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

Abstract

The present invention provides a photoelectric conversion element having excellent light resistance and small electric field strength dependence of quantum efficiency. The present invention also provides an imaging element, an optical sensor, a method for manufacturing an imaging element, and a method for manufacturing a photoelectric conversion element, all of which pertain to the photoelectric conversion element. A photoelectric conversion element according to the present invention has a conductive film, a photoelectric conversion film, and a transparent conductive film in the stated order. The photoelectric conversion film contains a first dye, a second dye that is a compound different from the first dye, a p-type semiconductor, and at least one of fullerene C70 and a fullerene C70 derivative.

Description

Photoelectric conversion element, image sensor, light sensor, method for manufacturing an image sensor, method for manufacturing a photoelectric conversion element

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

[0002] In recent years, the development of devices having photoelectric conversion films (for example, image sensors) has progressed. For example, Patent Document 1 discloses a photoelectric conversion device that has excellent quantum efficiency when receiving red-green light, comprising a conductive film, a photoelectric conversion film, and a transparent conductive film in that order, wherein the photoelectric conversion film contains a compound represented by formula (1).

[0003] International Publication No. 2024 / 185744

[0004] With the increasing demand for improved performance in image sensors and optical sensors, there is a need for photoelectric conversion elements that exhibit superior characteristics. The primary characteristic required of a photoelectric conversion element is excellent quantum efficiency; that is, it must maintain a constant quantum efficiency even when the voltage applied to the element is changed, i.e., have excellent electric field strength dependence of quantum efficiency. Furthermore, for practical use, photoelectric conversion elements must also possess excellent durability, even after prolonged and repeated use. Durability can be measured by, for example, light resistance. Specifically, excellent light resistance means that when the photoelectric conversion element is irradiated with light for a certain period, the change in dark current characteristics before and after light irradiation is minimal. Under these requirements, the present inventors fabricated and investigated a photoelectric conversion element containing the compound disclosed in Patent Document 1. Their findings revealed that the aforementioned electric field strength dependence of quantum efficiency and light resistance were not always sufficient, indicating room for improvement.

[0005] Therefore, the present invention aims to provide a photoelectric conversion element that has excellent light resistance and low dependence of quantum efficiency on electric field strength. Furthermore, the present invention also aims to provide an image sensor, a light sensor, a method for manufacturing an image sensor, and a method for manufacturing a photoelectric conversion element related to the above-mentioned photoelectric conversion element.

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

[0007] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film comprises a first dye, a second dye which is a compound different from the first dye, a p-type semiconductor, and fullerene C ７０ and fullerene C ７０ A photoelectric element comprising at least one of the derivatives. [2] The photoelectric element according to [1], wherein the first dye is a compound represented by formula (1) or formula (2). [3] The first dye and the second dye are D １ [2] A photoelectric element according to [2], wherein the compound represented by formula (1) is a group represented by formula (D-1), and the first dye and the second dye are compounds in which the k values ​​in formula (D-1) are different from each other. [4] A photoelectric element according to [2] or [3], wherein the second dye is a compound represented by formula (1) or formula (2). [5] A photoelectric element according to any one of [1] to [4], wherein the content of the first dye is more than 10% by volume and less than 90% by volume relative to the total amount of the first dye and the second dye. [6] A photoelectric element according to any one of [1] to [5], wherein there is one or more intermediate layers between the conductive film and the transparent conductive film in addition to the photoelectric conversion film. [7] An image sensor having a photoelectric element according to any one of [1] to [6]. [8] A light sensor having a photoelectric element according to any one of [1] to [6]. [9] A method for manufacturing an image sensor, comprising the step of manufacturing a photoelectric conversion element according to any one of [1] to [6].

[10] The first dye, the second dye, the p-type semiconductor, and the fullerene C ７０ and the above fullerene C ７０ A method for producing a photoelectric conversion element according to any one of [1] to [6], comprising a step of co-depositing at least one of the derivatives.

[0008] According to the present invention, it is possible to provide a photoelectric conversion element that has excellent light resistance and low dependence of quantum efficiency on electric field strength. Furthermore, according to the present invention, it is also possible to provide an image sensor, a light sensor, a method for manufacturing an image sensor, and a method for manufacturing a photoelectric conversion element related to the above-mentioned photoelectric conversion element.

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

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

[0011] The following definitions are used to express the meaning of each term in this specification. In this specification, a numerical range indicated by "~" means a range that includes the numbers indicated before and after "~" as the lower and upper limits. In this specification, a hydrogen atom may be a light hydrogen atom (a normal hydrogen atom) or a deuterium atom (for example, a double hydrogen atom).

[0012] In this specification, with respect to compounds that may have geometric isomers (cis-trans isomers), the general formula or structural formula representing the compound may, for convenience, be described only in either the cis or trans form. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form.

[0013] In this specification, the bonding direction of divalent groups (e.g., -CO-O-) is not limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", if Y is -CO-O-, the compound may be either "X-O-CO-Z" or "X-CO-O-Z".

[0014] The symbol "*" in a chemical formula indicates a bond position unless otherwise specified. In this specification, when there are multiple substituents and linking groups etc. (hereinafter also referred to as "substituents etc.") indicated by a specific symbol, or when multiple substituents etc. are specified simultaneously, it means that each substituent etc. may be identical or different from the others. The same applies to the specification of the number of substituents etc. In this specification, unless otherwise specified, "substituent" refers to the group exemplified by substituent W described later.

[0015] (Substituent W) The substituent W in this specification is described below. Substituent W is, for example, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, and iodine atom), an alkyl group (including cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups), an alkenyl group (including cycloalkenyl groups and bicycloalkenyl groups), an alkynyl group, an aryl group, a heterocyclic group (heteroaryl group, or aliphatic heterocyclic group), a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyl Examples of substituents include oxy groups, primary, secondary, or tertiary amino groups (including anilino groups), alkylthio groups, arylthio groups, heterocyclic thio groups, alkyl or arylsulfinyl groups, alkyl or arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, carboxyl groups, phosphoric acid groups, sulfonic acid groups, hydroxyl groups, thiol groups, acylamino groups, carbamoyl groups, ureido groups, and boronic acid groups. Furthermore, each of the above groups may have further substituents (for example, one or more of the above groups) if possible. For example, alkyl groups that may have substituents are also included as one form of substituent W. When substituent W has carbon atoms, the number of carbon atoms in substituent W is, for example, 1 to 20. The number of atoms other than hydrogen atoms in substituent W is, for example, 1 to 30. The first and second dyes, described later, may have substituents such as carboxyl group, salt of carboxyl group, salt of phosphate group, sulfonic acid group, salt of sulfonic acid group, hydroxyl group, thiol group, acylamino group, carbamoyl group, ureido group, and boronic acid group (-B(OH)). ２ ) and / or the absence of a primary amino group is also preferable.

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

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

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

[0019] In this specification, unless otherwise specified, aromatic rings constituting an aromatic ring or aromatic ring group may be monocyclic or polycyclic (e.g., 2 to 6 rings). A monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as its ring structure. A polycyclic (e.g., 2 to 6 rings) aromatic ring is an aromatic ring in which multiple (e.g., 2 to 6) aromatic ring structures are fused together as its ring structure. The number of ring member atoms of the above aromatic ring is preferably 4 to 15. The above aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. If the above aromatic ring is an aromatic heterocyclic ring, the number of heteroatoms having as ring member atoms is, for example, 1 to 10. Examples of the above heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron. Examples of the above aromatic hydrocarbon ring include a benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring.Examples of the above aromatic heterocycles include pyridine rings, pyrimidine rings, pyridazine rings, pyrazine rings, triazine rings (e.g., 1,2,3-triazine rings, 1,2,4-triazine rings, and 1,3,5-triazine rings), tetrazine rings (e.g., 1,2,4,5-tetrazine rings), quinoxaline rings, pyrrole rings, furan rings, thiophene rings, imidazole rings, oxazole rings, thiazole rings, benzopyrrole rings, benzofuran rings, benzothiophene rings, benzimidazole rings, benzoxazole rings, benzothiazole rings, naphthopyrrole rings, naphthofuran rings, naphthothiophene rings, naphtoimidazole rings, naphthoxazole rings, pyrroloimidazole rings (e.g., 5H-pyrrolo[1,2-a]imidazole rings), and imidazoxazole rings (e.g., imidazo[2,1-b]oxazole rings). , thienothiazole ring (e.g., thieno[2,3-d]thiazole ring, etc.), benzothiadiazole ring, benzodithiophene ring (e.g., benzo[1,2-b:4,5-b']dithiophene ring, etc.), thienothiophene ring (e.g., thieno[3,2-b]thiophene ring, etc.), thiazolothiazole ring (e.g., thiazolo[5,4-d]thiazole ring, etc.), naphthodithiophene ring (e.g., naphtho[2,3 Examples include the -b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring and 1,8-dithiadicyclopenta[b,g]naphthalene ring, etc., benzothienobenzothiophene ring, dithieno[3,2-b:2',3'-d]thiophene ring and 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring. In an aromatic ring which may have substituents, examples of substituents that the aromatic ring may have include the group exemplified by substituent W. The number of substituents in the aromatic ring which has substituents may be one or more (for example, 1 to 4). In this specification, when referring to an aromatic ring group, examples include a group obtained by removing one or more hydrogen atoms (for example, 1 to 5) from the above aromatic ring. In this specification, when referring to an aryl group, examples include a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic hydrocarbon ring among the aromatic rings mentioned above.In this specification, when referring to a heteroaryl group, for example, a group obtained by removing one hydrogen atom from a ring corresponding to an aromatic heterocycle among the above aromatic rings. In this specification, when referring to an arylene group, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic hydrocarbon ring among the above aromatic rings. In this specification, when referring to a heteroarylene group, for example, a group obtained by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the above 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 group exemplified by substituent W. When these optionally substituted groups have substituents, the number of substituents may be one or more (for example, 1 to 4).

[0020] In this specification, the number of ring members of the aliphatic heterocyclic group is preferably 5 to 20, more preferably 5 to 12, and even more preferably 6 to 8. Examples of heteroatoms that the aliphatic heterocyclic group has include sulfur, oxygen, nitrogen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, oxygen, or nitrogen atoms being preferred. Examples of aliphatic heterorings that constitute the aliphatic heterocyclic group include pyrrolidine rings, oxolane rings, thiolane rings, piperidine rings, tetrahydropyran rings, thiane rings, piperazine rings, morpholine rings, quinuclidine rings, azetidine rings, oxetane rings, aziridine rings, dioxane rings, and γ-butyrolactone.

[0021] In this specification, unless otherwise specified, if there are two or more bond positions represented by * in a formula, the direction of the bond is not particularly limited. For example, in a compound represented by the formula "X-Y-Z", if Y is a group represented by *-A-B-*, the compound may be either "X-A-B-Z" or "X-B-A-Z". Also, for example, a structure in which a ring represented by formula (X1) and a ring represented by formula (X2) are fused at a bond position represented by * may be either the structure represented by formula (X3) or the structure represented by formula (X4).

[0022]

[0023] [Photoelectric Conversion Element] The photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film comprises a first dye, a second dye that is a compound different from the first dye, a p-type semiconductor, and fullerene C ７０ and at least one of fullerene C ７０ derivatives. Although the mechanism by which the object of the present invention can be solved when the photoelectric conversion element of the present invention adopts the above configuration is not necessarily clear, the present inventors speculate as follows. It should be noted that the following speculation does not limit the mechanism by which the effect is obtained. That is, even when the effect is obtained by a mechanism other than the following, it is still included in the scope of the present invention.

[0024] A photoelectric conversion element needs to be excellent in durability upon repeated use, for example, it needs to have little performance degradation and excellent light resistance even after repeated light irradiation. Further, it is preferable that the photoelectric conversion element has an absorption wavelength covering the entire visible light region. As a result of various studies based on the above viewpoints, the present inventors found that, as an n-type semiconductor, fullerene C ７０ or fullerene C ７０ derivatives are useful. On the other hand, C ６０ , which is widely used as an n-type semiconductor, is replaced with C ７０ in the photoelectric conversion element fabricated by this replacement, it has been clarified that the quantum efficiency decreases when the electric field intensity is reduced, that is, the dependence of quantum efficiency on electric field intensity deteriorates. When the present inventors examined in detail the factors that caused the deterioration of the dependence of quantum efficiency on electric field intensity, it was found that C ７０ is more likely to aggregate than C ６０ , and as a result, phase separation occurs in the photoelectric conversion film, and the dyes used in combination in the photoelectric conversion film aggregate more strongly. Therefore, if the dye is not a single species, aggregation is less likely to occur, and the inclusion of multiple components allows C ７０Based on the idea that compatibility with the dye would be improved, the inventors used two dyes with different structures in combination, and as a result succeeded in achieving both light resistance and low electric field strength dependence of quantum efficiency. Hereinafter, if at least one of the light resistance and electric field strength dependence of the photoelectric conversion element is superior, this will also be referred to as a superior effect of the present invention. The configuration of the photoelectric conversion element of the present invention will be described in detail below.

[0025] Figure 1 shows a schematic cross-sectional view of one embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in Figure 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 that functions as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12, and a transparent conductive film (hereinafter also referred to as the "upper electrode") 15 that functions as an upper electrode are stacked in this order. Figure 2 shows an example of the configuration of another photoelectric conversion element. The photoelectric conversion element 10b shown in Figure 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked on the lower electrode 11 in this order. Note that the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in Figures 1 and 2 may be appropriately changed depending on the application and characteristics.

[0026] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15. Furthermore, when using the photoelectric conversion element 10a (or 10b), a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and between this pair of electrodes, 1 × 10⁻¹⁰ －５ ~1 x 10 ７ It is preferable to apply a voltage of V / cm. In terms of performance and power consumption, the applied voltage should be 1 × 10⁻⁶. －４ ~1 x 10 ７ V / cm is more preferable, 1 × 10 －３ ~5 x 10 ６A voltage of V / cm is even more preferable. Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side becomes the cathode and the photoelectric conversion film 12 side becomes the anode, as shown in Figures 1 and 2. The same method can be used to apply the voltage when the photoelectric conversion element 10a (or 10b) is used as a light sensor or when it is incorporated into an image sensor. As will be described in detail later, the photoelectric conversion element 10a (or 10b) is suitably applicable to image sensor applications. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.

[0027] [Photoelectric conversion film] The photoelectric conversion element of the present invention comprises a first dye, a second dye which is a compound different from the first dye, a p-type semiconductor, and fullerene C ７０ and fullerene C ７０ The photoelectric conversion film comprises at least one of the derivatives. Each of these compounds will be described in detail below.

[0028] <First and Second Dyes> The first and second dyes are preferably compounds having an absorption wavelength in the visible region, and more preferably the maximum absorption wavelength is in the visible light region, more preferably 400 to 700 nm, and even more preferably 450 to 650 nm. The maximum absorption wavelength is the value measured in solution (solvent: chloroform) after adjusting the concentration of the dye so that the absorption spectrum has an absorbance of 0.5 to 1.0. However, if the dye does not dissolve in chloroform, the maximum absorption wavelength of the dye is measured using the dye in a film state after deposition.

[0029] As described above, the second dye is a different compound from the first dye. In other words, the first and second dyes are not particularly limited as long as their structures are different from each other, but it is preferable that they be organic dyes with different structures. Among organic dyes, it is preferable that at least one of the first and second dyes is an acceptor-donor-acceptor type dye, a donor-acceptor type dye, or a donor-acceptor-donor type dye. It is more preferable that at least one is an acceptor-donor-acceptor type dye or a donor-acceptor type dye, and it is even more preferable that both are acceptor-donor-acceptor type dyes or donor-acceptor type dyes.

[0030] In particular, in terms of the superior effects of the present invention, the first dye is preferably a compound represented by formula (1) or formula (2), and more preferably a compound represented by formula (1). Also, the second dye is preferably a compound represented by formula (1) or formula (2), and more preferably a compound represented by formula (1). In particular, in terms of the superior effects of the present invention, the first dye and the second dye are D １ It is preferable that the compound is represented by formula (1) above, and more preferably that the compounds have different k values ​​in formula (D-1) described later.

[0031] [Compound represented by formula (1)]

[0032]

[0033] In formula (1), D １１ Each of these independently represents a base that can be expressed by one of the formulas (D-1) to (D-3). １１ These are, independently, single bonds and -CR bonds. Ｂ =CR Ｂ R represents -, or -C≡C-. Ｂ Each of these independently represents a hydrogen atom or a substituent. １１ A represents a hydrogen atom, a group represented by formula (A-1), or a group represented by formula (A-2). １２represents the base represented by formula (A-1) or formula (A-2) above. n11 represents an integer from 0 to 2. In formula (D-1), k represents an integer from 0 to 4. A and C each independently represent a ring represented by formula (d1) or formula (d2). B each independently represents a ring represented by any of formulas (d3) to (d7). In formulas (d1) to (d7), Z １ａ Each of these is independently -CR Ａ = or represents a nitrogen atom. R Ａ X represents a hydrogen atom or substituent. １ａ It consists of an oxygen atom, a sulfur atom, a selenium atom, and -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C (=CR) Ａ５ ２ ) represents X ２ａ is an oxygen atom, a sulfur atom, or -NR Ａ１ Represents -. R Ａ１ ~R Ａ６ Each of these independently represents a hydrogen atom or a substituent. Ａ２ Allies, R Ａ３ Allies, R Ａ４ Allies, R Ａ５ Allies, and R Ａ６ Each of them may be bonded to each other to form a ring which may have substituents. ３ａ represents an oxygen atom or a sulfur atom. * represents a bond position. The rings represented by formulas (d1) and (d2) above are fused at the two fused ring positions represented by *1. The rings represented by formulas (d3) to (d7) above are fused with one adjacent ring at the two fused ring positions represented by *2, and with the other adjacent ring at the two fused ring positions represented by *3. In formula (D-2), Z １１ａ ~Z １６ａ Two of them represent -C(*) = and the other four are independently -CR Ａ = or represents a nitrogen atom. R Ａ represents a hydrogen atom or substituent. * represents a bond position. In formula (D-3), X １１ａrepresents an oxygen atom, a sulfur atom, a selenium atom, -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C(=CR Ａ５ ２ )-. R Ａ１ to R Ａ５ each independently represent a hydrogen atom or a substituent. Two of Z ２１ａ to Z ２４ａ represent -C(*)=, and the other two each independently represent -CR Ａ = or a nitrogen atom. R Ａ represents a hydrogen atom or a substituent. * represents a binding position. In formula (A-1), R １１ to R １３ each independently represent a hydrogen atom or a substituent. m1 represents 0 or 1. C １１ represents a ring containing two or more carbon atoms, which may have a substituent. W １ represents an oxygen atom, a sulfur atom, =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ . R Ｗ１ represents a hydrogen atom or a substituent. R Ｗ２ and R Ｗ３ each independently represent a cyano group, -COOR Ｗ４ , -COR Ｗ５ , or -SO ２ R Ｗ６ . R Ｗ４ to R Ｗ６ each independently represent an aliphatic hydrocarbon group optionally having a substituent, an aromatic ring group optionally having a substituent, or an aliphatic heterocyclic group optionally having a substituent. * represents a binding position. In formula (A-2), R １４ to R １６ each independently represent a hydrogen atom or a substituent. m2 represents 0 or 1. W ２ and W ３ each independently represent a cyano group, -COOR Ｗ１１ , -COR Ｗ１２ , -SOR Ｗ１３ , or -SO ２R Ｗ１４ Represents R Ｗ１１ ~R Ｗ１４ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates the bond position.

[0034] The compound represented by formula (1) (hereinafter also referred to as "Specific Compound 1") will be described in detail below. Unless otherwise specified, the preferred embodiments of each group and structure in each formula are described in common to both the first and second dyes. In formula (1), D １１ Each of these independently represents a base that can be expressed by one of the formulas (D-1) to (D-3). In particular, n¹¹+1 D １１ Preferably, at least one of them is a group represented by formula (D-1), and n11+1 D １１ It is preferable that all of these are groups represented by formula (D-1). １１ These are, independently, single bonds and -CR bonds. Ｂ =CR Ｂ - or -C≡C- represents a single bond, and R is preferred. Ｂ Each of these independently represents a hydrogen atom or a substituent, with hydrogen atoms being preferred. Ｂ Examples of substituents represented by the above-mentioned substituent W include the group exemplified above. １１ Each of these independently represents a hydrogen atom, a group represented by formula (A-1), or a group represented by formula (A-2), with a hydrogen atom or a group represented by formula (A-1) being preferred. １２ Each independently represents either a group represented by formula (A-1) or a group represented by formula (A-2), with the group represented by formula (A-1) being preferred. Among these, A １１ and A １２ At least one (more preferably both) of these preferably has an aliphatic hydrocarbon group having 1 or 2 carbon atoms, and more preferably has an aliphatic hydrocarbon group having 2 carbon atoms. It is believed that the aggregation between dyes is suppressed by the aliphatic hydrocarbon group having 2 or more carbon atoms, and that the dependence of the quantum efficiency on the electric field strength in the photoelectric conversion element of the present invention is better. On the other hand, A １１ and A １２It is also preferable that at least one (more preferably both) of the components does not have an aliphatic hydrocarbon group having 3 or more carbon atoms. In other words, it is also preferable that both the first and second dyes do not have an aliphatic hydrocarbon group having 3 or more carbon atoms. When the dyes do not contain aliphatic hydrocarbon groups having 3 or more carbon atoms, the electron transfer between molecules in each component of the photoelectric conversion film is not inhibited by long-chain aliphatic hydrocarbon groups, and therefore the dependence of the quantum efficiency on the electric field strength is considered to be better. n11 represents an integer from 0 to 2, preferably 0 or 1, and more preferably 0.

[0035] In terms of superior effects of the present invention, when the first or second dye is specific compound 1, it is preferable that specific compound 1 is in one of the following embodiments. Embodiment 1: A １１ However, the group is represented by formula (A-1) or formula (A-2), n11+1 is 1 or 2, and n11 D １１ At least one of them is a group represented by formula (D-2) or a group represented by formula (D-3). Embodiment 2: A １１ The group is represented by formula (A-1) or formula (A-2), and n¹¹ + 1 D １１ At least one of them is a group represented by formula (D-1). Embodiment 3: A １１ These are hydrogen atoms, and n¹¹+1 D １１ At least one of these is a group represented by formula (D-1). When specific compound 1 is embodiment 2 or embodiment 3, it is also preferable that n11 is 1. Furthermore, it is also preferable that n11 is 0, in which case specific compound 1 is more preferably embodiment 4 or embodiment 5 below. Embodiment 4: A １１ is a group represented by formula (A-1) or formula (A-2), n11 is 0, and D １１ However, it is a base represented by formula (D-1). Appearance 5: A １１ is a hydrogen atom, n11 is 0, and D １１ However, this is the base represented by formula (D-1).

[0036] The bases represented by formulas (D-1) to (D-3), formula (A-1), and formula (A-2) will be described in detail below.

[0037]

[0038] In formula (D-1), k represents an integer from 0 to 4, and an integer from 0 to 2 is preferred, and 1 or 2 is more preferred, in terms of the superior effects of the present invention. Also, as described above, the first dye and the second dye are D １ When the compound represented by formula (1) is a group represented by formula (D-1) described later, it is preferable that the values ​​of k in formula (D-1) are different from each other. In particular, the combination of k values ​​for the first dye and the second dye is preferably k=2 in one and k=0 or 1 in the other, and more preferably k=2 in one and k=1 in the other.

[0039] In formula (D-1), A and C each independently represent a ring represented by formula (d1) or formula (d2). B each independently represents a ring represented by any of formulas (d3) to (d7). For B, the ring represented by formula (d3) or formula (d4) is preferred, and the ring represented by formula (d4) is more preferred. In formula (D-1), adjacent rings represented by A to C are fused at the fused ring positions indicated by *1 to *3 in formulas (d1) to (d7), which will be described later. That is, the group represented by formula (D-1) is a divalent fused ring group consisting of rings represented by A, k B, and C. For example, when k=0, A and C are fused; when k=1, A and B, and B and C are fused; and when k=2, A and B, two adjacent Bs, and B and C are fused.

[0040] In formulas (d1) to (d7), Z １ａ Each of these is independently -CR Ａ = or represents a nitrogen atom. R Ａ R represents a hydrogen atom or substituent. ＡExamples of substituents represented by include the substituent W described above, and preferably are an aliphatic hydrocarbon group which may have substituents, an aromatic ring group which may have substituents, an aliphatic heterocyclic group which may have substituents, an alkoxy group, an aryloxy group, an acyl group, a silyl group, a halogen atom, a cyano group, or a nitro group, and more preferably an aliphatic hydrocarbon group which may have substituents, an aromatic ring group which may have substituents, an aliphatic heterocyclic group which may have substituents, a silyl group, an alkoxy group, or a halogen atom. Examples of substituents which each of the above-mentioned groups which may have substituents include the substituents exemplified by substituent W described above, and substituents selected from the substituent group S described later are preferred.

[0041] The above aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the above aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The number of carbon atoms in a linear aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 4, and particularly preferably 1 or 2. The number of carbon atoms in a branched aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, even more preferably 3 to 7, and particularly preferably 3 to 5. The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in a cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 6.

[0042] The above aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The above aromatic ring group may be monocyclic or polycyclic, with monocyclic being preferred. The number of ring member atoms of the above aromatic ring group is preferably 5 to 18, more preferably 5 to 10, and even more preferably 5 to 8. The definition and specific examples of an aromatic hydrocarbon group are as described above, with a phenyl group or a naphthyl group being preferred, and a phenyl group being more preferred. Examples of heteroatoms that the above aromatic heterocyclic group may have are as described above, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. The definition and specific examples of an aromatic heterocyclic group are as described above, with a thiophene ring group, a furan ring group, a pyrrole ring, a thiazole ring, or a pyridine ring group being preferred. The above aromatic ring group may have substituents as described above. If the above aromatic ring group has substituents, the number is not particularly limited, but 1 to 3 is preferred.

[0043] The above aliphatic heterocyclic group may be monocyclic or polycyclic, with monocyclic being preferred. The number of ring member atoms of the above aliphatic heterocyclic group is preferably 3 to 18, more preferably 5 to 10, and even more preferably 5 to 8. Examples of heteroatoms of the above aliphatic heterocyclic group are as described above, with sulfur atoms, oxygen atoms, or nitrogen atoms being preferred. The definition and specific examples of the aliphatic heterocyclic group are as described above, with thiolane ring groups, piperidine ring groups, tetrahydrofuran ring groups, or tetrahydropyran ring groups being preferred. As described above, the above aliphatic heterocyclic group may have substituents. If the above aliphatic heterocyclic group has substituents, the number is not particularly limited, but 1 to 3 is preferred.

[0044] The alkyl group of the alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 1 to 3.

[0045] The aryl group in the above aryloxy group may be monocyclic or polycyclic, with monocyclic being preferred. The number of carbon atoms in the above aryloxy group is preferably 5 to 18, more preferably 6 to 10, and even more preferably 6 to 8.

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

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

[0048] Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or chlorine atoms being preferred.

[0049] In formulas (d1) to (d7), X １ａ It consists of an oxygen atom, a sulfur atom, a selenium atom, and -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C (=CR) Ａ５ ２ )- represents, and in terms of the superior effect of the present invention, oxygen atom, sulfur atom, -NR Ａ１ -, -SiR Ａ２ ２ - or -CR Ａ４ ２ - Preferably an oxygen atom, a sulfur atom, -NR Ａ１ - or -CR Ａ４ ２ This is more preferable. In particular, the present invention is more effective in that at least one of the k B groups is a group represented by formula (d4), and X １ａ ga-NR Ａ１- or -CR Ａ４ ２ It is preferable that this is the case. ２ａ is an oxygen atom, a sulfur atom, or -NR Ａ１ Represents -. X ３ａ This represents an oxygen atom or a sulfur atom.

[0050] R Ａ１ ~R Ａ６ Each of these independently represents a hydrogen atom or a substituent. Ａ１ ~R Ａ５ The substituents represented by the above-mentioned substituent W include the substituents exemplified above, and preferably are an aliphatic hydrocarbon group which may have substituents, an aromatic ring group which may have substituents, or an aliphatic heterocyclic group which may have substituents, more preferably an aliphatic hydrocarbon group which may have substituents or an aromatic ring group which may have substituents, and even more preferably an aliphatic hydrocarbon group which may have substituents. Ａ１ ~R Ａ５ The definitions and preferred embodiments of each group exemplified as substituents represented by the above R Ａ The substituents represented are the same as those exemplified, but among them, aliphatic hydrocarbon groups having 1 to 3 carbon atoms are preferred, and aliphatic hydrocarbon groups having 1 or 2 carbon atoms are more preferred.

[0051] R Ａ２ Allies, R Ａ３ Allies, R Ａ４ Allies, R Ａ５ Allies, and R Ａ６ These elements may be bonded to each other to form a ring which may have substituents. That is, R Ａ２ They may be bonded to each other to form a ring which may have substituents, R Ａ３ They may be bonded to each other to form a ring which may have substituents, R Ａ４ They may be bonded to each other to form a ring which may have substituents, R Ａ５ They may be bonded to each other to form a ring which may have substituents, R Ａ６The elements may be bonded to each other to form a ring which may have substituents. The ring may be either an aromatic ring or an aliphatic ring, with an aliphatic ring being preferred. The ring may be either a monocyclic or polycyclic ring. The number of ring member atoms in the ring is preferably 3 to 20, more preferably 5 to 12, and even more preferably 5 to 10. The ring may have heteroatoms. The heteroatoms are preferably sulfur atoms, nitrogen atoms, or oxygen atoms. The substituents that the ring may have include the substituent W mentioned above, and alkyl groups, aryl groups, or halogen atoms are preferred.

[0052] In equations (d1) to (d7), * represents a bond position. The bond positions represented by * in equations (d1) to (d7) correspond to the bond positions represented by * in equation (D-1). The rings represented in equations (d1) and (d2) are fused at the two fused ring positions represented by *1. The rings represented in equations (d3) to (d7) are fused with one adjacent ring at the two fused ring positions represented by *2, and with the other adjacent ring at the two fused ring positions represented by *3. For example, if A is a group represented by formula (d1), k is 1, B is a group represented by formula (d3), and C is a group represented by formula (d2), then A and B are fused at the fused ring position represented by *1 in formula (d1) and the fused ring position represented by *2 in formula (d3), and B and C are fused at the fused ring position represented by *3 in formula (d3) and the fused ring position represented by *1 in formula (d2), or A and B are fused at the fused ring position represented by *1 in formula (d1) and the fused ring position represented by *3 in formula (d3), and B and C are fused at the fused ring position represented by *2 in formula (d3) and the fused ring position represented by *1 in formula (d2).

[0053] In formula (D-2), Z １１ａ ~Z １６ａ Two of them represent -C(*) = and the other four are independently -CR Ａ = or represents a nitrogen atom. In particular, Z １１ａ ~Z １６ａ Two of them represent -C(*) = and the other four are independently -CR Ａ It is preferable to represent it as =. R Ａ R represents a hydrogen atom or substituent.Ａ This is as described above in equation (D-1).

[0054] In formula (D-3), X １１ａ It consists of an oxygen atom, a sulfur atom, a selenium atom, and -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C (=CR) Ａ５ ２ )- represents the effect of the present invention, and in terms of superiority, oxygen atoms, sulfur atoms, or -NR Ａ１ - is preferred, and an oxygen atom or a sulfur atom is more preferred. Ａ１ ~R Ａ５ Each of these independently represents a hydrogen atom or a substituent. ２１ａ ~Z ２４ａ Two of them represent -C(*) = and the other two independently represent -CR Ａ = or represents a nitrogen atom. R Ａ R represents a hydrogen atom or substituent. Ａ and R Ａ１ ~R Ａ５ This is as described above in equation (D-1).

[0055] The group represented by formula (D-1) is preferably a group represented by any of formulas (B1) to (B17), more preferably a group represented by any of formulas (B2) to (B6), (B8), (B10), (B12) to (B14), (B16), and (B17), and even more preferably a group represented by formulas (B3) to (B6), (B8), (B10), (B12) to (B14), and (B16). The group represented by formula (D-2) is preferably a group represented by any of formulas (A1) to (A3), more preferably a group represented by formula (A1) or (A2), and even more preferably a group represented by formula (A1). The group represented by formula (D-3) is preferably a group represented by formula (A4).

[0056]

[0057]

[0058] In the above formulas (A1) to (A4) and (B1) to (B17), Z is independently -CR Ａ = or represents a nitrogen atom, -CR Ａ = is preferable. X is independently an oxygen atom, a sulfur atom, a selenium atom, or -NR Ａ１ - represents an oxygen atom, a sulfur atom, or -NR Ａ１ - is preferred, and an oxygen atom or a sulfur atom is more preferred. Ｉ These are, independently, an oxygen atom, a sulfur atom, a selenium atom, and -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C (=CR) Ａ５ ２ ) - represents oxygen atom, sulfur atom, -NR Ａ１ -, -SiR Ａ２ ２ - or -CR Ａ４ ２ - is preferable. R Ａ and R Ａ１ ~R Ａ５ As described above in equation (D-1). Also, R Ａ２ Allies, R Ａ３ Allies, R Ａ４ Allies, and R Ａ５ These elements may be bonded to each other to form a ring which may have substituents. Details of the ring which may have substituents are as described above in formula (D-1).

[0059]

[0060] In formula (A-1), R １１ ~R １３ Each of these independently represents a hydrogen atom or a substituent, with hydrogen atoms being preferred. １１ ~R １３ Examples of substituents represented by the above-mentioned substituent W include the substituents exemplified by substituent W.

[0061] In formula (A-1), m1 represents 0 or 1, and 0 is preferred in that the effects of the present invention are superior.

[0062] In formula (A-1), C １１ C represents a ring containing two or more carbon atoms, which may have substituents. １１ The two carbon atoms included are the two carbon atoms explicitly shown in formula (A-1). The number of carbon atoms in the above ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the above ring is the number including the two carbon atoms explicitly shown in the formula. The above ring may be either an aromatic ring or an aliphatic ring. The above ring may be either a monocyclic or polycyclic ring, and a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferred. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The above ring may have heteroatoms. Examples of the above heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron, with sulfur, nitrogen, or oxygen being preferred. The number of heteroatoms in the above ring is preferably 0 to 10, and more preferably 0 to 5. １１ Among the carbon atoms constituting the ring represented by (A-1), carbon atoms other than those explicitly shown in formula (A-1) may be substituted with carbonyl carbons (>C=O) and thiocarbonyl carbons (>C=S), etc.

[0063] Examples of substituents that the above ring may have include the group exemplified by substituent W, and preferably a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic ring group, or a silyl group, more preferably a halogen atom or an alkyl group, and even more preferably an alkyl group. The alkyl group may be linear, branched, or cyclic, and linear is preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1 or 2. Preferred substituents that the alkyl group may have include a halogen atom, an aromatic ring group, or a silyl group. Preferred substituents that the aromatic ring group may have include a halogen atom, an alkyl group, or a silyl group.

[0064] In formula (A-1), W １This consists of an oxygen atom, a sulfur atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ In terms of exhibiting superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ R represents a hydrogen atom or substituent. Ｗ１ Examples of substituents represented by the above-mentioned substituent W include R. Ｗ２ and R Ｗ３ These are, independently, a cyano group and a -COOR group. Ｗ４ , -COR Ｗ５ , or -SO ２ R Ｗ６ Represents R Ｗ４ ~R Ｗ６ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. The definition of an aliphatic hydrocarbon group is as described above, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is preferred. The definition of an aromatic ring group is as described above, and an aromatic hydrocarbon group is preferred, with a phenyl group being more preferred. The definition of an aliphatic heterocyclic group is as described above, and the heteroatom of the above aliphatic heterocyclic group is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. Ｗ４ ~R Ｗ６ Examples of substituents that each group represented by the above-mentioned substituent W may have include alkyl groups, alkoxy groups, aromatic ring groups, or halogen atoms.

[0065] C １１The rings represented by are preferably rings used as acidic nuclei (for example, acidic nuclei of merocyanine dyes), and examples of nuclei include the following: (a) 1,3-dicarbonyl nuclei: for example, 1,3-indanedione nuclei, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-4,6-dione. (b) Pyrazolinone nuclei: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, and 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one. (c) Isoxazolinone nuclei: for example, 3-phenyl-2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one. (d) Oxindole nuclei: for example, 1-alkyl-2,3-dihydro-2-oxindole. (e) 2,4,6-trioxohexahydropyrimidine core: for example, barbituric acid, 2-thiobarbituric acid, and its derivatives. Examples of the above derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl, and 1,3-dibutyl, 1,3-diaryl compounds such as 1,3-diphenyl, 1,3-di(p-chlorophenyl), and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, and 1,3-diheteroaryl compounds such as 1,3-di(2-pyridyl). (f) 2-thio-2,4-thiazolidinedione core: for example, rhodanine and its derivatives. Examples of the above derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-allylrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and 3-heteroarylrhodanines such as 3-(2-pyridyl)rhodanine. (g) 2-thio-2,4-oxazolidinedione core (2-thio-2,4-(3H,5H)-oxazoledione core): For example, 3-ethyl-2-thio-2,4-oxazolidinedione. (h) thianaphthenone core: For example, 3(2H)-thianaphthenone-1,1-dioxide. (i) 2-thio-2,5-thiazolidinedione core: For example, 3-ethyl-2-thio-2,5-thiazolidinedione.(j) 2,4-thiazolidinedione nuclei: e.g., 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, and 3-phenyl-2,4-thiazolidinedione, etc. (k) thiazolin-4-one nuclei: e.g., 4-thiazolinone and 2-ethyl-4-thiazolinone, etc. (l) 2,4-imidazolidinedione (hydantoin) nuclei: e.g., 2,4-imidazolidinedione and 3-ethyl-2,4-imidazolidinedione, etc. (m) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nuclei: e.g., 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione, etc. (n) Imidazolin-5-one core: e.g., 2-propylmercapto-2-imidazolin-5-one. (o) 3,5-pyrazolidinedione core: e.g., 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione. (p) Benzothiophen-3(2H)-one core: e.g., benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, and dioxobenzothiophen-3(2H)-one. (q) Indanone core: e.g., 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, and 3,3-dimethyl-1-indanone. (r) Benzofuran-3-(2H)-one nucleus: e.g., benzofuran-3-(2H)-one. (s) 2,2-dihydrophenalen-1,3-dione nucleus, etc.

[0066] The group represented by formula (A-1) is preferred over the group represented by formula (A-11) in that it exhibits superior effects of the present invention.

[0067]

[0068] In formula (A-11), R １１ ~R １３ and m1 are, respectively, R in equation (A-1) １１ ~R １３ And it is the same as m1.

[0069] In formula (A-11), C １２ This represents a ring containing at least three carbon atoms, which may have substituents. １２The three carbon atoms included are the three carbon atoms explicitly shown in formula (A-11). The number of carbon atoms in the above ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The number of carbon atoms in the above ring is the number including the three carbon atoms explicitly shown in the formula. The above ring may be either an aromatic ring or an aliphatic ring. The above ring may be either a monocyclic or polycyclic ring, and a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferred. The number of carbon atoms in the fused ring containing at least one of a 5-membered ring and a 6-membered ring is preferably 6 to 20, more preferably 6 to 15, and even more preferably 8 to 10. The above ring may have heteroatoms. Examples of the above heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron, with sulfur, nitrogen, or oxygen being preferred. The number of heteroatoms in the above ring is preferably 0 to 10, and more preferably 0 to 5. The above CC １２ Of the carbon atoms constituting the ring represented by (A-11), carbon atoms other than those explicitly shown in formula (A-11) may be substituted with carbonyl carbons (>C=O) and thiocarbonyl carbons (>C=S), etc. Preferred embodiments of substituents that the above ring may have are the above-mentioned ring C １２ This is similar to the substituents that may be present.

[0070] In formula (A-11), W １１ and W １２ These are, independently, a sulfur atom, an oxygen atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ In terms of exhibiting superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ ~R Ｗ３ This is as described above in equation (A-1).

[0071] The group represented by formula (A-1) is more preferably the group represented by formula (A-12) or the group represented by formula (A-13).

[0072]

[0073] In equations (A-12) and (A-13), R １１~R １３ and m1 are, respectively, R in equation (A-1) １１ ~R １３ And it is the same as m1.

[0074] In formula (A-12), X ｃ１ and X ｃ２ These are, independently, a sulfur atom, an oxygen atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ In terms of exhibiting superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ ~R Ｗ３ As described above in formula (A-1). In terms of the superior effects of the present invention, X ｃ１ and X ｃ２ Preferably, one of them is an oxygen atom, X ｃ１ and X ｃ２ It is more preferable that it be an oxygen atom.

[0075] In formula (A-12), C １３ represents an aromatic ring which may have substituents. The aromatic ring may be monocyclic or polycyclic. The number of member atoms of the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 5 to 8. The number of member atoms of the aromatic ring is the number including the two carbon atoms explicitly shown in the formula. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. Specific examples of the aromatic ring are as described above, and are preferably a benzene ring, naphthalene ring, anthracene ring, pyrene ring, thiophene ring, furan ring, thiazole ring, oxazole ring, pyridine ring, thienothiophene cyclic ring, benzothiophene ring, benzofuran ring, pyrazine ring, pyrimidine ring, or pyridazine ring, more preferably a benzene ring, naphthalene ring, or thiophene ring, and even more preferably a benzene ring. Examples of substituents which the aromatic ring may have include the group exemplified by substituent W, and alkyl groups or halogen atoms are preferred. The number of substituents that the above aromatic ring may have is not particularly limited, but is preferably 0 to 8, and more preferably 0 to 4.

[0076] In formula (A-13), Xｃ３ ~X ｃ５ These are, independently, a sulfur atom, an oxygen atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ In terms of exhibiting superior effects of the present invention, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Ｗ１ ~R Ｗ３ As described above in formula (A-1). In terms of the superior effects of the present invention, X ｃ３ and X ｃ４ It is preferable that X is an oxygen atom. ｃ３ ~X ｃ５ It is more preferable that it be an oxygen atom.

[0077] In formula (A-13), Z ｃ１ and Z ｃ２ Each of these is independently -NR ｃ１ - or -CR ｃ２ ２ - indicates that the effects of the present invention are superior, and -NR ｃ１ - is preferable. R ｃ１ and R ｃ２ Each of these independently represents a hydrogen atom or a substituent. Examples of the substituent include the group exemplified by substituent W, and alkyl groups or aryl groups are preferred, with alkyl groups being more preferred. The alkyl group may be linear, branched, or cyclic, with linear being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. The aryl group may be monocyclic or polycyclic, with phenyl groups being preferred. The aryl group may have further substituents, and examples of substituents include the group exemplified by substituent W.

[0078] In formula (A-2), R １４ ~R １６ Each of these independently represents a hydrogen atom or a substituent, with hydrogen atoms being preferred. １４ ~R １６ Examples of substituents represented by the above-mentioned substituent W include the substituents exemplified by substituent W.

[0079] In formula (A-2), m² represents 0 or 1, and 0 is preferred in that the effects of the present invention are superior.

[0080] In formula (A-2), W ２ and W ３ These are, independently, a cyano group and a -COOR group. Ｗ１１ , -COR Ｗ１２ , -SOR Ｗ１３ , or -SO ２ R Ｗ１４ Represents R Ｗ１１ ~R Ｗ１４ Each of these independently represents an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. Ｗ１１ ~R Ｗ１４ The definitions and preferred embodiments of each group represented by formula (A-1) are as follows: Ｗ４ ~R Ｗ６ Each of the groups represented is the same as R. Ｗ１１ ~R Ｗ１４ Among these, aliphatic hydrocarbon groups or phenyl groups having 1 to 4 carbon atoms are preferred.

[0081] The substituent group S is described in detail below. Substituent group S: linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 7 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, aromatic ring groups having 5 to 12 ring member atoms which may have substituents, alkoxy groups having 1 to 5 carbon atoms, acyl groups having 2 to 6 carbon atoms, silyl groups, and halogen atoms.

[0082] The number of carbon atoms in the linear aliphatic hydrocarbon group in the substituent group S is 1 to 3, more preferably 1 or 2. The number of carbon atoms in the branched aliphatic hydrocarbon group in the substituent group S is 3 to 7, more preferably 3 or 4. The cyclic aliphatic hydrocarbon group in the substituent group S is preferably monocyclic.

[0083] The aromatic ring group in the substituent group S may be monocyclic or polycyclic, with monocyclic being preferred. The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with aromatic hydrocarbon groups being preferred. The heteroatoms of the aromatic heterocyclic group are preferably oxygen atoms, nitrogen atoms, or sulfur atoms. The number of ring member atoms of the aromatic ring group is 5 to 12, preferably 5 to 10, and more preferably 5 or 6. Examples of substituents that the aromatic ring group may have are the substituents exemplified by substituent W described above, with substituents selected from substituent group S being preferred, and more preferably linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 7 carbon atoms, silyl groups, alkoxy groups having 1 to 5 carbon atoms, or halogen atoms. If the aromatic ring group has substituents, the number of substituents is preferably 1 to 3.

[0084] The number of carbon atoms in the alkoxy group in the above substituent group S is 1 to 5, more preferably 1 to 4, and even more preferably 1 or 2. The number of carbon atoms in the acyl group in the above substituent group S is 2 to 6, more preferably 2 to 5, and even more preferably 2 or 3.

[0085] The definition and preferred embodiment of the silyl group in the above substituent group S is as described above in R Ａ The substituent represented by is the same as the silyl group exemplified. In particular, R Ｓｉ However, each is independently a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 7 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic ring group having 5 to 12 ring member atoms, which may have substituents, -SiR Ｓｉ ３ A base represented by is preferred.

[0086] Examples of halogen atoms in the above substituent group S include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or chlorine atoms being preferred.

[0087] Specific examples of specific compound 1 include the following compounds.

[0088]

[0089] In the above compound examples, R independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-propyl group, a neopentyl group, an n-hexyl group, a 2-ethylhexyl group, a phenyl group, a 2,6-dimethylphenyl group, a 2,6-diisopropylphenyl group, a fluorine atom, a chlorine atom, or a cyano group. X and X Ｉ These are X and X in equations (A1) to (A4) and equations (B1) to (B17), respectively. Ｉ It is the same as above. Each A independently represents one of the following groups. Note that Ph represents a phenyl group and Me represents a methyl group.

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] [Compound represented by formula (2)] Next, we will describe in detail the compound represented by formula (2).

[0096]

[0097] In formula (2), R ２１ represents a hydrogen atom or substituent. A ２１ Ar represents the group represented by the above formula (A-1) or the group represented by the above formula (A-2). ２１ R represents an aromatic ring group which may have substituents. ２２ This is an aryl group which may have a substituent, -C(R Ｌ１ ) (Caution Ｌ２ ) (Caution Ｌ３ R represents a heteroaryl group which may have substituents. Ｌ１ ~R Ｌ３ Each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, or a hydrogen atom, RＬ１ ~R Ｌ３ Of these, at least two independently represent an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. Ｌ１ ~R Ｌ３ The optionally substituted alkyl group, optionally substituted aryl group, and optionally substituted heteroaryl group represented by the above may be bonded to each other via single bonds or divalent linking groups to form an optionally substituted ring. ２１ -NR １ｓ -, -CR ２ｓ ２ - represents a sulfur atom, oxygen atom, or selenium atom. １ｓ and R ２ｓ Each of these independently represents a substituent. ２ｓ These elements may be bonded to each other to form a ring that may have substituents.

[0098] In formula (2), R ２１ R represents a hydrogen atom or a substituent, with a hydrogen atom being preferred. ２１ Examples of substituents represented by the above-mentioned substituent W include the substituents exemplified by substituent W.

[0099] In formula (2), A ２１ This represents a group represented by formula (A-1) or a group represented by formula (A-2), and the group represented by formula (A-2) is preferred in that it provides superior effects of the present invention. Details of the group represented by formula (A-1) and the group represented by formula (A-2) are as described above in formula (1).

[0100] In formula (2), Ar ２１represents an aromatic ring which may have substituents. The aromatic ring may be monocyclic or polycyclic, and polycyclic is preferred in that it provides superior effects of the present invention. The number of ring fusions of the polycyclic is preferably 2 to 4, and more preferably 2. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic, and an aromatic heterocyclic is preferred. Examples of heteroatoms of the aromatic heterocyclic are as described above, and oxygen, nitrogen, or sulfur atoms are preferred, with nitrogen atoms being more preferred. The number of ring member atoms of the aromatic ring is preferably 5 to 20, more preferably 6 to 14, and even more preferably 8 to 10. Among the aromatic rings, polycyclic rings including nitrogen-containing aromatic rings are preferred. Examples of substituents that the aromatic ring may have include the substituent W described above, and preferably a substituted aliphatic hydrocarbon group, a substituted aromatic ring group, a substituted aliphatic heterocyclic group, a substituted alkoxy group, a halogen atom, a silyl group, or a cyano group, and more preferably a substituted aliphatic hydrocarbon group, a substituted alkoxy group, or a halogen atom. The definitions and preferred embodiments of each of the groups exemplified as substituents are described above in R. Ａ These are the same groups as the substituents exemplified by the formulas.

[0101] In formula (2), R ２２ This is an aryl group which may have a substituent, -C(R Ｌ１ ) (Caution Ｌ２ ) (Caution Ｌ３ ), or a heteroaryl group which may have a substituent, and an aryl group which may have a substituent or -C (R Ｌ１ ) (Caution Ｌ２ ) (Caution Ｌ３ ) is preferred, and a substituted aryl group is more preferred.

[0102] R ２２The aryl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the aryl group is preferably 6 to 12, more preferably 6 to 10. The aryl group is preferably a phenyl group, naphthyl group, anthryl group, or fluorenyl group, more preferably a phenyl group. The substituent that the aryl group may have is the substituent W mentioned above, which is preferably an alkyl group, an aryl group which may have a substituent, an aryl group which may have a substituent, a cyano group, an alkoxy group, or a halogen atom, more preferably an alkyl group, an aryl group which may have an alkyl group, or a halogen atom, and even more preferably a phenyl group which may have an alkyl group or an alkyl group having 2 or more carbon atoms. The alkyl group exemplified as a substituent that the aryl group may have may be linear, branched, or cyclic, and is preferably branched in that it provides better effects of the present invention. The number of carbon atoms in the alkyl group is preferably 2 or more in that it provides better effects of the present invention. The upper limit is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. The number of substituents on the aryl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2 or 3.

[0103] -C(R Ｌ１ ) (Caution Ｌ２ ) (Caution Ｌ３ ) Medium, R Ｌ１ ~R Ｌ３ Each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, or a hydrogen atom, R Ｌ１ ~R Ｌ３ Of these, at least two independently represent an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. Examples of substituents that each of the above groups may have include the substituent W described above, and alkyl groups, aryl groups, or halogen atoms are preferred. Ｌ１１ ~R Ｌ１３ The alkyl group represented by may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3.Ｌ１１ ~R Ｌ１３ The definitions and preferred embodiments of the aryl group and heteroaryl group represented by R ２２ These are the same as the aryl and heteroaryl groups represented by .

[0104] R Ｌ１１ ~R Ｌ１３ The optionally substituted alkyl group, optionally substituted aryl group, and optionally substituted heteroaryl group represented by may be bonded to each other via single bonds or divalent linking groups to form a ring. For example, R Ｌ１１ and R Ｌ１２ Alkyl groups that may have substituents represented by R may be bonded to each other via single bonds or divalent linking groups to form a ring that may have substituents, Ｌ１１ An aryl group which may have a substituent represented by R Ｌ１２ An alkyl group which may have substituents represented by can be bonded to each other via a single bond or a divalent linking group to form a ring which may have substituents. Examples of divalent linking groups include a divalent hydrocarbon group (e.g., an alkylene group or an arylene group), -O-, -CO-, -SO ２ Examples include -, -NH-, and groups formed by combining these. The ring is preferably an aliphatic ring. The number of ring member atoms in the ring is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. The ring may have heteroatoms. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron atoms, with sulfur, nitrogen, or oxygen atoms being preferred. Substituents that the ring may have include the substituent W mentioned above, with alkyl groups, aryl groups, or halogen atoms being preferred.

[0105] R ２２The heteroaryl group represented by may be monocyclic or polycyclic. Examples of heteroatoms of the heteroaryl group are as described above, with nitrogen, sulfur, or oxygen atoms being preferred. The number of ring member atoms of the heteroaryl group is preferably 5 to 20, and more preferably 5 to 12. The definitions and preferred embodiments of substituents that the heteroaryl group may have are given above. ２２ The definition of substituents that the aryl group represented by may have and preferred embodiments are the same as those defined above.

[0106] In formula (2), X ２１ -NR １ｓ -, -CR ２ｓ ２ - represents a sulfur atom, an oxygen atom, or a selenium atom, and -NR is used in terms of having superior effects of the present invention. １ｓ - or -CR ２ｓ ２ - is preferable. R １ｓ and R ２ｓ Each of these independently represents a hydrogen atom or a substituent. １ｓ Examples of substituents represented by include the substituent W mentioned above, and may have substituents, such as an aryl group, -C(R Ｌ１ ) (Caution Ｌ２ ) (Caution Ｌ３ A heteroaryl group, which may have substituents, is preferred. １ｓ The definitions and preferred embodiments of each group exemplified as substituents represented by the above R ２２ It is the same as the group represented by R. ２ｓ The substituents represented are preferably an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group, with an optionally substituted aliphatic hydrocarbon group being more preferred. ２ｓ The definitions and preferred embodiments of each group exemplified as substituents represented by the above R Ａ１ ~R Ａ６ These are the same groups as the substituents exemplified by the formulas.

[0107] R ２ｓ These elements may be bonded to each other to form a ring that may have substituents. ２ｓA preferred embodiment of the ring, which may have substituents that may be formed by bonding with each other, is the R described above. Ａ２ Allies, R Ａ３ Allies, R Ａ４ Allies, R Ａ５ Allies, and R Ａ６ This is the same as a ring which may have substituents that can be formed by bonding with each other.

[0108] Of the compounds represented by formula (2), the compound represented by formula (2-1) is preferred.

[0109]

[0110] In formula (2-1), R ２１ , R ２２ A ２１ , and X ２１ These are R in equation (2), respectively. ２１ , R ２２ A ２１ , and X ２１ It is the same as this.

[0111] In formula (2-1), R ２１ｔ and R ２２ｔ Each of these independently represents a hydrogen atom or a substituent. ２１ｔ and R ２２ｔ The definition and preferred embodiment of the substituent represented by the above formula (2) is Ar ２１ R is the same substituent that may be present on the aromatic ring represented by . ２１ｔ and R ２２ｔ These atoms may be bonded to each other to form a ring which may have substituents. The ring may be an aromatic ring, an aliphatic ring, or a fused ring of an aromatic ring and an aliphatic ring, with an aromatic ring being preferred. The ring may be monocyclic or polycyclic, with a monocyclic ring being preferred. The number of ring member atoms of the ring is preferably 5 to 14, more preferably 6 to 10, and even more preferably 6. The ring may have heteroatoms. Examples of heteroatoms include nitrogen, sulfur, oxygen, selenium, tellurium, phosphorus, silicon, and boron, with sulfur, nitrogen, or oxygen being preferred. Examples of substituents that the ring may have and preferred embodiments are shown in the above formula (2) Ar ２１These are the same substituents that the aromatic ring represented by may have.

[0112] Specific examples of compounds represented by formula (2) include the following compounds.

[0113]

[0114] In the above compound, A represents any of the groups exemplified as A in the first compound described above.

[0115] In addition to compounds represented by formula (1) or formula (2) above, the first and second dyes may include, for example, cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azametine dyes, coumarin dyes, allylidene dyes, anthraquinone dyes, and triphenylmethane dyes. Organic dyes such as azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, and metal complex dyes can also be used.

[0116] The molecular weights of the first and second dyes are preferably 300 to 1,200, more preferably 350 to 1,000, and even more preferably 400 to 800.

[0117] The first and second dyes are preferably single-film ionization potentials of -5.0 to -6.0 eV, in terms of stability when used as p-type organic semiconductors and energy level matching with n-type organic semiconductors.

[0118] The first and second dyes may be purified as needed. Examples of methods for purifying the first and second dyes include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, slurry washing, reprecipitation purification, and purification and recrystallization using adsorbents such as activated carbon.

[0119] The content of the first dye in the photoelectric conversion film (= film thickness of the first dye on a single-layer basis / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 5 to 40 volume%, more preferably 10 to 30 volume%, and even more preferably 10 to 20 volume%. The preferred content of the second dye is the same as the preferred content of the first dye described above. Furthermore, the total amount of the first and second dyes (= film thickness of the first and second dyes on a single-layer basis / film thickness of the photoelectric conversion film × 100) is not particularly limited, but is preferably 15 to 75 volume%, more preferably 20 to 60 volume%, and even more preferably 20 to 50 volume%. Two or more types of the first and second dyes may be used. In other words, the photoelectric conversion film may contain a third dye different from both the first and second dyes, and if a third dye is used, it is preferable that the total amount of the first, second, and third dyes be within the above range. In particular, for the effects of the present invention to be superior, the content of the first dye (or second dye) is preferably 10% by volume or more, more preferably more than 10% by volume, even more preferably 20% by volume or more, and especially preferably 35% by volume or more, relative to the total amount of the first dye and the second dye. Furthermore, the upper limit is preferably 95% by volume or less, more preferably 90% by volume or less, even more preferably less than 90% by volume, and especially preferably 80% by volume or less.

[0120] <Fullerene C ７０ , Fullerene C ７０ Derivatives > Fullerene C ７０ and fullerene C ７０ Derivatives (hereinafter simply referred to as "fullerene C") ７０ Also called "type". ) For example, fullerene C ７０ This is preferable. Fullerene C ７０Examples of derivatives include compounds obtained by adding substituents to the fullerene described above. Preferred substituents are alkyl groups, aryl groups, or heterocyclic groups. Specific examples of fullerene derivatives include the compounds described in Japanese Patent Application Publication No. 2007-123707, the details of which are incorporated herein by reference.

[0121] The photoelectric conversion film comprises the first dye and the second dye, and fullerene C ７０ or fullerene C ７０ It is preferable to have a bulk heterostructure formed in a mixed state with the derivative. The bulk heterostructure is a layer in which the first dye and the second dye and an n-type organic semiconductor are mixed and dispersed within the photoelectric conversion film. The photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. The bulk heterostructure is described in detail in paragraphs

[0013] to

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

[0122] Fullerene C ７０ or fullerene C ７０ The derivatives may be used individually or in combination of two or more. Fullerene C in the photoelectric conversion film ７０ Content of the type (fullerene C ７０ The film thickness (single-layer equivalent / film thickness of photoelectric conversion film × 100) is preferably 15 to 75 volume%, more preferably 20 to 60 volume%, and even more preferably 20 to 50 volume%. Furthermore, in terms of the superior effects of the present invention, the first dye and the second dye and fullerene C ７０ Fullerene C as a percentage of the total content of all related categories ７０ Content of the type (fullerene C ７０ Single-layer film thickness of the type / (Single-layer film thickness of the first and second dyes + Fullerene C ７０ The film thickness (on a single-layer basis) × 100 is preferably 20 to 80 volume%, and more preferably 40 to 60 volume%. Also, fullerene C ７０ Content of the type (fullerene C ７０ Film thickness in single layer equivalent for the type / (Fullerene C ７０The film thickness (single-layer equivalent) of the type + film thickness (single-layer equivalent) of the first and second dyes + film thickness (single-layer equivalent) of the p-type semiconductor) × 100) is preferably 5 to 75 volume%, and more preferably 15 to 50 volume%.

[0123] <p-type semiconductor> A p-type semiconductor is a compound different from the first and second dyes described above. A p-type organic semiconductor is preferred as the p-type semiconductor. A p-type organic semiconductor is an organic compound that does not have a maximum absorption in the visible light region, is a donor-type organic semiconductor material (compound), and has the property of readily donating electrons. In other words, a p-type organic semiconductor is the organic compound with the smaller ionization potential when two organic compounds are used in contact. It is preferable that the p-type semiconductor is a compound with a smaller ionization potential than both the first and second dyes.

[0124] Examples of p-type organic semiconductors include triarylamine compounds (for example, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), compounds described in paragraphs

[0128] to

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

[0052] to

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

[0119] to

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

[0044] to

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

[0086] to

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

[0031] to

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

[0043] to

[0045] of WO 2016 / 194630, compounds described in paragraphs

[0025] to

[0037] and

[0099] to

[0109] of WO 2017 / 159684, compounds described in paragraphs

[0029] to

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

[0015] to

[0025] of WO 2018 / 207722, and compounds described in paragraph

[004] of JP 2019-054228. Compounds described in paragraphs [5] to

[0053] , compounds described in paragraphs

[0045] to

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

[0063] to

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

[0033] to

[0036] of JP 2019-080052, compounds described in paragraphs

[0044] to

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

[0041] to

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

[0034] to

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

[0033] to

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

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

[0019] to

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

[0031] to

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

[0036] to

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

[0055] to

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

[0041] to

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

[0044] to

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

[0041] to

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

[0042] to

[0049] of Japanese Patent Application Publication No. 2018-046267, paragraphs

[0042] to

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

[0031] to

[0036] , compounds described in paragraphs

[0036] to

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

[0045] to

[0048] of Japanese Patent Application Publication No. 2020-010024, etc.), cyanine compounds, oxonol compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives and fluorantene derivatives, etc.), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, aminosubstituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having nitrogen-containing heterocyclic compounds as ligands. Examples of p-type organic semiconductors include compounds with a lower ionization potential than n-type organic semiconductors. If this condition is met, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as p-type organic semiconductors are given below.

[0125]

[0126]

[0127]

[0128]

[0129] The difference in ionization potential between the first dye, the second dye, and the p-type semiconductor is preferably 0.1 eV or greater.

[0130] The p-type semiconductor may be used alone or in combination of two or more types. When the photoelectric conversion film contains a p-type semiconductor, the p-type semiconductor content in the photoelectric conversion film (film thickness of the p-type semiconductor on a single-layer basis / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75 volume%, more preferably 20 to 60 volume%, and even more preferably 25 to 50 volume%.

[0131] The photoelectric conversion film containing the first and second dyes is a non-luminescent film and has characteristics different from those of an organic light-emitting diode (OLED). A non-luminescent film means a film with a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less. The lower limit is often 0% or more.

[0132] <n-type organic semiconductor> The photoelectric conversion film is made of the above-mentioned fullerene C ７０ It may also include n-type organic semiconductors other than those described above. The n-type organic semiconductor is a compound different from the first and second dyes described above. An n-type organic semiconductor is an acceptor organic semiconductor material (compound), which is an organic compound that readily accepts electrons. In other words, an n-type organic semiconductor is the organic compound with the greater electron affinity when two organic compounds are brought into contact. In other words, any organic compound that has electron-accepting properties can be used as an acceptor organic semiconductor. An example of an n-type organic semiconductor is the fullerene C described above. ７０Fullerenes selected from the group consisting of fullerenes other than those of the same class and their derivatives, condensed aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives and fluorantene derivatives, etc.); heterocyclic compounds of 5 to 7 membered rings having at least one atom selected from the group consisting of nitrogen, oxygen and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, i Examples include: midazole and thiazole (etc.); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives and oxadiazole derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; basocuproine, basophenanthroline and their derivatives; triazole compounds; distylyl arylene derivatives; metal complexes having nitrogen-containing heterocyclic compounds as ligands; silole compounds; and compounds described in paragraphs

[0056] to

[0057] of Japanese Patent Publication No. 2006-100767. ７０ Examples of fullerenes selected from the group consisting of fullerenes other than those of the same class and their derivatives include fullerene C ６０ , Fullerene C ７６ , Fullerene C ７８ , Fullerene C ８０ , Fullerene C ８２ , Fullerene C ８４ , Fullerene C ９０ , Fullerene C ９６ , Fullerene C ２４０ , Fullerene C ５４０ Examples include mixed fullerenes and their derivatives.

[0133] n-type organic semiconductors may also be organic dyes. Examples of organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azametine dyes, coumarin dyes, allylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridinone dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, and metal complex dyes.

[0134] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.

[0135] 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.

[0136] The difference in electron affinity between the first dye, the second dye, and the n-type organic semiconductor is preferably 0.1 eV or greater.

[0137] n-type organic semiconductors may be used individually or in combination of two or more types. The photoelectric conversion film is the fullerene C mentioned above. ７０ When other n-type organic semiconductors are included, the content of n-type organic semiconductors in the photoelectric conversion film (film thickness of n-type organic semiconductor on a single-layer basis / film thickness of photoelectric conversion film × 100) is preferably 15 to 75 volume%, more preferably 20 to 60 volume%, and even more preferably 20 to 50 volume%.

[0138] <Method of forming the film> The method of forming the above photoelectric conversion film is not particularly limited, but the first dye, the second dye, the p-type semiconductor, and the fullerene C ７０ and the above fullerene C ７０One example is a method that includes a step of co-depositing at least one of the derivatives. A more specific method for forming the above-mentioned photoelectric conversion film is, for example, a dry deposition method. Examples of dry deposition methods include physical vapor deposition methods such as evaporation (especially vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization, with vacuum deposition being preferred. When forming a photoelectric conversion film by vacuum deposition, manufacturing conditions such as the degree of vacuum and deposition temperature can be set according to conventional methods.

[0139] The film thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and even more preferably 50 to 500 nm.

[0140] [Electrodes] The photoelectric conversion element preferably has electrodes. The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of conductive materials include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include conductive metal oxides such as antimony tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); thin metal films of gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, as well as nanocarbon materials such as carbon nanotubes and graphene. Conductive metal oxides are preferred in terms of high conductivity and transparency.

[0141] Typically, when a conductive film is made thinner than a certain range, its resistance often increases sharply. In the solid-state image sensor incorporating the photoelectric conversion element according to this embodiment, the sheet resistance may be 100 to 10000 Ω / □, and there is a great degree of freedom in the range of film thickness that can be thinned. Also, the thinner the upper electrode (transparent conductive film) 15, the less light it absorbs, and generally the light transmittance increases. An increase in light transmittance is desirable because it increases light absorption in the photoelectric conversion film and increases the photoelectric conversion ability. Considering the suppression of leakage current, the increase in the resistance of the thin film, and the increase in transmittance associated with thinning, the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0142] The lower electrode 11 may be made transparent or opaque to reflect light, depending on the application. Examples of materials that make up the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and zinc indium oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and grampene.

[0143] The method for forming electrodes can be appropriately selected depending on the electrode material. Specifically, examples include wet methods such as printing and coating; physical methods such as vacuum deposition, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD. When the electrode material is ITO, examples include electron beam methods, sputtering, resistance heating deposition, chemical reaction methods (sol-gel method, etc.), and coating of indium tin oxide dispersions.

[0144] [Charge-blocking films: electron-blocking films, hole-blocking films] It is preferable that the photoelectric conversion element has one or more intermediate layers between the conductive film and the transparent conductive film, in addition to the photoelectric conversion film. An example of the above intermediate layer is a charge-blocking film. When the photoelectric conversion element has this film, the characteristics of the resulting photoelectric conversion element (quantum efficiency, response speed, etc.) are better. Examples of charge-blocking films include electron-blocking films and hole-blocking films.

[0145] [Electron Blocking Film] The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. Polymer materials can also be used as electron blocking films. Examples of polymer materials include polymers such as phenylenevinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, as well as their derivatives.

[0146] Furthermore, the electron blocking film may be composed of multiple films. The electron blocking film may also be composed of inorganic materials. Generally, inorganic materials have a higher dielectric constant than organic materials, so when inorganic materials are used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher quantum efficiency. Examples of inorganic materials that can be used as electron blocking films include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

[0147] [Hole Blocking Film] The hole blocking film is an acceptor-type organic semiconductor material (compound), and the above-mentioned n-type organic semiconductor can be used. The hole blocking film may also be composed of multiple films.

[0148] Examples of methods for manufacturing charge-blocking films include dry deposition and wet deposition. Examples of dry deposition methods include vapor deposition and sputtering. Vapor deposition can be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with physical vapor deposition methods such as vacuum deposition being preferred. Examples of wet deposition methods include inkjet, spray, nozzle printing, spin coating, dip coating, casting, die coating, roll coating, bar coating, and gravure coating, with inkjet being preferred in terms of high-precision patterning.

[0149] The thickness of the charge blocking film (electron blocking film and hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm, respectively.

[0150] [Substrate] The photoelectric conversion element may further have a substrate. Examples of substrates include semiconductor substrates, glass substrates, and plastic substrates. Typically, the substrates are layered on the substrate in the following order: conductive film, photoelectric conversion film, and transparent conductive film.

[0151] [Sealing Layer] The photoelectric conversion element may further have a sealing layer. Photoelectric conversion materials can be significantly degraded in performance due to the presence of degradation factors such as water molecules. Therefore, the entire photoelectric conversion film can be sealed by covering it with a sealing layer made of a dense metal oxide, metal nitride or metal nitride oxide ceramic, or diamond-like carbon (DLC), which does not allow water molecules to penetrate, thereby preventing the above-mentioned degradation. Examples of sealing layers include those described in paragraphs

[0210] to

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

[0152] [Method for manufacturing a photoelectric conversion element] The method for manufacturing a photoelectric conversion element is not particularly limited, but for example, the first dye, the second dye, the p-type semiconductor, and the fullerene C ７０ and the above fullerene C ７０One example is a method for producing the photoelectric conversion film, which includes a step of co-depositing at least one of the derivatives.

[0153] [Image Sensor] An example of an application of the photoelectric conversion element is an image sensor. Furthermore, there are no particular limitations on the method of manufacturing the image sensor, but an example of an image sensor manufacturing method having a process for manufacturing the photoelectric conversion element of the present invention is provided. An image sensor is an element that converts the optical information of an image into an electrical signal, and usually multiple photoelectric conversion elements are arranged in a matrix on the same plane, and each photoelectric conversion element (pixel) converts the optical signal into an electrical signal and outputs that electrical signal to the outside of the image sensor sequentially for each pixel. For this purpose, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.

[0154] [Optical Sensor] Other applications of the photoelectric conversion element include, for example, photocells and optical sensors, and the photoelectric conversion element of the present invention is preferably used as an optical sensor. As an optical sensor, the photoelectric conversion element may be used alone, or it may be used as a line sensor in which the photoelectric conversion elements are arranged in a straight line or as a two-dimensional sensor arranged on a plane.

[0155] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0156] [Compounds used in photoelectric conversion films] The following lists the materials used in the photoelectric conversion films.

[0157] [First pigment or second pigment]

[0158]

[0159] [n-type organic semiconductor] ・C ７０ : Fullerene C ７０ ・C ６０ : Fullerene C ６０

[0160] [p-type organic semiconductor]

[0161]

[0162] [Evaluation] Using the above materials, photoelectric conversion elements for each example and comparative example are fabricated according to the procedure shown below. Subsequently, the photoresistance of each photoelectric conversion element, as well as the quantum efficiency when receiving light with a wavelength of 560 nm, and the electric field strength dependence of the quantum efficiency are evaluated by the following tests using the method described below.

[0163] 〔test〕

[0164] <Fabrication of Photoelectric Conversion Element> A photoelectric conversion element in the form shown in Figure 2 is fabricated using the various components shown above. Here, the photoelectric conversion element consists of a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15. Specifically, amorphous ITO is deposited on a glass substrate by sputtering to form the lower electrode 11 (thickness: 30 nm), and then a compound (EB-1) is deposited on the lower electrode 11 by vacuum heating deposition to form the electron blocking film 16A (thickness: 30 nm). Subsequently, with the temperature of the glass substrate controlled to 25°C, the dyes (first dye and second dye) shown in the table below, an n-type organic semiconductor, and a p-type organic semiconductor (compound P-1) are co-deposited on the electron blocking film 16A by vacuum deposition so that each layer is 80 nm in thickness. The ratio of the first and second dyes in the photoelectric conversion film 12 is shown in the table below. This forms a photoelectric conversion film 12 having a bulk heterostructure of 240 nm. The deposition rate of the photoelectric conversion film 12 is set to 1.0 Å / sec. Furthermore, a compound (EB-2) is deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO is deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). An SiO film is formed on the upper electrode 15 as a sealing layer by vacuum deposition, and then aluminum oxide (Al) is deposited thereon by ALCVD (Atomic Layer Chemical Vapor Deposition). ２ O ３A layer is formed, and the resulting laminate is heated in a glove box at 150°C for 30 minutes to obtain a photoelectric conversion element.

[0165]

[0166] <Light Resistance (Measurement of Dark Current)> The light resistance of each obtained photoelectric conversion element will be evaluated by the following method. Each photoelectric conversion element will be sealed in a sealed container with a lid made of partially alkali-free glass that allows light to pass through, under a nitrogen atmosphere, and the surroundings will be shielded from light. Then, a light irradiation test will be conducted by irradiating the photoelectric conversion element with light for 10 hours using a 300W xenon light source MAX-350 (manufactured by Asahi Spectroscopic Co., Ltd.) so that the illuminance on the photoelectric conversion element is 1.13 million lux (lux). Before and after the light irradiation test, the lower electrode and upper electrode of each photoelectric conversion element will be measured with 0.5 × 10⁻⁶ ５ A voltage is applied to achieve an electric field strength of V / cm, and the current value in the dark (dark current) is measured. The dark current value of the photoelectric conversion element after the light irradiation test is evaluated based on the ratio of the dark current value of the photoelectric conversion element after the light irradiation test to the dark current value of the photoelectric conversion element before the light irradiation test, according to the following classifications. Light resistance of B or higher is preferable, and A is the most preferable.

[0167] A: Less than 10 B: 10 or more but less than 50 C: 50 or more

[0168] <Dependence of quantum efficiency on electric field strength (photoelectric conversion efficiency ratio)> For each photoelectric conversion element, the quantum efficiency and the electric field strength dependence of the quantum efficiency when receiving light with a wavelength of 560 nm will be evaluated using the following method. 2.5 × 10⁻¹⁰ ５ After applying a voltage to achieve an electric field strength of V / cm, a light intensity of 50 μW / cm is applied from the upper electrode (transparent conductive film) side. ２ The light is irradiated, and an IPCE (Incident photon-to-current conversion efficiency) measurement is performed using an Optel constant-energy quantum efficiency measuring device to extract the photoelectric conversion efficiency (external quantum efficiency) at a wavelength of 560 nm. Furthermore, in the above measurement, except for changing the electric field strength of the applied voltage, the same procedure is used to obtain 0.5 × 10⁻¹⁰. ５ The photoelectric conversion efficiency at V / cm is measured. 2.5 × 10⁻¹⁰ of the photoelectric conversion element in Example 1. ５The photoelectric conversion efficiency of each photoelectric conversion element is calculated when the photoelectric conversion efficiency at V / cm is normalized to 1, and the result is 2.5 × 10⁻⁶. ５ 0.5 × 10⁻⁶ for photoelectric conversion efficiency at V / cm ５ The photoelectric conversion efficiency ratio in V / cm is evaluated according to the following classifications. A photoelectric conversion efficiency ratio of C or higher is preferable, and A is most preferable. In each example and comparative example, the photoelectric conversion elements are measured at a wavelength of 560 nm and an electric field strength of 2.5 × 10⁻⁶. ５ At V / cm, it exhibits a photoelectric conversion efficiency of 40% or more, confirming that it possesses a certain level of external quantum efficiency as a photoelectric conversion element.

[0169] A: 0.80 or higher B: 0.70 or higher but less than 0.80 C: 0.60 or higher but less than 0.70 D: 0.50 or higher but less than 0.60 E: Less than 0.50

[0170] [Results] The evaluation results are shown in the table below. In the table, the ratios listed in the "Composition Ratio" column represent the volume ratio of the first and second dyes (first dye: second dye).

[0171]

[0172] The results shown in the table indicate that the photoelectric conversion element of the present invention has excellent light resistance and low dependence of quantum efficiency on electric field strength (high efficiency ratio). From a comparison of Examples 1 to 3 and Examples 13 to 16, it can be seen that the first dye and the second dye are D １ A is a compound represented by formula (1), in which A is a group represented by formula (D-1), and in formula (1) above A １１ and A １２ However, when the groups are independently represented by formula (A-12) or formula (A-13), it is shown that the dependence of the quantum efficiency on the electric field strength is smaller. From a comparison between Examples 1 and 4, it is shown that the first dye and the second dye are D １ A is a compound represented by formula (1) in which the group is represented by formula (D-1), and A １１ and A １２It is shown that when at least one of the compounds has an aliphatic hydrocarbon group with 2 carbon atoms, the dependence of the quantum efficiency on the electric field strength is smaller. This is presumed to be because aggregation between the pigments is suppressed by the aliphatic hydrocarbon group with 2 or more carbon atoms. From a comparison of Examples 4 to 6, it is shown that the first pigment and the second pigment are D １ It is shown that the dependence of quantum efficiency on electric field strength is smaller when the compound represented by formula (1) is a group represented by formula (D-1), and the first dye and the second dye are compounds with different k values ​​in formula (D-1). From a comparison of Example 1 with Examples 7 and 8, it is shown that the dependence of quantum efficiency on electric field strength is smaller when the content of the first dye is greater than 10% by volume and less than 90% by volume relative to the total amount of the first and second dyes. From a comparison of Example 1 with Examples 9 to 12, it was confirmed that the dependence of quantum efficiency on electric field strength is smaller when both the first and second dyes do not have aliphatic hydrocarbon groups with 3 or more carbon atoms. It is inferred that when the dye contains aliphatic hydrocarbon groups with 3 or more carbon atoms, the electric field strength dependence of quantum efficiency may have decreased because it inhibited intermolecular electron transfer for each component contained in the photoelectric conversion film.

[0173] 10a, 10b Photoelectric conversion element 11 Conductive film (lower electrode) 12 Photoelectric conversion film 15 Transparent conductive film (upper electrode) 16A Electron blocking film 16B Hole blocking film

Claims

1. A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film comprises a first dye, a second dye which is a compound different from the first dye, a p-type semiconductor, and fullerene C ７０ and fullerene C ７０ A photoelectric conversion element comprising at least one of a derivative.

2. The photoelectric conversion element according to claim 1, wherein the first dye is a compound represented by formula (1) or formula (2). In formula (1), D １１ each independently represent a group represented by any one of formulas (D-1) to (D-3). L １１ each independently represent a single bond, -CR Ｂ =CR Ｂ -, or -C≡C-. R Ｂ each independently represent a hydrogen atom or a substituent. A １１ represents a hydrogen atom, a group represented by formula (A-1), or a group represented by formula (A-2). A １２ represents the group represented by formula (A-1) or the group represented by formula (A-2). n11 represents an integer of 0 to 2. In formula (D-1), k represents an integer of 0 to 4. A and C each independently represent a ring represented by formula (d1) or formula (d2). B each independently represents a ring represented by any one of formulas (d3) to (d7). In formulas (d1) to (d7), Z １ａ each independently represents -CR Ａ = or a nitrogen atom. R Ａ represents a hydrogen atom or a substituent. X １ａ is an oxygen atom, a sulfur atom, a selenium atom, -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C(=CR Ａ５ ２ )-. X ２ａ is an oxygen atom, a sulfur atom, or -NR Ａ１ -. R Ａ１ to R Ａ６ each independently represent a hydrogen atom or a substituent. R Ａ２ groups, R Ａ３ groups, R Ａ４ groups, R Ａ５ groups, and R Ａ６ groups may each be bonded to each other to form an optionally substituted ring. X ３ａ represents an oxygen atom or a sulfur atom. * represents a bonding position. The rings represented by formulas (d1) and (d2) are fused at the two fused ring positions represented by *1. The rings represented by formulas (d3) to (d7) are fused with one adjacent ring at the two fused ring positions represented by *2, and with the other adjacent ring at the two fused ring positions represented by *3. In formula (D-2), Z １１ａ ~Z １６ａ Two of them represent -C(*) = and the other four are independently -CR Ａ = or represents a nitrogen atom. R Ａ represents a hydrogen atom or substituent. * represents a bond position. In formula (D-3), X １１ａ It consists of an oxygen atom, a sulfur atom, a selenium atom, and -NR Ａ１ -, -SiR Ａ２ ２ -, -GeR Ａ３ ２ -, -CR Ａ４ ２ -, or -C (=CR) Ａ５ ２ ) represents R Ａ１ ~R Ａ５ Each of these independently represents a hydrogen atom or a substituent. ２１ａ ~Z ２４ａ Two of them represent -C(*) = and the other two independently represent -CR Ａ = or represents a nitrogen atom. R Ａ represents a hydrogen atom or substituent. * represents a bond position. In formula (A-1), R １１ ~R １３ Each of these independently represents a hydrogen atom or a substituent. m1 represents 0 or 1. C １１ This represents a ring containing two or more carbon atoms, which may have substituents. １ This consists of an oxygen atom, a sulfur atom, and =NR Ｗ１ , or =CR Ｗ２ R Ｗ３ Represents R Ｗ１ R represents a hydrogen atom or substituent. Ｗ２ and R Ｗ３ These are, independently, a cyano group and a -COOR group. Ｗ４ , -COR Ｗ５ , or -SO ２ R Ｗ６ represents. R Ｗ４ to R Ｗ６ each independently represent an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * indicates a bonding position. In formula (A-2), R １４ to R １６ each independently represent a hydrogen atom or a substituent. m2 represents 0 or 1. W ２ and W ３ each independently represent a cyano group, -COOR Ｗ１１ , -COR Ｗ１２ , -SOR Ｗ１３ , or -SO ２ R Ｗ１４ represents. R Ｗ１１ to R Ｗ１４ each independently represent an optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group. * represents a bonding position. In formula (2), R ２１ represents a hydrogen atom or a substituent. A ２１ represents a group represented by formula (A-1) or a group represented by formula (A-2). Ar ２１ represents an optionally substituted aromatic ring. R ２２ represents an optionally substituted aryl group, -C(R Ｌ１ )(R Ｌ２ )(R Ｌ３ ), or an optionally substituted heteroaryl group. R Ｌ１ to R Ｌ３ each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, or a hydrogen atom, and among R Ｌ１ to R Ｌ３ , at least two each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. R Ｌ１ to R Ｌ３ The optionally substituted alkyl group, optionally substituted aryl group, and optionally substituted heteroaryl group represented by may be bonded to each other via a single bond or a divalent linking group to form an optionally substituted ring. X ２１ represents -NR １ｓ -, -CR ２ｓ ２ -, a sulfur atom, an oxygen atom, or a selenium atom. R １ｓ and R ２ｓ each independently represent a hydrogen atom or a substituent. R ２ｓ groups may be bonded to each other to form an optionally substituted ring.

3. The first dye and the second dye are D １ The photoelectric conversion element according to claim 2, wherein the compound represented by formula (1) is a group represented by formula (D-1), and the first dye and the second dye are compounds in which the k values ​​in formula (D-1) are different from each other.

4. The photoelectric conversion element according to claim 2, wherein the second dye is a compound represented by formula (1) or formula (2).

5. The photoelectric conversion element according to claim 1, wherein the content of the first dye is more than 10% by volume and less than 90% by volume relative to the total amount of the first dye and the second dye.

6. The photoelectric conversion element according to claim 1, wherein one or more intermediate layers are provided between the conductive film and the transparent conductive film, in addition to the photoelectric conversion film.

7. An image sensor having a photoelectric conversion element according to any one of claims 1 to 6.

8. A light sensor having a photoelectric conversion element according to any one of claims 1 to 6.

9. A method for manufacturing an image sensor, comprising the step of manufacturing a photoelectric conversion element according to any one of claims 1 to 6.

10. The first dye, the second dye, the p-type semiconductor, and the fullerene C ７０ and the fullerene C ７０ A method for manufacturing a photoelectric conversion element according to any one of claims 1 to 6, comprising a step of co-depositing at least one of the derivatives.

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