ｂ , and Ar ４ｂ It has been confirmed that when each of the groups represented by the following formula (I) satisfies requirement 2, the effects of the present invention are more excellent.

[0183] 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 composition comprising a compound represented by formula (1) and a compound represented by formula (2), wherein the content of the compound represented by formula (2) is 0.2 to 7.5% by mass relative to the total mass of the compound represented by formula (1). In formula (1) and formula (2), A to D each independently represent a monocyclic aromatic ring selected from group X, which may have a substituent. Group X: a benzene ring, a furan ring, a thiophene ring, a selenophene ring, and a thiazole ring. q represents an integer of 1 to 4. Ar １ａ and Ar ４ａ each independently represents a monocyclic aromatic ring group selected from Group X, a bicyclic aromatic ring group composed of aromatic rings selected from Group X, or a tricyclic aromatic ring group composed of aromatic rings selected from Group X, which may have a substituent different from the group represented by Formula (3). ２ａ and Ar ３ａ each independently represents a monocyclic aromatic ring group selected from Group X, or a bicyclic aromatic ring group composed of aromatic rings selected from Group X, which may have a substituent different from the group represented by Formula (3). １ｂ and Ar ４ｂ each independently represents a monocyclic aromatic ring group selected from Group X, a bicyclic aromatic ring group composed of aromatic rings selected from Group X, or a tricyclic aromatic ring group composed of aromatic rings selected from Group X, each of which may have a substituent. ２ｂ and Ar ３ｂ each independently represents a monocyclic aromatic ring group selected from Group X, or a bicyclic aromatic ring group composed of aromatic rings selected from Group X, which may have a substituent. １ｂ , Ar ２ｂ , Ar ３ｂ , and Ar ４ｂ In the group represented by the formula (3), the total number of groups represented by the formula (3) contained as the substituent is 1 or more. n and m each independently represent an integer of 0 to 2. １ａ has a substituent different from the group represented by formula (3), Ar １ｂ is Ar １ａ has the same substituent as the substituent that Ar has, ２ａ has a substituent different from the group represented by formula (3), Ar ２ｂ is Ar ２ａ has the same substituent as the substituent that Ar has, ３ａ has a substituent different from the group represented by formula (3), Ar ３ｂ is Ar ３ａ has the same substituent as the substituent that Ar has, ４ａ has a substituent different from the group represented by formula (3), Ar ４ｂ is Ar ４ａ In addition, A to D, n, m, and q in the formula (2) are the same as A to D, n, m, and q in the formula (1), respectively. １ ~R ３ each independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.

2. In the formula (2), Ar １ｂ and Ar ２ｂ In the group represented by the formula (3), the total number of groups represented by the formula (3) contained as the substituent is 1, and Ar ３ｂ and Ar ４ｂ The composition according to claim 1, wherein the total number of groups represented by formula (3) contained as the substituent in the group represented by formula (3) is 0.

3. In the formula (3), R １ ~R ３ The composition of claim 1 , wherein is a branched alkyl group having 3 carbon atoms.

4. In the formula (1), the number of aromatic rings represented by A to D and Ar １ａ ~Ar ４ａ and the number of aromatic rings in the group represented by Ar １ｂ ~Ar ４ｂ The composition according to claim 1 , wherein the total number of aromatic rings in the group represented by the formula (I) is 9 or 10.

5. Ar １ａ , Ar ２ａ , Ar ３ａ , and Ar ４ａ Each satisfies requirement 1, and Ar １ｂ , Ar ２ｂ , Ar ３ｂ , and Ar ４ｂ The composition according to claim 1, wherein each of the following satisfies Requirement 2. Requirement 1: The composition has no substituent, or has a fluorine atom or a chlorine atom as a substituent. Requirement 2: The composition has no substituent, or has a fluorine atom, a chlorine atom, or a group represented by formula (3) as a substituent.

6. 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 the composition according to claim 1 and an n-type organic semiconductor.

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

8. The photoelectric conversion element according to claim 6, wherein the photoelectric conversion film further contains a dye.

9. The photoelectric conversion element according to claim 6, further comprising one or more intermediate layers in addition to said photoelectric conversion film between said conductive film and said transparent conductive film.

10. An imaging device comprising the photoelectric conversion element according to any one of claims 6 to 9.

11. An optical sensor comprising the photoelectric conversion element according to any one of claims 6 to 9.

12. A method for manufacturing an imaging device, comprising the step of manufacturing the photoelectric conversion device according to any one of claims 6 to 9.

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