Photoelectric conversion element, imaging element, optical sensor, compound

Abstract

The present invention provides a photoelectric conversion element which is reduced in the electric field intensity dependency of a photoelectric conversion efficiency. The present invention also provides an imaging element, an optical sensor and a compound. The photoelectric conversion element according to the present invention comprises an electroconductive film, a photoelectric conversion film and a transparent electroconductive film in this order, in which the photoelectric conversion film contains a compound represented by formula (1).

Description

Technical Field

[0001] The present invention relates to a photoelectric conversion element, an imaging element, an optical sensor, and a compound.

Background Art

[0002] In recent years, the development of elements having a photoelectric conversion film (for example, imaging elements) has been progressing. For example, in Patent Document 1, the following organic semiconductor material is disclosed as a material related to the photoelectric field. In the following structural formula, R is a predetermined alkyl group.

[0003]

Chemical Formula

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, with the demand for performance improvement of imaging elements and optical sensors, etc., further improvement has been demanded for various characteristics required for the photoelectric conversion elements used in these. For example, it is required to be able to realize a stable photoelectric conversion efficiency even when the voltage applied to the photoelectric conversion element fluctuates. When the present inventors examined a photoelectric conversion element using the material disclosed in Patent Document 1, it was confirmed that it is difficult to suppress the dependence of the photoelectric conversion efficiency on the applied voltage for such a photoelectric conversion element.

[0006] In view of the above circumstances, an object of the present invention is to provide a photoelectric conversion element in which the dependence of the photoelectric conversion efficiency on the electric field strength is suppressed. The present invention also aims to provide an imaging element, an optical sensor, and a compound related to the above photoelectric conversion element.

Means for Solving the Problems

[0007] As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.

[0008] [1] A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by the following formula (1): a photoelectric conversion element. [2] Ar 11 ~Ar 14 are each independently a group represented by any one of the following formulas (2) to (7): the photoelectric conversion element according to [1]. [3] Ar 15 ~Ar 16 are each independently a group represented by any one of the following formulas (8) to (15) and formulas (47) to (53): the photoelectric conversion element according to [1] or [2]. [4] n11 to n12 represent 1, n13 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2: the photoelectric conversion element according to any one of [1] to [3]. [5] n11 to n14 represent 1, n15 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2: the photoelectric conversion element according to any one of [1] to [3]. [6] n11 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2: the photoelectric conversion element according to any one of [1] to [3]. [7] n11 to n12 represent 1, n13 to n14 represent 0, n15 to n16 represent 1, n17 represents 1, and n18 represents 1 or 2: the photoelectric conversion element according to any one of [1] to [3]. [8] The photoelectric conversion element according to any one of [1] to [3], wherein n11 to n14 represent 0, n15 to n16 each independently represent 0 or 1, n17 represents 2, and n18 represents 1. [9] The photoelectric conversion element according to any one of [1] to [3], wherein the compound represented by the above formula (1) is a compound represented by any one of the following formulas (16) to (46) and formulas (54) to (60) described later.

[10] The compound represented by the above formula (1) is Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (16) in which -CR=, and R is a hydrogen atom, Y 41 ~Y 42 and Y 111 ~Y 115 The compound represented by the above formula (17) in which -CR=, and R is a hydrogen atom, Y 21 ~Y 24 and Y 111 ~Y 115 The compound represented by the above formula (21) in which -CR=, and R is a hydrogen atom, Y 21 ~Y 24 and Y 151 ~Y 157 The compound represented by the above formula (22) in which -CR=, and R is a hydrogen atom, Y 61 ~Y 62 and Y 81 ~Y 85 The compound represented by the above formula (24) in which -CR=, and R is a hydrogen atom, Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (27) in which -CR=, and R is a hydrogen atom, Y 151 ~Y 157 The compound represented by the above formula (28) in which -CR=, and R is a hydrogen atom, Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (29) in which -CR=, and R is a hydrogen atom, Y 41 ~Y42 and Y 91 ~Y 97 wherein in the above formula (44), -CR= and R is a hydrogen atom, Y 51 ~Y 54 and Y 81 ~Y 85 a compound represented by the above formula (45) wherein -CR= and R is a hydrogen atom, Y 21 ~Y 24 , Y 41 ~Y 42 and Y 81 ~Y 85 a compound represented by the above formula (46) wherein -CR= and R is a hydrogen atom, Y 471 ~Y 475 a compound represented by the above formula (54) wherein -CR= and R is a hydrogen atom, Y 481 ~Y 485 a compound represented by the above formula (55) wherein -CR= and R is a hydrogen atom, Y 491 ~Y 497 a compound represented by the above formula (56) wherein -CR= and R is a hydrogen atom, Y 501 ~Y 505 a compound represented by the above formula (57) wherein -CR= and R is a hydrogen atom, Y 511 ~Y 515 a compound represented by the above formula (58) wherein -CR= and R is a hydrogen atom, Y 521 ~Y 528 a compound represented by the above formula (59) wherein -CR= and R is a hydrogen atom, or, Y 531 ~Y 539 a compound represented by the above formula (59) wherein -CR= and R is a hydrogen atom, the photoelectric conversion element according to [9].

[11] The photoelectric conversion element according to [9], wherein the compound represented by the above formula (1) is a compound represented by any one of the above formula (16), the above formula (31), the above formula (32), the above formula (35), the above formula (37), the above formula (39), and the above formula (42).

[12] X 11 and X 12 represent a sulfur atom, the photoelectric conversion element according to any one of [1] to

[11] .

[13] The photoelectric conversion element according to any one of [1] to

[12] , wherein the photoelectric conversion film further contains an n-type semiconductor material. 〔14〕 The photoelectric conversion element according to

[13] , wherein the n-type semiconductor material contains fullerenes selected from the group consisting of fullerene and its derivatives. 〔15〕 The photoelectric conversion element according to any one of [1] to

[14] , wherein the photoelectric conversion film further contains a p-type semiconductor material. 〔16〕 The photoelectric conversion element according to any one of [1] to

[15] , wherein the photoelectric conversion film contains two compounds represented by the above formula (1). 〔17〕 The photoelectric conversion element according to any one of [1] to

[16] , wherein the photoelectric conversion film further contains a dye. 〔18〕 The photoelectric conversion element according to any one of [1] to

[17] , which has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. 〔19〕 An imaging device having the photoelectric conversion element according to any one of [1] to

[18] . 〔20〕 A photosensor having the photoelectric conversion element according to any one of [1] to

[18] . 〔21〕 The compound represented by formula (1) described below. 〔22〕 Ar 11 ~Ar 14 The compound according to

[21] , wherein each of Ar~Ar is independently a group represented by any one of formulas (2) to (7) described below. 〔23〕 Ar 15 ~Ar 16 The compound according to

[21] or

[22] , wherein each of Ar~Ar is independently a group represented by any one of formulas (8) to (15) and formulas (47) to (53) described below. 〔24〕 The compound according to any one of

[21] to

[23] , wherein n11~n12 represent 1, n13~n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

[25] A compound according to any one of

[21] to

[23] , wherein n11 to n14 represent 1, n15 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

[26] A compound according to any one of

[21] to

[23] , wherein n11 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

[27] A compound according to any one of

[21] to

[23] , wherein n11 to n12 represent 1, n13 to n14 represent 0, n15 to n16 represent 1, n17 represents 1, and n18 represents 1 or 2.

[28] A compound according to any one of

[21] to

[23] , wherein n11 to n14 represent 0, n15 to n16 each independently represent 0 or 1, n17 represents 2, and n18 represents 1.

[29] A compound according to any one of

[21] to

[23] , wherein the compound represented by the above formula (1) is a compound represented by any one of the following formulas (16) to (46) and formulas (54) to (60).

[30] The compound represented by the above formula (1) is Y 41 ~Y 42 and Y 81 ~Y 85 is -CR=, and the compound represented by the above formula (16) wherein R is a hydrogen atom, Y 41 ~Y 42 and Y 111 ~Y 115 is -CR=, and the compound represented by the above formula (17) wherein R is a hydrogen atom, Y 21 ~Y 24 and Y 111 ~Y 115 is -CR=, and the compound represented by the above formula (21) wherein R is a hydrogen atom, Y 21 ~Y 24 and Y 151 ~Y 157 is -CR=, and the compound represented by the above formula (22) wherein R is a hydrogen atom, Y 61 ~Y 62 and Y 81 ~Y 85The compound represented by the above formula (24) where it is -CR= and R is a hydrogen atom, Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (27) where it is -CR= and R is a hydrogen atom, Y 151 ~Y 157 The compound represented by the above formula (28) where it is -CR= and R is a hydrogen atom, Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (29) where it is -CR= and R is a hydrogen atom, Y 41 ~Y 42 and Y 91 ~Y 97 The compound represented by the above formula (44) where it is -CR= and R is a hydrogen atom, Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (45) where it is -CR= and R is a hydrogen atom, Y 21 ~Y 24 , Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (46) where it is -CR= and R is a hydrogen atom, Y 471 ~Y 475 The compound represented by the above formula (54) where it is -CR= and R is a hydrogen atom, Y 481 ~Y 485 The compound represented by the above formula (55) where it is -CR= and R is a hydrogen atom, Y 491 ~Y 497 The compound represented by the above formula (56) where it is -CR= and R is a hydrogen atom, Y 501 ~Y 505 The compound represented by the above formula (57) where it is -CR= and R is a hydrogen atom, Y 511 ~Y 515 The compound represented by the above formula (58) where it is -CR= and R is a hydrogen atom, Y 521 ~Y 528 The compound represented by the above formula (59) where it is -CR= and R is a hydrogen atom, or, Y 531 ~Y 539The compound described in

[29] , which is a compound represented by the above formula (59) wherein -CR= and R is a hydrogen atom.

[31] The compound described in

[29] , wherein the compound represented by the above formula (1) is a compound represented by any one of the above formula (16), the above formula (31), the above formula (32), the above formula (35), the above formula (37), the above formula (39), and the above formula (42).

[32] X 11 and X 12 The compound according to any one of

[21] to

[31] , wherein represents a sulfur atom. [Advantages of the Invention]

[0009] According to the present invention, a photoelectric conversion element excellent in photoelectric conversion efficiency can be provided. Further, according to the present invention, an imaging element, a photosensor, and a compound related to the above photoelectric conversion element can be provided. [Brief Description of the Drawings]

[0010]

Figure 1

Figure 2

[0011] Hereinafter, preferred embodiments of the photoelectric conversion element of the present invention will be described.

[0012] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.

[0013] In this specification, unless otherwise specified, the aromatic ring group may be monocyclic or polycyclic (e.g., bicyclic to hexacyclic). The monocyclic aromatic ring group is an aromatic ring group having only a single aromatic ring structure as the ring structure. The polycyclic (e.g., bicyclic to hexacyclic) aromatic ring group is an aromatic ring group in which a plurality (e.g., 2 to 6) of aromatic ring structures are fused as the ring structure. The number of ring member atoms of the above aromatic ring group is preferably an integer of 5 to 15. The above aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. When the above aromatic ring group is an aromatic heterocyclic group, the number of heteroatoms as ring member atoms is, for example, 1 to 10. Examples of the heteroatoms include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. Examples of the above aromatic hydrocarbon ring group include a benzene ring group, a naphthalene ring group, an anthracene ring group, and a phenanthrene ring group. Examples of the aromatic heterocyclic group include a pyridine ring group, a pyrimidine ring group, a pyridazine ring group, a pyrazine ring group, a triazine ring group (such as 1,2,3-triazine ring group, 1,2,4-triazine ring group, 1,3,5-triazine ring group, etc.), and a tetrazine ring group (such as 1,2,4,5-tetrazine ring, etc.), a quinoxaline ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a benzimidazole ring group, a benzoxazole ring group, a benzothiazole ring group, a naphthopyrrole ring group, a naphthofuran ring group, a naphthothiophene ring group, a naphthimidazole ring group, a naphthoxazole ring group, a 3H-pyrrolidine ring group, a pyrroloimidazole ring group (such as 5H-pyrrolo[1,2-a]imidazole ring group, etc.), an imidazoxazole ring group (such as imidazo[2,1-b]oxazole ring group, etc.), a thienothiazole ring group (such as thieno[2,3-d]thiazole ring group, etc.), a benzothiadiazole ring group, a benzodithiophene ring group (such as benzo[1,2-b:4,5-b']dithiophene ring group, etc.), a thienothiophene ring group (such as thieno[3,2-b]thiophene ring group, etc.), a thiazolothiazole ring group (such as thiazolo[5,4-d]thiazole ring group, etc.), a naphthodithiophene ring group (such as naphtho[2,3-b:6,7-b']dithiophene ring group, naphtho[2,1-b:6,5-b']dithiophene ring group, naphtho[1,2-b:5,6-b']dithiophene ring group, 1,8-dithiadicyclopenta[b,g]naphthalene ring group, etc.), a benzothienobenzothiophene ring group, a dithieno[3,2-b:2',3'-d]thiophene ring group, and a 3,4,7,8-tetrathiadicyclopenta[a,e]pentalene ring group. In this specification, when simply referring to an aromatic ring, for example, the aromatic rings constituting the above aromatic ring groups are included. When the aromatic ring group is monovalent, examples of such an aromatic ring group include a group formed by removing one hydrogen atom from the aromatic ring in the above-mentioned aromatic ring groups. The aromatic ring group in this case is a so-called aryl group or heteroaryl group. When the aromatic ring group is divalent, examples of such an aromatic ring group include a group formed by removing two hydrogen atoms from the aromatic ring in the above-mentioned aromatic ring group. The aromatic ring group in this case is a so-called aryl group or heteroaryl group. The aromatic ring group in this case is a so-called arylene group or heteroarylene group.

[0014] In this specification, when there are a plurality of the same symbols indicating the type or number of groups in one formula (general formula) showing a chemical structure, unless otherwise specified, the contents of these plurality of the same symbols are independent of each other, and the contents of the same symbols may be the same or different. In this specification, when there are a plurality of the same kind of groups (such as aromatic ring groups) in one formula (general formula) showing a chemical structure, unless otherwise specified, the specific contents of these plurality of the same kind of groups are independent of each other, and the specific contents of the same kind of groups may be the same or different.

[0015] Also, in this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0016] In this specification, the hydrogen atom may be a light hydrogen atom (ordinary hydrogen atom) or a deuterium atom (such as a deuterium atom).

[0017] [Photovoltaic conversion element] The photovoltaic conversion element of the present invention is a photovoltaic conversion element having a conductive film, a photovoltaic conversion film, and a transparent conductive film in this order, and the photovoltaic conversion film contains a compound represented by formula (1) (hereinafter, also referred to as "specific compound"). Although the mechanism by which the photovoltaic conversion element of the present invention can solve the above problems by having such a configuration is not necessarily clear, the present inventors presume as follows. That is, the specific compound has a parent nucleus with nitrogen-containing aromatic five-membered rings at both ends, and further, the parent nucleus has predetermined substituents at both ends of the parent nucleus. Since the parent nucleus has good crystallinity and the types and arrangements of the substituents that the parent nucleus can have are also limited to a range that does not inhibit the crystallinity of the specific compound, in the photoelectric conversion film, the charge transport property between specific compounds is good, and good charge transport property can be maintained even under a low voltage. As a result, in the photoelectric conversion element of the present invention in which the photoelectric conversion film contains the specific compound, it is considered that the field strength dependence of the photoelectric conversion efficiency is suppressed. In addition, the photoelectric conversion element of the present invention has good photoelectric conversion efficiency (particularly, the photoelectric conversion efficiency with respect to light having a wavelength of 400 to 700 nm), and the dark current is also suppressed. Hereinafter, the fact that the field strength dependence of the photoelectric conversion efficiency in the photoelectric conversion element is more suppressed, the photoelectric conversion efficiency is more excellent, and / or the dark current is more suppressed is also referred to as "the effect of the present invention is more excellent".

[0018] Fig. 1 shows a cross-sectional schematic view of an embodiment of the photoelectric conversion element of the present invention. The photoelectric conversion element 10a shown in Fig. 1 has a structure in which a conductive film (hereinafter, also referred to as a lower electrode) 11 that functions as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound described later, and a transparent conductive film (hereinafter, also referred to as an upper electrode) 15 that functions as an upper electrode are laminated in this order. Fig. 2 shows a configuration example of another photoelectric conversion element. The photoelectric conversion element 10b shown in Fig. 2 has a structure in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are laminated in this order on the lower electrode 11. Note that the lamination order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in Figs. 1 and 2 may be appropriately changed according to the use and characteristics.

[0019] In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 through the upper electrode 15. Also, 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 a voltage of 1×10 -5 ~1×10 7 V / cm is preferably applied between this pair of electrodes. From the viewpoints of performance and power consumption, the applied voltage is preferably 1×10 -4 ~1×10 7 V / cm, more preferably 1×10 -3 ~5×10 6 V / cm. Regarding the voltage application method, in FIGS. 1 and 2, it is preferable to apply the voltage such that the side of the electron blocking film 16A becomes the cathode and the side of the photoelectric conversion film 12 becomes the anode. When the photoelectric conversion element 10a (or 10b) is used as an optical sensor or when incorporated into an imaging element, the voltage can be applied by the same method. As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably applied to imaging element applications.

[0020] Hereinafter, the forms of each layer constituting the photoelectric conversion element of the present invention will be described in detail.

[0021] 〔Photoelectric conversion film〕 The photoelectric conversion film is a film containing a specific compound. Hereinafter, the specific compound will be described in detail.

[0022] <Compound represented by formula (1) (specific compound)> The specific compound is a compound represented by the following formula (1).

[0023]

Chemical formula

[0024] In formula (1), X 11 and X 12 each independently represents a sulfur atom or an oxygen atom. Among them, X 11 and X 12 are preferably sulfur atoms.

[0025] Ar 11 ~Ar 16 each independently represents a monocyclic, bicyclic, or tricyclic aromatic ring group. Further, the aromatic ring group may have, as a substituent, one or more groups selected from the group consisting of a halogen atom (preferably a fluorine atom), a cyano group, and a trifluoromethyl group. In other words, the aromatic ring group does not have a substituent other than one or more groups selected from the group consisting of a halogen atom (preferably a fluorine atom), a cyano group, and a trifluoromethyl group. Ar 11 ~Ar 16 The total number of the one or more groups that the aromatic ring group represented by Ar~Ar has as a substituent is, for example, each independently 0 to 5. Ar 11 ~Ar 14 is a divalent aromatic ring group. Ar 15 ~Ar 16 is a monovalent aromatic ring group. Ar 11 ~Ar 16 The aromatic ring group represented by Ar~Ar is preferably each independently a nitrogen-containing aromatic ring group having one or more (for example, 1 to 3) nitrogen atoms as ring member atoms. Ar 11 and Ar 12 are preferably the same aromatic ring groups, and Ar 13 and Ar 14 are preferably the same aromatic ring groups, and Ar 15 and Ar 16 are preferably the same aromatic ring groups. That each aromatic ring group is the same means that each aromatic ring group to be compared is the same group, and the positional relationship of each structure (heteroatoms, substituents, etc. that the aromatic ring group can have) constituting those aromatic ring groups is also the same with respect to the parent nucleus of the specific compound (the partial structure surrounded by the parentheses with n17 in formula (1)).

[0026] From the viewpoint of more excellent effects of the present invention, Ar 11 ~Ar 14is preferably a group represented by any one of formulas (2) to (7), independently of each other.

[0027]

Chemical formula

[0028] In formulas (2) to (7), * represents a bonding position. The two bonding positions each existing in formulas (2) to (7) may have the left bonding position (*) bonded to the parent nucleus side or the right bonding position (*) bonded to the parent nucleus side.

[0029] In formulas (2) to (7), the group represented by Y N represents -CR= or a nitrogen atom. Y N The "N" in it is an integer. That is, in formulas (2) to (7), Y 21 ~Y 24 、Y 31 ~Y 36 、Y 41 ~Y 42 、Y 51 ~Y 54 、Y 61 ~Y 62 、and Y 71 each independently represents -CR= or a nitrogen atom (-N=). R in -CR= represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a cyano group, or a trifluoromethyl group.

[0030] In formulas (2) to (7), the group represented by X N represents a sulfur atom (-S-), an oxygen atom (-O-), or a selenium atom (-Se-). The "N" in X N is an integer. That is, in formulas (2) to (7), X 41 、X 51 、X 61 ~X 62 、and X 71Each independently represents a sulfur atom (-S-), an oxygen atom (-O-), or a selenium atom (-Se-), with a sulfur atom or an oxygen atom being preferred.

[0031] From the point that the effects of the present invention are more excellent, Ar 15 ~Ar 16 Each is preferably a group represented by any one of Formula (8) to Formula (15) and Formula (47) to Formula (53).

[0032]

Chemical formula

[0033]

Chemical formula

[0034] In Formula (8) to Formula (15) and Formula (47) to Formula (53), * represents the bonding position.

[0035] In Formula (8) to Formula (15) and Formula (47) to Formula (53), the group represented by Y N represents -CR= or a nitrogen atom. The "N" in Y N is an integer. That is, in Formula (8) to Formula (15) and Formula (47) to Formula (53), Y 81 ~Y 85 、Y 91 ~Y 97 、Y 101 ~Y 103 、Y 111 ~Y 115 、Y 121 ~Y 123 、Y 131 ~Y 137 、Y 141 ~Y 145 、Y 151 ~Y 157 、Y 471 ~Y 475 、Y 481 ~Y 485 、Y 491 ~Y 497 、Y 501 ~Y505 and Y 511 to Y 515 and Y 521 to Y 529 and, and Y 531 to Y 539 each independently represents -CR= or a nitrogen atom (-N=). R in -CR= represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a cyano group, or a trifluoromethyl group. Among them, Y 81 to Y 85 and Y 91 to Y 97 and Y 101 to Y 103 and Y 111 to Y 115 and Y 121 to Y 123 and Y 131 to Y 137 and Y 141 to Y 145 and Y 151 to Y 157 and Y 471 to Y 475 and Y 481 to Y 485 and Y 491 to Y 497 and Y 501 to Y 505 and Y 511 to Y 515 and Y 521 to Y 529 and, and Y 531 to Y 539 As, -CR= is preferred, and -CR= with R being a hydrogen atom is more preferred. That is, Y 81 to Y 85 and Y 91 to Y 97 and Y 101 to Y 103 and Y 111 to Y 115 and Y 121 to Y 123 and Y 131 to Y 137 and Y 141 to Y 145 and Y 151 to Y 157 and Y 471 to Y 475 and Y 481 to Y485 , Y 491 ~Y 497 , Y 501 ~Y 505 , Y 511 ~Y 515 , Y 521 ~Y 529 , and, Y 531 ~Y 539 is preferably -CH=.

[0036] In formulas (8) to (15) and formulas (47) to (53), the group represented by X N represents a sulfur atom (-S-), an oxygen atom (-O-), or a selenium atom (-Se-). The "N" in X N is an integer. That is, in formulas (8) to (15) and formulas (47) to (53), X 101 , X 111 , X 121 ~X 122 , X 141 , X 151 , X 471 ~X 472 , X 481 ~X 482 , X 491 , X 501 ~X 502 , and, X 511 ~X 512 each independently represents a sulfur atom (-S-), an oxygen atom (-O-), or a selenium atom (-Se-), and a sulfur atom or an oxygen atom is preferred.

[0037] In formula (1), X 13 and X 14 each independently represents an oxygen atom (=O) or a sulfur atom (=S), and an oxygen atom is preferred. X 13 and X 14 are preferably the same atom.

[0038] In formula (1), n11 to n16 each independently represent 0 or 1. It is preferable that n11 and n12 have the same value, it is preferable that n13 and n14 have the same value, and it is preferable that n15 and n16 have the same value. When n11 to n16 are 0, there is no group enclosed by parentheses with n11 to n16 attached. For example, when n11 is 1 and n13 and n15 are 0, Ar in formula (1) 11 and Ar 15 are bonded by a single bond. However, when all of n11 to n16 are 0 and n17 is 1, Ar 15 and Ar 16 The above aromatic ring group represented by is a tricyclic aromatic ring group.

[0039] In addition, when a specific compound is applied to formula (1), if there is a specific compound for which both interpretations, that is, the interpretation that n11 is 1 and n13 is 0 and the interpretation that n11 is 0 and n13 is 1, are possible, it is preferable to interpret that specific compound as a compound in which n11 is 1 and n13 is 0 in formula (1). Similarly, when a specific compound is applied to formula (1), if there is a specific compound for which both interpretations, that is, the interpretation that n12 is 1 and n14 is 0 and the interpretation that n12 is 0 and n14 is 1, are possible, it is preferable to interpret that specific compound as a compound in which n12 is 1 and n14 is 0 in formula (1).

[0040] In formula (1), n17 represents 1 or 2. When n17 is 2, the parent nucleus of the specific compound has a structure in which two 4-ring or 5-ring aromatic ring groups are bonded by a single bond. When n17 is 2, it is also preferable that X 11 and X 12 existing outside the parent nucleus are the same atom. When n17 is 2, it is also preferable that X 11 and X 12 existing inside the parent nucleus are the same atom.

[0041] In formula (1), n18 represents 1 or 2.

[0042] Among them, examples of preferable combinations of n11 to n18 in formula (1) include the following. Example A: A combination in which n11 to n12 represent 1, n13 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2. Example B: A combination in which n11 to n14 represent 1, n15 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2. Example C: A combination in which n11 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2. Example D: A combination in which n11 to n12 represent 1, n13 to n14 represent 0, n15 to n16 represent 1, n17 represents 1, and n18 represents 1 or 2. Example E: A combination in which n11 to n14 represent 0, n15 to n16 each independently represent 0 or 1, n17 represents 2, and n18 represents 1.

[0043] Among them, from the viewpoint of more excellent effects of the present invention, the specific compound is preferably a compound represented by any one of the following formulas (16) to (46) and formulas (54) to (60).

[0044]

Chemical formula

[0045]

Chemical formula

[0046]

Chemical formula

[0047]

Chemical formula

[0048]

Chemical formula

[0049]

Chemical formula

[0050]

Chem.

[0051]

Chem.

[0052]

Chem.

[0053] In formulas (16) to (46) and formulas (54) to (60), Y N The group represented by represents -CR= or a nitrogen atom. Y N The "N" in is an integer. That is, in formulas (16) to (46), Y 21 ~Y 24 、Y 41 ~Y 42 、Y 51 ~Y 54 、Y 61 ~Y 62 、Y 71 、Y 81 ~Y 85 、Y 91 ~Y 97 、Y 101 ~Y 103 、Y 111 ~Y 115 、Y 121 ~Y 123 、Y 151 ~Y 157 、Y 471 ~Y 475 、Y 481 ~Y 485 、Y 491 ~Y 497 、Y 501 ~Y 505 、Y 511 ~Y 515 、Y 521 ~Y 528 、and Y 531 ~Y539 Each independently represents -CR= or a nitrogen atom (-N=). R in -CR= represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a cyano group, or a trifluoromethyl group. Among them, Y 81 ~Y 85 Y 91 ~Y 97 Y 101 ~Y 103 Y 111 ~Y 115 Y 121 ~Y 123 Y 131 ~Y 137 Y 141 ~Y 145 Y 151 ~Y 157 Y 471 ~Y 475 Y 481 ~Y 485 Y 491 ~Y 497 Y 501 ~Y 505 Y 511 ~Y 515 Y 521 ~Y 529 and Y 531 ~Y 539 As, -CR= is preferred, and -CR= with R being a hydrogen atom is more preferred. That is, Y 81 ~Y 85 Y 91 ~Y 97 Y 101 ~Y 103 Y 111 ~Y 115 Y 121 ~Y 123 Y 131 ~Y 137 Y 141 ~Y 145 Y 151 ~Y 157 Y 471 ~Y 475 Y 481 ~Y 485 Y 491 ~Y 497 Y 501 ~Y 505 Y 511 ~Y515 , Y 521 ~Y 529 , and, Y 531 ~Y 539 Preferably, it is -CH=.

[0054] In Formulas (16) to (46) and Formulas (54) to (60), X 11 and X 12 each independently represents a sulfur atom (-S-) or an oxygen atom (-O-). In Formulas (16) to (46), X 13 and X 14 each independently represents a sulfur atom (=S) or an oxygen atom (=O). In Formulas (16) to (46), X 11 ~X 14 Excluding X N The group represented by represents a sulfur atom (-S-), an oxygen atom (-O-), or a selenium atom (-Se-). X N "N" in is an integer. In Formulas (16) to (46) and Formulas (54) to (60), X 41 , X 51 , X 61 ~X 62 , X 71 , X 101 , X 111 , X 121 ~X 122 , X 151 , X 471 , X 481 ~X 482 , X 491 , X 501 ~X 502 , and, X 511 ~X 512 each independently represents a sulfur atom (-S-), an oxygen atom (-O-), or a selenium atom (-Se-), and a sulfur atom or an oxygen atom is preferred.

[0055] The specific compound (particularly, when used as an n-type material described later) has an aromatic ring group containing a group with -N= in the ring structure as Ar 11 and Ar 12 or satisfies at least one of the requirements that n15 and n16 are 1, and Ar15 and Ar 16 is Y 81 ~Y 85 is preferably a group represented by formula (8) in which Y~Y is -CF=, -C(CN)=, or -N=.

[0056] The specific compound (particularly, when used as a p-type material described later), where Y~Y 41 ~Y 42 and Y 81 ~Y 85 is -CR= and R is a hydrogen atom, the compound represented by the above formula (16), Y 41 ~Y 42 and Y 111 ~Y 115 is -CR= and R is a hydrogen atom, the compound represented by the above formula (17), Y 21 ~Y 24 and Y 111 ~Y 115 is -CR= and R is a hydrogen atom, the compound represented by the above formula (21), Y 21 ~Y 24 and Y 151 ~Y 157 is -CR= and R is a hydrogen atom, the compound represented by the above formula (22), Y 61 ~Y 62 and Y 81 ~Y 85 is -CR= and R is a hydrogen atom, the compound represented by the above formula (24), Y 51 ~Y 54 and Y 81 ~Y 85 is -CR= and R is a hydrogen atom, the compound represented by the above formula (27), Y 151 ~Y 157 is -CR= and R is a hydrogen atom, the compound represented by the above formula (28), Y 41 ~Y 42 and Y 81 ~Y 85 is -CR= and R is a hydrogen atom, the compound represented by the above formula (29), Y 41 ~Y 42 and Y 91 ~Y 97 is -CR= and R is a hydrogen atom, the above formula (44), Y 51 ~Y54 and Y 81 ~Y 85 The compound represented by the above formula (45) wherein -CR= and R is a hydrogen atom, Y 21 ~Y 24 , Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (46) wherein -CR= and R is a hydrogen atom, Y 471 ~Y 475 The compound represented by the above formula (54) wherein -CR= and R is a hydrogen atom, Y 481 ~Y 485 The compound represented by the above formula (55) wherein -CR= and R is a hydrogen atom, Y 491 ~Y 497 The compound represented by the above formula (56) wherein -CR= and R is a hydrogen atom, Y 501 ~Y 505 The compound represented by the above formula (57) wherein -CR= and R is a hydrogen atom, Y 511 ~Y 515 The compound represented by the above formula (58) wherein -CR= and R is a hydrogen atom, Y 521 ~Y 528 The compound represented by the above formula (59) wherein -CR= and R is a hydrogen atom, or, Y 531 ~Y 539 Preferably, it is the compound represented by the above formula (59) wherein -CR= and R is a hydrogen atom. In addition, the notation of the above compound indicates an embodiment in which the group represented by Y N (N is a number) is -CR= (R represents a hydrogen atom). More specifically, for example, "Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (16) wherein -CR= and R is a hydrogen atom" means a compound in which Y in formula (16) 41 ~Y 42 and Y 81 ~Y 85 is -CR= (R represents a hydrogen atom).

[0057] The specific compound is preferably a compound represented by any one of the above formula (16), the above formula (31), the above formula (32), the above formula (35), the above formula (37), the above formula (39), and the above formula (42) (particularly when used as the n-type material described later).

[0058] Specific examples of the specific compound are shown below.

[0059] [Chemical formula]

[0060] [Chemical formula]

[0061] [Chemical formula]

[0062] [Chemical formula]

[0063] [Chemical formula]

[0064] [Chemical formula]

[0065] [Chemical formula]

[0066] [Chemical formula]

[0067] [Chemical formula]

[0068]

Chem.

[0069]

Chem.

[0070]

Chem.

[0071]

Chem.

[0072]

Chem.

[0073]

Chem.

[0074]

Chem.

[0075]

Chem.

[0076]

Chem.

[0077]

Chem.

[0078] [Chemistry]

[0079] [Chemistry]

[0080] The molecular weight of the specific compound is not particularly limited, preferably 550 or more, more preferably 600 or more. The molecular weight of the specific compound is preferably 1200 or less, more preferably 1000 or less. If the molecular weight is 1200 or less, the deposition temperature does not increase, and the decomposition of the compound hardly occurs. If the molecular weight is 550 or more, the glass transition point of the deposited film does not decrease, and the heat resistance of the photoelectric conversion element is improved.

[0081] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging device, a photosensor, or a photovoltaic cell. Further, the specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic agent material.

[0082] The maximum absorption wavelength of the specific compound is not particularly limited, and is preferably in the range of 300 to 550 nm, more preferably in the range of 400 to 550 nm, for example. The above maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) by adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance is 0.5 to 1. However, when the specific compound is not soluble in chloroform, the value measured using the specific compound in a film state obtained by depositing the specific compound is taken as the maximum absorption wavelength of the specific compound.

[0083] The maximum absorption wavelength of the photoelectric conversion film is not particularly limited, and is preferably in the range of 300 to 700 nm, more preferably in the range of 400 to 700 nm, for example.

[0084] In addition, the specific compound can be used as a p-type material (a material with excellent hole transportability) or an n-type material (a material with excellent electron transportability).

[0085] When the specific compound is used as an n-type material, the specific compound preferably satisfies one or more of the following requirements. Requirement 1: The specific compound has 3 or more (for example, 4 to 16) fluorine atoms (preferably fluorine atoms present as substituents of the aromatic ring group represented by Ar 11 ~Ar 16 in the formula (1)) in the molecule. Requirement 2: One or more (preferably 2 to 4) of Ar 11 ~Ar 14 is a nitrogen-containing aromatic ring group containing a nitrogen atom as a ring member atom, and the molecule has a total of 1 or more (for example, 2 to 16) fluorine atoms or cyano groups (preferably fluorine atoms present as substituents of the aromatic ring group represented by Ar 11 ~Ar 16 in the formula (1)). When the specific compound is used as a p-type material, the specific compound is preferably a compound that does not satisfy any of the above requirements.

[0086] When the specific compound is used as a p-type material, the ionization potential of the specific compound is preferably 5.0 to 6.0 eV.

[0087] In addition, when the specific compound is used as an n-type material, the electron affinity of the specific compound is preferably 3.0 to 4.5 eV. In this specification, as the value of the electron affinity, the value of the reciprocal of the value of LUMO (the value multiplied by minus 1) obtained by the calculation of B3LYP / 6-31G(d) using Gaussian '09 (software manufactured by Gaussian, Inc.) is used.

[0088] The specific compound contained in the photoelectric conversion film may be only the specific compound substantially used as a p-type material, may be only the specific compound substantially used as an n-type material, or may be both the specific compound used as a p-type material and the specific compound used as an n-type material.

[0089] When the specific compound contained in the photoelectric conversion film is only the specific compound substantially used as a p-type material, it means that the content of the specific compound used as a p-type material (= film thickness in monolayer conversion of the specific compound used as a p-type material / total film thickness in monolayer conversion of all specific compounds × 100) is more than 90% by volume and 100% by volume or less (preferably 95 - 100% by volume, more preferably 99 - 100% by volume) with respect to all the specific compounds contained in the photoelectric conversion film.

[0090] When the specific compound contained in the photoelectric conversion film is only the specific compound substantially used as an n-type material, it means that the content of the specific compound used as an n-type material (= film thickness in monolayer conversion of the specific compound used as an n-type material / total film thickness in monolayer conversion of all specific compounds × 100) is more than 90% by volume and 100% by volume or less (preferably 95 - 100% by volume, more preferably 99 - 100% by volume) with respect to all the specific compounds contained in the photoelectric conversion film.

[0091] When the specific compound contained in the photoelectric conversion film is both the specific compound used as a p-type material and the specific compound used as an n-type material, the ratio of the content of the specific compound used as a p-type material to the content of the specific compound used as an n-type material in the photoelectric conversion film (= film thickness in monolayer conversion of the specific compound used as a p-type material / film thickness in monolayer conversion of the specific compound used as an n-type material) is preferably 10 / 90 - 90 / 10, more preferably 40 / 60 - 60 / 40, and even more preferably 47 / 53 - 53 / 47.

[0092] The photoelectric conversion film may contain only one kind of the specific compound, may contain two kinds, or may contain three or more kinds.

[0093] When the photoelectric conversion film contains only one specific compound, it means that there should be substantially only one specific compound contained in the photoelectric conversion film. When the specific compound contained in the photoelectric conversion film is substantially only one kind, it means that for all the specific compounds contained in the photoelectric conversion film, the content of the most contained specific compound (= the film thickness of the most contained specific compound in monolayer conversion / the total film thickness of all specific compounds in monolayer conversion × 100) is more than 90% by volume and 100% by volume or less (preferably 95 - 100% by volume, more preferably 99 - 100% by volume). When the photoelectric conversion film contains only one specific compound, the above one specific compound may be a specific compound used as a p - type material or a specific compound used as an n - type material.

[0094] When the photoelectric conversion film contains two specific compounds, it means that there should be substantially only two specific compounds contained in the photoelectric conversion film. When the specific compounds contained in the photoelectric conversion film are substantially only two kinds, it means that for all the specific compounds contained in the photoelectric conversion film, the total content of the two most contained specific compounds (= the total film thickness of the two most contained specific compounds in monolayer conversion / the total film thickness of all specific compounds in monolayer conversion × 100) is more than 90% by volume and 100% by volume or less (preferably 95 - 100% by volume, more preferably 99 - 100% by volume). When the two most contained specific compounds are respectively defined as specific compound A and specific compound B, the ratio of the content of specific compound A and specific compound B in the photoelectric conversion film (= the film thickness of specific compound A in monolayer conversion / the film thickness of specific compound B in monolayer conversion) is preferably 10 / 90 - 90 / 10, more preferably 40 / 60 - 60 / 40, and even more preferably 47 / 53 - 53 / 47. When the photoelectric conversion film contains only two specific compounds, both of the two specific compounds may be specific compounds used as p - type materials, or both may be specific compounds used as n - type materials, or it is also preferable that one is a specific compound used as a p - type material and the other is a specific compound used as an n - type material.

[0095] From the viewpoint of the responsivity of the photoelectric conversion element, the content of the specific compound in the photoelectric conversion film (= film thickness in terms of a single layer of the specific compound / film thickness of the photoelectric conversion film × 100) is preferably 15 to 85% by volume. Among them, when the photoelectric conversion element contains only one kind of the specific compound, the content of the specific compound in the photoelectric conversion film is more preferably 20 to 60% by volume, and still more preferably 25 to 40% by volume. When the photoelectric conversion element contains two kinds of the specific compounds, the content of the specific compounds in the photoelectric conversion film is more preferably 40 to 80% by volume, and still more preferably 60 to 75% by volume.

[0096] <Dye> The photoelectric conversion film preferably contains a dye as another component other than the above-described specific compound. The above dye is preferably an organic dye. Examples of the above-mentioned pigment include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridinone dyes, quinoxaline dyes, diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complex dyes, compounds described in paragraphs

[0083] to

[0089] of JP-A No. 2014-82483, compounds described in paragraphs

[0029] to

[0033] of JP-A No. 2009-167348, compounds described in paragraphs

[0197] to

[0227] of JP-A No. 2012-077064, compounds described in paragraphs

[0035] to

[0038] of WO2018-105269, compounds described in paragraphs

[0041] to

[0043] of WO2018-186389, compounds described in paragraphs

[0059] to

[0062] of WO2018-186397, compounds described in paragraphs

[0078] to

[0083] of WO2019-009249, compounds described in paragraphs

[0054] to

[0056] of WO2019-049946, compounds described in paragraphs

[0059] to

[0063] of WO2019-054327, compounds described in paragraphs

[0086] to

[0087] of WO2019-098161, and compounds described in paragraphs

[0085] to

[0114] of WO2020-013246.

[0097] The content of the pigment in the photoelectric conversion film (= film thickness in terms of a single layer of the pigment / film thickness of the photoelectric conversion film × 100) is preferably 15 to 85% by volume, more preferably 20 to 60% by volume, and still more preferably 25 to 40% by volume. In the photoelectric conversion film, the content of the dye relative to the total content of the specific compound and the dye (=(film thickness in terms of a single layer of the dye / (film thickness in terms of a single layer of the specific compound + film thickness in terms of a single layer of the dye)) × 100) is preferably 15 to 75% by volume, more preferably 20 to 65% by volume, and still more preferably 25 to 60% by volume. Note that the dye may be used alone or in combination of two or more.

[0098] <n-type semiconductor material> The photoelectric conversion film preferably contains an n-type semiconductor material as another component other than the specific compound and the dye described above. Among them, when the photoelectric conversion film contains the specific compound used as a p-type material, it is preferable to contain an n-type semiconductor material. When the specific compound contained in the photoelectric conversion film is only the specific compound used as a p-type material, it is more preferable for the photoelectric conversion film to contain an n-type semiconductor material. When the photoelectric conversion film contains only one kind of specific compound and the above-mentioned one kind of specific compound is the specific compound used as a p-type material, it is still more preferable for the photoelectric conversion film to contain an n-type semiconductor material. The n-type semiconductor material is an acceptor-type organic semiconductor material (compound), which refers to an organic compound having a property of easily accepting electrons. More specifically, when the n-type semiconductor material is used in contact with the above-mentioned specific compound, an organic compound having a larger electron affinity than the specific compound is preferable. Also, when the n-type semiconductor material is used in contact with the above-mentioned dye, it is preferably an organic compound having a larger electron affinity than the dye. The electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV.

[0099] The n-type semiconductor material includes, for example, fullerenes selected from the group consisting of fullerenes and their derivatives, condensed aromatic carbon ring compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having at least one of a nitrogen atom, an oxygen atom, and a sulfur atom (for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole, etc.); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives, oxadiazole derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and their derivatives; triazole compounds; distyrylarylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silole compounds; and the compounds described in paragraphs

[0056] to

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

[0100] Among them, the n-type semiconductor material preferably contains fullerenes selected from the group consisting of fullerenes and their derivatives. Examples of fullerenes include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C80, fullerene C82, fullerene C84, fullerene C90, fullerene C96, fullerene C240, fullerene C540, and mixed fullerenes. Examples of fullerene derivatives include compounds in which substituents are added to the above fullerenes. The substituents are preferably an alkyl group, an aryl group, or a heterocyclic group. The fullerene derivatives are preferably the compounds described in JP-A No. 2007-123707.

[0101] When the photoelectric conversion film contains an n-type semiconductor material, the content of the n-type semiconductor material in the photoelectric conversion film (= film thickness in terms of a single layer of the n-type semiconductor material / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and still more preferably 25 to 50% by volume. Note that the n-type semiconductor material may be used alone or in combination of two or more.

[0102] When the n-type semiconductor material contains fullerenes, the content of fullerenes with respect to the total content of the n-type semiconductor material (= (film thickness in terms of a single layer of fullerenes / total film thickness of each n-type semiconductor material in terms of a single layer) × 100) is preferably 50 to 100% by volume, and more preferably 80 to 100% by volume. Note that fullerenes may be used alone or in combination of two or more.

[0103] The molecular weight of the n-type semiconductor material is preferably 200 to 1200, and more preferably 200 to 1000.

[0104] It is also preferable that the photoelectric conversion film is substantially composed of only a specific compound, a pigment, and an n-type semiconductor material. That the photoelectric conversion film is substantially composed of only a specific compound, a pigment, and an n-type semiconductor material means that the total content of the specific compound, the pigment, and the n-type semiconductor material is 95 to 100% by mass with respect to the total mass of the photoelectric conversion film.

[0105] <p-type semiconductor material> It is also preferable that the photoelectric conversion film contains a p-type semiconductor material as other components in addition to the specific compound and the pigment described above. Among them, it is preferable that the photoelectric conversion film contains a p-type semiconductor material when the photoelectric conversion film contains the specific compound used as the n-type material. It is more preferable that the photoelectric conversion film contains a p-type semiconductor material when the specific compound contained in the photoelectric conversion film is only the specific compound used as the n-type material. It is still more preferable that the photoelectric conversion film contains a p-type semiconductor material when the photoelectric conversion film contains only one kind of specific compound and the above one kind of specific compound is the specific compound used as the n-type material. The p-type semiconductor material is a donor-type organic semiconductor material (compound), which refers to an organic compound having a property of easily donating electrons. More specifically, the p-type semiconductor material is preferably an organic compound having better hole transport properties than a specific compound in the photoelectric conversion film, and more preferably an organic compound having better hole transport properties than both the specific compound and the dye. In this specification, the hole transport property (hole carrier mobility) of a compound can be evaluated, for example, by the Time-of-Flight method (time-of-flight method, TOF method), or using a field effect transistor element. The hole carrier mobility of the p-type semiconductor material is preferably 10 -4 cm 2 / V·s or more, more preferably 10 -3 cm 2 / V·s or more, and even more preferably 10 -2 cm 2 / V·s or more. The upper limit of the above hole carrier mobility is not particularly limited, but from the point of suppressing the flow of a small amount of current in the state of not being irradiated with light, for example, 10 cm 2 / V·s or less is preferred. Also, the p-type semiconductor material preferably has a smaller ionization potential than a specific compound in the photoelectric conversion film, and more preferably has a smaller ionization potential than both the specific compound and the dye.

[0106] The p-type semiconductor material is, for example, a triarylamine compound (e.g., N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD), the compounds described in paragraphs

[0128] to

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

[0052] to

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

[0119] to

[0158] of JP-A-2011-225544, the compounds described in

[0044] to

[0051] of JP-A-2015-153910, and the compounds described in paragraphs

[0086] to

[0090] of JP-A-2012-094660, etc.), a pyrazoline compound, a styrylamine compound, a hydrazone compound, a polysilane compound, a thiophene compound (e.g., a thienothiophene derivative, a dibenzothiophene derivative, a benzodithiophene derivative, a dithienothiophene derivative, [1]benzothieno[3,2-b]thiophene (BTBT) derivative, thieno[3,2-f:4,5-f´]Bis[1]benzothiophene (TBBT) derivatives, compounds described in paragraphs

[0031] to

[0036] of JP-A No. 2018-014474, compounds described in paragraphs

[0043] to

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

[0025] to

[0037] ,

[0099] to

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

[0029] to

[0034] of JP-A No. 2017-076766, compounds described in paragraphs

[0015] to

[0025] of WO2018-207722, compounds described in paragraphs

[0045] to

[0053] of JP-A No. 2019-054228, compounds described in paragraphs

[0045] to

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

[0063] to

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

[0033] to

[0036] of JP-A No. 2019-080052, compounds described in paragraphs

[0044] to

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

[0041] to

[0046] of WO2019-093188, 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 fluoranthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand.

[0107] Further, the p-type semiconductor material is preferably a compound represented by formula (p1), a compound represented by formula (p2), a compound represented by formula (p3), a compound represented by formula (p4), or a compound represented by formula (p5).

[0108]

Chemical formula

[0109] In formulas (p1) to (p6), the two Rs each independently represent a hydrogen atom or a substituent (alkyl group, alkoxy group, halogen atom, alkylthio group, (hetero)arylthio group, alkylamino group, (hetero)arylamino group, or (hetero)aryl group, etc.). These groups may further have substituents if possible. For example, the (hetero)aryl group may be an arylaryl group (i.e., biaryl group, at least one of the aryl groups constituting this group may be a heteroaryl group) which may further have a substituent) Also, as R, a group represented by R in formula (IX) of WO2019 - 081416 is also preferable. X and Y each independently represent -CR 2 2-, sulfur atom (-S-), oxygen atom (-O-), -NR 2 -, or -SiR 2 2-. R 2 represents a hydrogen atom, an alkyl group which may have a substituent (preferably a methyl group or a trifluoromethyl group), an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Two or more Rs 2 may be the same or different from each other. Ar represents an aromatic ring group (preferably a benzene ring group).

[0110] Among them, for the p-type semiconductor material, a compound represented by formula (p1) is preferable.

[0111] When the photoelectric conversion film contains a p-type semiconductor material, the content of the p-type semiconductor material in the photoelectric conversion film (= film thickness of the p-type semiconductor material in monolayer conversion / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and still more preferably 25 to 50% by volume. Note that the n-type semiconductor material may be used alone or in combination of two or more.

[0112] The photoelectric conversion film is preferably substantially composed of only a specific compound, a pigment, and a p-type semiconductor material. That the photoelectric conversion film is substantially composed of only a specific compound, a pigment, and a p-type semiconductor material means that the total content of the specific compound, the pigment, and the p-type semiconductor material is 95 to 100% by mass based on the total mass of the photoelectric conversion film.

[0113] The photoelectric conversion film is preferably substantially composed of only a specific compound, a pigment, an n-type semiconductor material, and a p-type semiconductor material. That the photoelectric conversion film is substantially composed of only a specific compound, a pigment, an n-type semiconductor material, and a p-type semiconductor material means that the total content of the specific compound, the pigment, the n-type semiconductor material, and the p-type semiconductor material is 95 to 100% by mass based on the total mass of the photoelectric conversion film.

[0114] When the photoelectric conversion film contains a pigment, the photoelectric conversion film is preferably a mixed layer formed in a state where the specific compound and the pigment are mixed. Also, when the photoelectric conversion film contains an n-type semiconductor material and / or a p-type semiconductor material, the photoelectric conversion film is preferably a mixed layer formed in a state where the specific compound and the n-type semiconductor material and / or the p-type semiconductor material are mixed. When the photoelectric conversion film contains a pigment and an n-type semiconductor material and / or a p-type semiconductor material, the photoelectric conversion film is preferably a mixed layer formed in a state where the specific compound, the pigment, and the n-type semiconductor material and / or the p-type semiconductor material are mixed. The mixed layer is a layer in which two or more materials are mixed in a single layer.

[0115] The photoelectric conversion film containing the specific compound is a non-luminescent film and has characteristics different from those of an organic light-emitting diode (OLED). The non-luminescent film is intended to be a film with a luminescence quantum efficiency of 1% or less, and the luminescence quantum efficiency is preferably 0.5% or less, more preferably 0.1% or less.

[0116] <Film formation method> The photoelectric conversion film can mainly be formed by a dry film-forming method. Examples of the dry film-forming method include physical vapor deposition methods such as evaporation (especially vacuum evaporation), sputtering, ion plating, and MBE (Molecular Beam Epitaxy) methods, as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization. Among these, the vacuum evaporation method is preferred. When forming the photoelectric conversion film by the vacuum evaporation method, manufacturing conditions such as the degree of vacuum and evaporation temperature can be set according to conventional methods.

[0117] The thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, still more preferably 50 to 500 nm, and particularly preferably 50 to 400 nm.

[0118] 〔Electrode (Conductive Film)〕 The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are composed of a conductive material. Examples of the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected. Examples of the material constituting the upper electrode 15 include conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO: Antimony Tin Oxide, FTO: Fluorine doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO: Indium zinc oxide); metal thin films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as graphene and carbon nanotubes. Among these, conductive metal oxides are preferred in terms of high conductivity and transparency.

[0119] Generally, when the conductive film is made thinner than a certain range, it causes a sharp increase in the resistance value. However, in the solid-state imaging device incorporating the photoelectric conversion element according to this embodiment, the sheet resistance may be, for example, 100 to 10,000 Ω / sq, and the degree of freedom in the range of film thickness that can be thinned is large. Further, the thinner the upper electrode (transparent conductive film) 15 is, the less light it absorbs, and generally the light transmittance increases. The increase in light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability. Considering the suppression of leakage current, the increase in the resistance value of the thin film, and the increase in transmittance accompanying the thinning, the film thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0120] The lower electrode 11 may or may not have transparency depending on the application. Materials constituting the lower electrode 11 include, for example, conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides or nitrides of these metals (e.g., titanium nitride (TiN) as an example); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as graphene and carbon nanotubes.

[0121] The method for forming the electrode is not particularly limited and can be appropriately selected according to the electrode material. Specifically, wet methods such as printing methods and coating methods; physical methods such as vacuum evaporation, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD methods can be mentioned. When the electrode material is ITO, methods such as electron beam method, sputtering method, resistance heating evaporation method, chemical reaction method (sol-gel method, etc.), and coating of a dispersion of indium tin oxide can be mentioned.

[0122] [Charge blocking film: Electron blocking film, Hole blocking film] It is also preferable that the photoelectric conversion element of the present invention has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. Examples of the intermediate layer include a charge blocking film. By having this film in the photoelectric conversion element, the characteristics of the obtained photoelectric conversion element (such as photoelectric conversion efficiency and responsiveness) are more excellent. Examples of the charge blocking film include an electron blocking film and a hole blocking film. Each film will be described in detail below.

[0123] <Electron blocking film> The electron blocking film is a donor-type organic semiconductor material (compound). For example, a p-type organic semiconductor as described above can be used. The p-type organic semiconductor may be used alone or in combination of two or more.

[0124] In addition, examples of the p-type organic semiconductor used in the electron blocking film include compounds having a smaller ionization potential than the n-type semiconductor material. If this condition is satisfied, a dye as described above can also be used.

[0125] In addition, a polymer material can also be used as the electron blocking film. Examples of the polymer material include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.

[0126] Note that the electron blocking film may be composed of a plurality of films. The electron blocking film may be composed of an inorganic material. Generally, since the dielectric constant of an inorganic material is larger than that of an organic material, when an inorganic material is used for the electron blocking film, a large voltage is applied to the photoelectric conversion film, and the photoelectric conversion efficiency is increased. Examples of the inorganic material that can be an electron blocking film include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

[0127] <Positive hole blocking film> The positive hole blocking film is an acceptor-type organic semiconductor material (compound), and the above-described n-type semiconductor material or the like can be used.

[0128] The method for manufacturing the charge blocking film is not particularly limited, and examples thereof include a dry film forming method and a wet film forming method. Examples of the dry film forming method include a vapor deposition method and a sputtering method. The vapor deposition method may be either a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method, and a physical vapor deposition method such as a vacuum vapor deposition method is preferred. Examples of the wet film forming method include an inkjet method, a spray method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, and a gravure coating method. From the viewpoint of high-precision patterning, the inkjet method is preferred.

[0129] The thickness of the charge blocking film (electron blocking film and positive hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and still more preferably 5 to 30 nm, respectively.

[0130] 〔Substrate〕 The photoelectric conversion element may further include a substrate. The type of the substrate used is not particularly limited, and examples thereof include a semiconductor substrate, a glass substrate, and a plastic substrate. Note that the position of the substrate is not particularly limited, and usually, a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated on the substrate in this order.

[0131] 〔Sealing layer〕 The photoelectric conversion element may further include a sealing layer. The performance of the photoelectric conversion material may be significantly deteriorated in the presence of deterioration factors such as water molecules. Therefore, the entire photoelectric conversion film is covered and sealed with a sealing layer such as a dense metal oxide, a metal nitride, or a metal oxynitride ceramic that does not allow water molecules to penetrate, or diamond-like carbon (DLC), thereby preventing the above deterioration. Note that the sealing layer may be selected and manufactured according to the description in paragraphs

[0210] to

[0215] of JP-A-2011-082508.

[0132] [Image pickup device, optical sensor] As an application of the photoelectric conversion element, for example, an image pickup device can be mentioned. An image pickup device is an element that converts optical information of an image into an electrical signal. Usually, a plurality of photoelectric conversion elements are arranged in a matrix on the same plane, and in each photoelectric conversion element (pixel), an optical signal is converted into an electrical signal, and the electrical signal can be sequentially output outside the image pickup device for each pixel. For this purpose, each pixel is composed of one or more photoelectric conversion elements and one or more transistors. The image pickup device is mounted on image pickup devices such as digital cameras and digital video cameras, electronic endoscopes, and imaging modules such as mobile phones.

[0133] The photoelectric conversion element of the present invention is also preferably used for an optical sensor having the photoelectric conversion element of the present invention. The optical sensor may be used alone with the above-described photoelectric conversion element, or may be used as a line sensor in which the above-described photoelectric conversion elements are arranged linearly, or a two-dimensional sensor arranged in a plane.

[0134] [Compound] The present invention also relates to a compound. The compound of the present invention is the same as the above-described specific compound (the compound represented by formula (1)), and the preferred conditions are also the same.

Examples

[0135] The present invention will be described in more detail based on the following examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0136] [Compound (evaluation compound)] [Synthesis of Compound (1-7)] Compound (1-7), a specific compound, was synthesized according to the following scheme.

[0137] [Chemical formula]

[0138] (Synthesis of compound (1-7-3)) Into a glass reaction vessel, compound (1-7-1) (1.0 mmol), compound (1-7-2) (4.0 mmol), triethylamine (20 mmol), and 20 mL of tetrahydrofuran were added to obtain a mixed solution. After replacing the inside of the reaction vessel with nitrogen, the mixed solution was reacted under heating under reflux for 5 hours. After allowing the mixed solution to cool to room temperature (25 °C), 40 mL of methanol was added to the mixed solution, and the precipitated precipitate was collected by filtration. The obtained solid (filtrate) was suspended in 20 mL of tetrahydrofuran, heated under reflux for 1 hour, and then collected by filtration. By drying the obtained solid (filtrate) under reduced pressure, 0.79 mmol of compound (1-7-3) was obtained. For compound (1-7-3) 1 The results of the analysis by 1H NMR (nuclear magnetic resonance method) are shown below. Compound (1-7-3): 1 1H NMR (DMSO-d6) δ (ppm) 7.31 (2H, t, J = 7.4 Hz), 7.39 (2H, t, J = 8.9 Hz), 7.48 (2H, s), 7.67 (2H, d, J = 8.4 Hz), 7.71 (2H, d, J = 8.4 Hz), 7.78 (2H, d, J = 4.0 Hz), 8.12 (2H, d, J = 4.0 Hz), 8.22 (2H, s), 8.32 (2H, s), 10.5 (2H, s).

[0139] (Synthesis of compound (1-7-4)) To a glass reaction vessel, compound (1-7-3) (0.75 mmol), Lawesson's reagent (3.75 mmol), and 20 mL of o-dichlorobenzene were added to obtain a mixed solution. After purging the inside of the reaction vessel with nitrogen, the above mixed solution was reacted at 150 °C for 5 hours. After allowing the mixed solution to cool to room temperature (25 °C), the precipitated precipitate was collected by filtration. The obtained solid (filtrate) was suspended in 20 mL of tetrahydrofuran, heated under reflux for 1 hour, and then collected by filtration. By drying the obtained solid (filtrate) under reduced pressure, 0.60 mmol of compound (1-7-4) was obtained. Of compound (1-7-4) 1 The results of the analysis by 1H NMR are shown below. Compound (1-7-4): 1 1H NMR (DMSO-d6) δ (ppm) 7.31 (2H, t, J = 8.0 Hz), 7.37 (2H, t, J = 8.0 Hz), 7.50 (2H, s), 7.66 (2H, d, J = 8.3 Hz), 7.71 (2H, d, J = 8.3 Hz), 7.79 (2H, d, J = 4.1 Hz), 8.03 (2H, d, J = 4.1 Hz), 8.18 (2H, s) 8.37 (2H, s), 11.9 (2H, s).

[0140] (Synthesis of compound (1-7)) To a glass reaction vessel, compound (1-7-4) (0.60 mmol), cesium carbonate (2.4 mmol), and 17 mL of N,N-dimethylacetamide were added to obtain a mixed solution. After purging the inside of the reaction vessel with nitrogen, the above mixed solution was reacted at 150 °C for 5 hours. After allowing the mixed solution to cool to room temperature (25 °C), the precipitate deposited in the above mixed solution was collected by filtration. The obtained solid (filtrate) was suspended in water and then collected by filtration. After drying the obtained solid (filtrate) under reduced pressure and subjecting it to sublimation purification, 0.45 mmol of compound (1-7) was obtained. Since compound (1-7) was poorly soluble, its structure was identified by LDI-MS (soft laser desorption ionization mass spectrometry). The results of the identification are shown below. Compound (1-7): LDI-MS: 638.1 (M + )

[0141] Other specific compounds were also synthesized with reference to the above synthesis method. The specific compounds and comparative compounds used in the tests are shown below. Hereinafter, Compounds (1-1) to (1-36) and Compounds (2-1) to (2-17) are specific compounds. Hereinafter, the specific compounds and comparative compounds are collectively referred to as evaluation compounds.

[0142] [Chemical formula]

[0143] [Chemical formula]

[0144] [Chemical formula]

[0145] [Chemical formula]

[0146] [Chemical formula]

[0147] [Chemical formula]

[0148] [Dye (evaluation dye)] The dyes shown below were used as the dyes for evaluation in the fabrication of the photoelectric conversion elements described later.

[0149] [Chemical formula]

[0150] [Chemical formula]

[0151] [Chemical formula]

[0152] [n-type semiconductor material] Fullerene C60 was used as the n-type semiconductor material for evaluation in the fabrication of a photoelectric conversion element described below.

[0153] [p-type semiconductor material] The p-type semiconductor material shown below was used as the p-type semiconductor material for evaluation in the fabrication of a photoelectric conversion element described below.

[0154] [Chemical formula]

[0155] [Test] Using each of the materials shown above, the following Tests X, Y, and Z were conducted. In Test X, a photoelectric conversion film was fabricated and evaluated using a specific compound, an n-type semiconductor material, and a dye. In Test Y, a photoelectric conversion film was fabricated and evaluated using two specific compounds and a dye. In Test Z, a photoelectric conversion film was fabricated and evaluated using a specific compound, a p-type semiconductor material, and a dye.

[0156] [Test X] [Examples and Comparative Examples: Fabrication of Photoelectric Conversion Element] A photoelectric conversion element in the form of Figure 2 was fabricated using the obtained compound. Here, the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15. Specifically, amorphous ITO was deposited on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm). Further, the following compound (C-1) was deposited on the lower electrode 11 by vacuum thermal evaporation to form an electron blocking film 16A (thickness: 30 nm). Further, on the electron blocking film 16A, each component shown in each example or comparative example described in the table in the subsequent stage was co-deposited to form a photoelectric conversion film 12 which is a mixed layer. The ratio of the deposition rates of each component was adjusted so that the film thickness in terms of a single layer of each component in the photoelectric conversion film became the ratio shown in the "component ratio" column in the table. Further, the following compound (C-2) was deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). On the hole blocking film 16B, amorphous ITO was deposited by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After forming a SiO film as a sealing layer on the upper electrode 15 by vacuum evaporation, an aluminum oxide (Al2O3) layer was formed thereon by ALCVD (Atomic Layer Chemical Vapor Deposition) method, and a photoelectric conversion element of each example or comparative example was fabricated.

[0157]

Chemical formula

[0158] In the photoelectric conversion film of the example in Test X, Compounds (1-1) to (1-36) exhibit properties as a p-type semiconductor.

[0159] <Evaluation of dark current> For each of the obtained photoelectric conversion elements, the dark current was measured by the following method. A voltage was applied to the lower electrode and the upper electrode of each photoelectric conversion element so as to obtain an electric field strength of 2.5×10 5 V / cm, and the current value (dark current) in the dark was measured. Next, similarly, a voltage was applied so as to obtain an electric field strength of 7.5×10 4 V / cm, and the current value (dark current) in the dark was measured. From the following formula, the relative ratio of the dark current was calculated and evaluated according to the following criteria. Relative ratio of dark current = (Dark current at 2.5×10 5 V / cm) / (Dark current at 7.5×10 4 V / cm) A: Relative ratio of dark current is 2.0 or less B: Relative ratio of dark current is 2.0 or more and less than 2.5 C: Relative ratio of dark current is 2.5 or more and less than 3.0 D: Relative ratio of dark current is 3.0 or more and less than 3.5 E: Relative ratio of dark current is 3.5 or more

[0160] <Evaluation of Photovoltaic Conversion Efficiency (Quantum Efficiency)> The drive of each obtained photovoltaic conversion element was confirmed by the following method. A voltage was applied to each photovoltaic conversion element so that the electric field strength became 7.5×10 4 V / cm. Then, light was irradiated from the upper electrode (transparent conductive film) side, and the photovoltaic conversion efficiency (external quantum efficiency) in the visible light region (400 - 700 nm) was evaluated. Using the integrated value of the photovoltaic conversion efficiency at 400 - 700 nm, the relative ratio of the integrated value of the photovoltaic conversion efficiency was calculated from Equation (S) and evaluated according to the following criteria. Equation (S): Relative ratio = (Integrated value of the photovoltaic conversion efficiency at 400 - 700 nm of the photovoltaic conversion element to be evaluated) / (Integrated value of the photovoltaic conversion efficiency at 400 - 700 nm of the photovoltaic conversion element of Example 1-1) A: Relative ratio of the integrated value of the photovoltaic conversion efficiency is 1.4 or more B: Relative ratio of the integrated value of the photovoltaic conversion efficiency is 1.2 or more and less than 1.4 C: Relative ratio of the integrated value of the photovoltaic conversion efficiency is 1.0 or more and less than 1.2 D: Relative ratio of the integrated value of the photovoltaic conversion efficiency is 0.8 or more and less than 1.0 E: Relative ratio of the integrated value of the photovoltaic conversion efficiency is less than 0.8

[0161] <Evaluation of the Dependence of Photovoltaic Conversion Efficiency on Electric Field Strength> The dependence of the quantum efficiency on the electric field strength of each obtained photovoltaic conversion element was confirmed by the following method. A voltage of 7.5×10 was applied to each photovoltaic conversion element 4A voltage was applied so that the electric field strength became V / cm. Then, light was irradiated from the upper electrode (transparent conductive film) side, and the photoelectric conversion efficiency (external quantum efficiency) in the visible light region (400 to 700 nm) was evaluated. Furthermore, a voltage was applied to each photoelectric conversion element so that the electric field strength became 2.5×10 5 V / cm. Then, light was irradiated from the upper electrode (transparent conductive film) side, and the photoelectric conversion efficiency (external quantum efficiency) in the visible light region (400 to 700 nm) was evaluated. Using the integrated value of the photoelectric conversion efficiency at 400 to 700 nm measured at each electric field strength, the photoelectric conversion efficiency ratio was calculated from the following formula, and the electric field strength dependence of the photoelectric conversion efficiency was evaluated according to the following criteria. Photoelectric conversion efficiency ratio = (Integrated value of the photoelectric conversion efficiency at 400 to 700 nm under the condition that a voltage is applied so that the electric field strength becomes 7.5×10 4 V / cm) / (Integrated value of the photoelectric conversion efficiency at 400 to 700 nm under the condition that a voltage is applied to the photoelectric conversion element to be evaluated so that the electric field strength becomes 2.5×10 5 V / cm) A: The photoelectric conversion efficiency ratio is 0.9 or more B: The photoelectric conversion efficiency ratio is 0.8 or more and less than 0.9 C: The photoelectric conversion efficiency ratio is 0.7 or more and less than 0.8 D: The photoelectric conversion efficiency ratio is 0.6 or more and less than 0.7 E: The photoelectric conversion efficiency ratio is less than 0.6

[0162] <Results of Test X> The characteristics of the photoelectric conversion elements of each example or comparative example in this test (Test X), and the results of the tests conducted using the photoelectric conversion elements of each example or comparative example are shown in Table 1 below. In addition, in the table, the "Formula" column indicates which compound the evaluation compound corresponds to among the compounds represented by the above formulas. For example, the evaluation compound 1-1 used in Example 1-1 corresponds to the compound represented by Formula (16).

[0163]

Table 1

[0164]

Table 2

[0165] From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention using a photoelectric conversion film containing a specific compound has excellent effects of the present invention.

[0166] Among them, Y 41 ~Y 42 and Y 81 ~Y 85 being -CR= and R being a hydrogen atom, the compound represented by the above formula (16), Y 41 ~Y 42 and Y 111 ~Y 115 being -CR= and R being a hydrogen atom, the compound represented by the above formula (17), Y 21 ~Y 24 and Y 111 ~Y 115 being -CR= and R being a hydrogen atom, the compound represented by the above formula (21), Y 21 ~Y 24 and Y 151 ~Y 157 being -CR= and R being a hydrogen atom, the compound represented by the above formula (22), Y 61 ~Y 62 and Y 81 ~Y 85 being -CR= and R being a hydrogen atom, the compound represented by the above formula (24), Y 51 ~Y 54 and Y 81 ~Y 85 being -CR= and R being a hydrogen atom, the compound represented by the above formula (27), Y 151 ~Y 157 being -CR= and R being a hydrogen atom, the compound represented by the above formula (28), Y 41 ~Y 42 and Y 91 ~Y 97 being -CR= and R being a hydrogen atom, the above formula (44), Y 51 ~Y 54 and Y 81 ~Y85 The compound represented by the above formula (45) wherein -CR= and R is a hydrogen atom, Y 21 ~Y 24 Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (46) wherein -CR= and R is a hydrogen atom, Y 471 ~Y 475 The compound represented by the above formula (54) wherein -CR= and R is a hydrogen atom, Y 481 ~Y 485 The compound represented by the above formula (55) wherein -CR= and R is a hydrogen atom, Y 491 ~Y 497 The compound represented by the above formula (56) wherein -CR= and R is a hydrogen atom, Y 501 ~Y 505 The compound represented by the above formula (57) wherein -CR= and R is a hydrogen atom, Y 511 ~Y 515 The compound represented by the above formula (58) wherein -CR= and R is a hydrogen atom, Y 521 ~Y 528 The compound represented by the above formula (59) wherein -CR= and R is a hydrogen atom, or Y 531 ~Y 539 When it is the compound represented by the above formula (59) wherein -CR= and R is a hydrogen atom (Examples 1-1 to 1-33, Examples 1-46 to 1-47, Examples 1-52 to 1-58), the effect was more excellent.

[0167] 〔Test Y〕 <Examples and Comparative Examples: Fabrication of Photoelectric Conversion Element> In the same manner as in Test X, a photoelectric conversion element of each example or comparative example was fabricated. In the photoelectric conversion film of the example in Test Y, Compound (1-7) exhibits properties as a p-type semiconductor, and Compounds (2-1) to (2-17) exhibit properties as n-type semiconductors.

[0168] <Evaluation of Dark Current> For each of the obtained photoelectric conversion elements, the dark current was measured by the following method. A voltage was applied to the lower electrode and the upper electrode of each photoelectric conversion element so that the electric field strength became 2.5×10 5 V / cm, and the current value in the dark (dark current) was measured. As a result, in any of the photoelectric conversion elements, the dark current was 50 nA / cm 2 or less, and it was confirmed that a sufficiently low dark current was exhibited.

[0169] <Evaluation of photoelectric conversion efficiency (quantum efficiency)> In the same manner as in Test X, the photoelectric conversion efficiency (quantum efficiency) of each obtained photoelectric conversion element was evaluated. However, in this test (Test Y), the following formula was adopted as Formula (S). Formula (S): Relative ratio = (Integrated value of the photoelectric conversion efficiency of the photoelectric conversion element to be evaluated at 400 to 700 nm) / (Integrated value of the photoelectric conversion efficiency of the photoelectric conversion element of Example 2-1 at 400 to 700 nm)

[0170] <Evaluation of the dependence of photoelectric conversion efficiency on electric field strength> In the same manner as in Test X, the dependence of the photoelectric conversion efficiency on the electric field strength of each obtained photoelectric conversion element was evaluated. However, the applied voltage was 2.0×10 5 V / cm and 2.5×10 5 V / cm, and the photoelectric conversion efficiency ratio was calculated by the following formula. Photoelectric conversion efficiency ratio =(Integrated value of the photoelectric conversion efficiency at 400 to 700 nm under the condition that a voltage is applied so that the electric field strength becomes 2.0×10 5 V / cm) / (Integrated value of the photoelectric conversion efficiency at 400 to 700 nm under the condition that a voltage is applied to the photoelectric conversion element to be evaluated so that the electric field strength becomes 2.5×10 5 V / cm)

[0171] <Results of Test Y> The characteristics of the photoelectric conversion elements of each example or comparative example in this test (Test Y), and the results of the tests conducted using the photoelectric conversion elements of each example or comparative example are shown in Table 2 below. The "Formula" column in Table 2 indicates which formula the compound described in Evaluation Compound No. 1 corresponds to.

[0172]

Table 3

[0173] From the results shown in Table 2, it was confirmed that even when using a photoelectric conversion film containing two specific compounds, the photoelectric conversion element of the present invention has excellent effects of the present invention.

[0174] Among them, the specific compound used as the n-type material (the compound described in the "Evaluation Compound No. 1" column) has an aromatic ring group containing a group with -N= in the ring structure as Ar 11 and Ar 12 satisfies at least one of the requirements that n15 and n16 are 1, and Ar 15 and Ar 16 is a group represented by formula (8) in which Y 81 ~Y 85 is -CF=, -C(CN)―, or -N=, and it was confirmed that the effects of the present invention are more excellent (see the results of Examples 2-3, 2-7, 2-9, 2-10, 2-12 to 2-17, etc.).

[0175] 〔Test Z〕 <Examples and Comparative Examples: Fabrication of Photoelectric Conversion Elements> In the same manner as in Test X, photoelectric conversion elements of each example or comparative example were fabricated. In addition, in the photoelectric conversion film of the examples in Test Z, Compounds (2-1) to (2-17) exhibit properties as an n-type material.

[0176] <Evaluation of Dark Current> In the same manner as in Test Y, the dark current of each obtained photoelectric conversion element was evaluated. As a result, in any of the photoelectric conversion elements, the dark current was 50 nA / cm 2 or less, and it was confirmed that a sufficiently low dark current was shown.

[0177] <Evaluation of Photovoltaic Conversion Efficiency (Quantum Efficiency)> In the same manner as in Test X, the photovoltaic conversion efficiency (quantum efficiency) of each obtained photovoltaic conversion element was evaluated. However, in this test (Test Z), the following formula was adopted as formula (S). Formula (S): Relative ratio = (Integrated value of the photovoltaic conversion efficiency of the photovoltaic conversion element to be evaluated at 400 to 700 nm) / (Integrated value of the photovoltaic conversion efficiency of the photovoltaic conversion element of Example 3-1 at 400 to 700 nm)

[0178] <Evaluation of the Dependence of Photovoltaic Conversion Efficiency on Electric Field Strength> In the same manner as in Test Y, the dependence of the photovoltaic conversion efficiency on the electric field strength of each obtained photovoltaic conversion element was evaluated.

[0179] <Results of Test Z> The characteristics of the photovoltaic conversion elements of each example or comparative example in this test (Test Z), and the results of the tests conducted using the photovoltaic conversion elements of each example or comparative example are shown in Table 3 below.

[0180]

Table 4

[0181] From the results shown in Table 3, even when using a photovoltaic conversion film containing a specific compound and a p-type semiconductor material, it was confirmed that the photovoltaic conversion element of the present invention has excellent effects of the present invention.

[0182] Among them, the specific compound used as the n-type material has an aromatic ring group containing a group with -N= in the ring structure as Ar 11 and Ar 12 and satisfies at least one of the requirements that n15 and n16 are 1, and Ar 15 and Ar 16 is Y 81 ~Y 85When the group represented by the formula (8) is -CF=, -C(CN)=, or -N=, it was confirmed that the effects of the present invention are more excellent (see the results of Examples 3-8, 3-12, 3-14, 3-15, 3-17 to 3-22, etc.).

Explanation of symbols

[0183] 10a, 10b Photoelectric conversion element 11 Conductive film (lower electrode) 12 Photoelectric conversion film 15 Transparent conductive film (upper electrode) 16A Electron blocking film 16B Hole blocking film

Claims

1. A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1). 【Chemical 1】 In formula (1), X １１ and X １２ each independently represents a sulfur atom or an oxygen atom. Ar １１ ~Ar １６ each independently represents a monocyclic, bicyclic, or tricyclic aromatic ring group. The aromatic ring group may have, as a substituent, one or more groups selected from the group consisting of a halogen atom, a cyano group, and a trifluoromethyl group. X １３ and X １４ each independently represents an oxygen atom or a sulfur atom. n11 to n16 each independently represent 0 or 1. However, when all of n11 to n16 are 0 and n17 is 1, Ar １５ and Ar １６ is the tricyclic aromatic ring group. n17 represents 1 or 2. n18 represents 1 or 2.

2. Ar １１ ~Ar １４ The photoelectric conversion element according to claim 1, wherein Ar and ~Ar are each independently a group represented by any one of formulas (2) to (7). 【Chemical Formula 2】 In formulas (2) to (7), * represents a bonding position. Y ２１ to Y ２４ , Y ３１ to Y ３６ , Y ４１ to Y ４２ , Y ５１ to Y ５４ , Y ６１ to Y ６２ , and, Y ７１ each independently represents -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. X ４１ , X ５１ , X ６１ ~X ６２ , and X ７１ each independently represents a sulfur atom, an oxygen atom, or a selenium atom.

3. Ar １５ ~Ar １６ The photoelectric conversion element according to claim 1 or 2, wherein Ar and ~Ar are each independently a group represented by any one of formula (8) to formula (15) and formula (47) to formula (53). [Chemical Formula 3] 【Chemical Formula 4】 In formulas (8) to (15) and formulas (47) to (53), * represents a bonding position. Y ８１ ~Y ８５ 、Y ９１ ~Y ９７ 、Y １０１ ~Y １０３ 、Y １１１ ~Y １１５ 、Y １２１ ~Y １２３ 、Y １３１ ~Y １３７ 、Y １４１ ~Y １４５ 、Y １５１ ~Y １５７ 、Y ４７１ ~Y ４７５ 、Y ４８１ ~Y ４８５ 、Y ４９１ ~Y ４９７ 、Y ５０１ ~Y ５０５ 、Y ５１１ ~Y ５１５ 、Y ５２１ ~Y ５２９ 、and Y ５３１ ~Y ５３９ each independently represents -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. X １０１ 、 X １１１ 、 X １２１ ~ X １２２ 、 X １４１ 、 X １５１ 、 X ４７１ ~ X ４７２ 、 X ４８１ ~ X ４８２ 、 X ４９１ 、 X ５０１ ~ X ５０２ 、 and X ５１１ ~ X ５１２ each independently represents a sulfur atom, an oxygen atom, or a selenium atom.

4. The photoelectric conversion element according to any one of Claims 1 to 3, wherein n11 to n12 represent 1, n13 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

5. The photoelectric conversion element according to any one of Claims 1 to 3, wherein n11 to n14 represent 1, n15 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

6. The photoelectric conversion element according to any one of Claims 1 to 3, wherein n11 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

7. The photoelectric conversion element according to any one of Claims 1 to 3, wherein n11 to n12 represent 1, n13 to n14 represent 0, n15 to n16 represent 1, n17 represents 1, and n18 represents 1 or 2.

8. The photoelectric conversion element according to any one of Claims 1 to 3, wherein n11 to n14 represent 0, n15 to n16 each independently represent 0 or 1, n17 represents 2, and n18 represents 1.

9. The photoelectric conversion element according to any one of Claims 1 to 3, wherein the compound represented by formula (1) is a compound represented by any of formulas (16) to (46) and formulas (54) to (60). 【Chemical Formula 5】 【Chemical Formula 6】 【Chemical Formula 7】 【Chemical Formula 8】 【Chemical Formula 9】 【Chemical 10】 【Chemical Formula 11】 【Chemical 12】 【Chemical 13】 In formulas (16) to (46) and formulas (54) to (60), Y ２１ to Y ２４ 、Y ４１ to Y ４２ 、Y ５１ to Y ５４ 、Y ６１ to Y ６２ 、Y ７１ 、Y ８１ to Y ８５ 、Y ９１ to Y ９７ 、Y １０１ to Y １０３ 、Y １１１ to Y １１５ 、Y １２１ to Y １２３ 、Y １５１ to Y １５７ 、Y ４７１ to Y ４７５ 、Y ４８１ to Y ４８５ 、Y ４９１ to Y ４９７ 、Y ５０１ to Y ５０５ 、Y ５１１ to Y ５１５ 、Y ５２１ to Y ５２８ 、and Y ５３１ to Y ５３９ each independently represents -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. X １１ to X １４ each independently represents a sulfur atom or an oxygen atom. X ４１ 、 X ５１ 、 X ６１ ~X ６２ 、 X ７１ 、 X １０１ 、 X １１１ 、 X １２１ ~X １２２ 、 X １５１ 、 X ４７１ 、 X ４８１ ~X ４８２ 、 X ４９１ 、 X ５０１ ~X ５０２ 、 and X ５１１ ~X ５１２ each independently represents a sulfur atom, an oxygen atom, or a selenium atom.

10. The compound represented by the formula (1) is Y ４１ ~Y ４２ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (16) where R is a hydrogen atom, Y ４１ ~Y ４２ and Y １１１ ~Y １１５ is -CR=, and the compound represented by the formula (17) where R is a hydrogen atom, Y ２１ ~Y ２４ and Y １１１ ~Y １１５ is -CR=, and the compound represented by the formula (21) where R is a hydrogen atom, Y ２１ ~Y ２４ and Y １５１ ~Y １５７ is -CR=, and the compound represented by the formula (22) where R is a hydrogen atom, Y ６１ ~Y ６２ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (24) where R is a hydrogen atom, Y ５１ ~Y ５４ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (27) where R is a hydrogen atom, Y １５１ ~Y １５７ is -CR=, and the compound represented by the formula (28) where R is a hydrogen atom, Y ４１ ~Y ４２ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (29) where R is a hydrogen atom, Y ４１ ~Y ４２ and Y ９１ ~Y ９７ is -CR=, and the compound represented by the formula (44) where R is a hydrogen atom, Y ５１ ~Y ５４ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (45) where R is a hydrogen atom, Y ２１ ~Y ２４ , Y ４１ ~Y ４２ and Y ８１ ~Y ８５ The compound represented by the formula (46) wherein Y is -CR= and R is a hydrogen atom, Y ４７１ ~Y ４７５ The compound represented by the formula (54) wherein Y is -CR= and R is a hydrogen atom, Y ４８１ ~Y ４８５ The compound represented by the formula (55) wherein Y is -CR= and R is a hydrogen atom, Y ４９１ ~Y ４９７ The compound represented by the formula (56) wherein Y is -CR= and R is a hydrogen atom, Y ５０１ ~Y ５０５ The compound represented by the formula (57) wherein Y is -CR= and R is a hydrogen atom, Y ５１１ ~Y ５１５ The compound represented by the formula (58) wherein Y is -CR= and R is a hydrogen atom, Y ５２１ ~Y ５２８ The compound represented by the formula (59) wherein Y is -CR= and R is a hydrogen atom, or Y ５３１ ~Y ５３９ The photoelectric conversion element according to claim 9, which is the compound represented by the formula (59) wherein Y is -CR= and R is a hydrogen atom.

11. The photoelectric conversion element according to Claim 9, wherein the compound represented by formula (1) is a compound represented by any of formula (16), formula (31), formula (32), formula (35), formula (37), formula (39), and formula (42).

12. X １１ and X １２ The photoelectric conversion device according to any one of claims 1 to 11, wherein X and X represent sulfur atoms.

13. The photoelectric conversion element according to any one of claims 1 to 12, wherein the photoelectric conversion film further contains an n-type semiconductor material.

14. The photoelectric conversion element according to claim 13, wherein the n-type semiconductor material contains fullerenes selected from the group consisting of fullerene and its derivatives.

15. The photoelectric conversion element according to any one of claims 1 to 14, wherein the photoelectric conversion film further contains a p-type semiconductor material.

16. The photoelectric conversion element according to any one of claims 1 to 15, wherein the photoelectric conversion film contains two kinds of compounds represented by the formula (1).

17. The photoelectric conversion element according to any one of claims 1 to 16, wherein the photoelectric conversion film further contains a dye.

18. The photoelectric conversion element according to any one of claims 1 to 17, having one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.

19. An imaging device having the photoelectric conversion element according to any one of claims 1 to 18.

20. An optical sensor having the photoelectric conversion element according to any one of claims 1 to 18.

21. A compound represented by the formula (1). 【Chemical 14】 In formula (1), X １１ and X １２ each independently represents a sulfur atom or an oxygen atom. Ar １１ ~Ar １６ Each independently represents a monocyclic, bicyclic, or tricyclic aromatic ring group. The aromatic ring group may have, as a substituent, one or more groups selected from the group consisting of a halogen atom, a cyano group, and a trifluoromethyl group. X １３ and X １４ each independently represents an oxygen atom or a sulfur atom. n11 to n16 each independently represent 0 or 1. However, when all of n11 to n16 are 0 and n17 is 1, Ar １５ and Ar １６ are the tricyclic aromatic ring groups described above. n17 represents 1 or 2. n18 represents 1 or 2.

22. Ar １１ ~Ar １４ The compound according to claim 21, wherein Ar and ~Ar are each independently a group represented by any one of formulas (2) to (7). 【Chemical 15】 In the formulas (2) to (7), * represents the bonding position. Y ２１ ~Y ２４ 、Y ３１ ~Y ３６ 、Y ４１ ~Y ４２ 、Y ５１ ~Y ５４ 、Y ６１ ~Y ６２ 、and Y ７１ each independently represents -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. X ４１ , X ５１ , X ６１ ~X ６２ , and X ７１ each independently represents a sulfur atom, an oxygen atom, or a selenium atom.

23. Ar １５ ~Ar １６ The compound according to claim 21 or 22, wherein Ar and ~Ar are each independently a group represented by any one of formulas (8) to (15) and formulas (47) to (53). 【Chemical 16】 【Chemical 17】 In the formulas (8) to (15) and the formulas (47) to (53), * represents the bonding position. Y ８１ ~Y ８５ 、Y ９１ ~Y ９７ 、Y １０１ ~Y １０３ 、Y １１１ ~Y １１５ 、Y １２１ ~Y １２３ 、Y １３１ ~Y １３７ 、Y １４１ ~Y １４５ 、Y １５１ ~Y １５７ 、Y ４７１ ~Y ４７５ 、Y ４８１ ~Y ４８５ 、Y ４９１ ~Y ４９７ 、Y ５０１ ~Y ５０５ 、Y ５１１ ~Y ５１５ 、Y ５２１ ~Y ５２８ 、and, Y ５３１ ~Y ５３９ each independently represents -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. X １０１ 、 X １１１ 、 X １２１ ~ X １２２ 、 X １４１ 、 X １５１ 、 X ４７１ 、 X ４８１ ~ X ４８２ 、 X ４９１ 、 X ５０１ ~ X ５０２ 、 and X ５１１ ~ X ５１２ each independently represents a sulfur atom, an oxygen atom, or a selenium atom.

24. The compound according to any one of claims 21 to 23, wherein n11 to n12 represent 1, n13 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

25. The compound according to any one of claims 21 to 23, wherein n11 to n14 represent 1, n15 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

26. The compound according to any one of claims 21 to 23, wherein n11 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

27. The compound according to any one of claims 21 to 23, wherein n11 to n12 represent 1, n13 to n14 represent 0, n15 to n16 represent 1, n17 represents 1, and n18 represents 1 or 2.

28. The compound according to any one of claims 21 to 23, wherein n11 to n14 represent 0, n15 to n16 each independently represent 0 or 1, n17 represents 2, and n18 represents 1.

29. The compound according to any one of claims 21 to 23, wherein the compound represented by the formula (1) is a compound represented by any one of the formulas (16) to (46) and the formulas (54) to (60). 【Chemical 18】 【Chemical 19】 【Chemical 20】 【Chemical 21】 【Chemical formula 22】 【Chemical 23】 【Chemical 24】 ​ 【Chemical 26】 In Formula (16) to Formula (46) and Formula (54) to Formula (60), Y ２１ to Y ２４ 、Y ４１ to Y ４２ 、Y ５１ to Y ５４ 、Y ６１ to Y ６２ 、Y ７１ 、Y ８１ to Y ８５ 、Y ９１ to Y ９７ 、Y １０１ to Y １０３ 、Y １１１ to Y １１５ 、Y １２１ to Y １２３ 、Y １５１ to Y １５７ 、Y ４７１ to Y ４７５ 、Y ４８１ to Y ４８５ 、Y ４９１ to Y ４９７ 、Y ５０１ to Y ５０５ 、Y ５１１ to Y ５１５ 、Y ５２１ to Y ５２８ 、and Y ５３１ to Y ５３９ each independently represents -CR= or a nitrogen atom. R represents a hydrogen atom, a halogen atom, a cyano group, or a trifluoromethyl group. X １１ to X １４ each independently represents a sulfur atom or an oxygen atom. X ４１ 、 X ５１ 、 X ６１ ~ X ６２ 、 X ７１ 、 X １０１ 、 X １１１ 、 X １２１ ~ X １２２ 、 X １５１ 、 X ４７１ 、 X ４８１ ~ X ４８２ 、 X ４９１ 、 X ５０１ ~ X ５０２ 、 and X ５１１ ~ X ５１２ each independently represents a sulfur atom, an oxygen atom, or a selenium atom.

30. The compound represented by the formula (1) is Y ４１ ~Y ４２ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (16) wherein R is a hydrogen atom, Y ４１ ~Y ４２ and Y １１１ ~Y １１５ is -CR=, and the compound represented by the formula (17) wherein R is a hydrogen atom, Y ２１ ~Y ２４ and Y １１１ ~Y １１５ is -CR=, and the compound represented by the formula (21) wherein R is a hydrogen atom, Y ２１ ~Y ２４ and Y １５１ ~Y １５７ is -CR=, and the compound represented by the formula (22) wherein R is a hydrogen atom, Y ６１ ~Y ６２ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (24) wherein R is a hydrogen atom, Y ５１ ~Y ５４ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (27) wherein R is a hydrogen atom, Y １５１ ~Y １５７ is -CR=, and the compound represented by the formula (28) wherein R is a hydrogen atom, Y ４１ ~Y ４２ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (29) wherein R is a hydrogen atom, Y ４１ ~Y ４２ and Y ９１ ~Y ９７ is -CR=, and the compound represented by the formula (44) wherein R is a hydrogen atom, Y ５１ ~Y ５４ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (45) wherein R is a hydrogen atom, Y ２１ ~Y ２４ , Y ４１ ~Y ４２ and Y ８１ ~Y ８５ is -CR=, and the compound represented by the formula (46) wherein R is a hydrogen atom, Y ４７１ ~Y ４７５ is -CR=, and the compound represented by the formula (54) wherein R is a hydrogen atom, Y ４８１ ~Y ４８５ is -CR=, and the compound represented by the formula (55) wherein R is a hydrogen atom, Y ４９１ ~Y ４９７ is -CR=, and the compound represented by the formula (56) wherein R is a hydrogen atom, Y ５０１ ~Y ５０５ is -CR=, and the compound represented by the formula (57) wherein R is a hydrogen atom, Y ５１１ ~Y ５１５ is -CR=, and the compound represented by the formula (58) wherein R is a hydrogen atom, Y ５２１ ~Y ５２８ is -CR=, and the compound represented by the formula (59) wherein R is a hydrogen atom, or, Y ５３１ ~Y ５３９ is -CR=, and the compound represented by the formula (59) wherein R is a hydrogen atom, the compound according to claim 29.

31. The compound according to claim 29, wherein the compound represented by the formula (1) is a compound represented by any one of the formula (16), the formula (31), the formula (32), the formula (35), the formula (37), the formula (39), and the formula (42).

32. X １１ and X １２ The compound according to any one of claims 21 to 31, wherein X represents a sulfur atom.

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