Photoelectric conversion elements, imaging elements, optical sensors, and compounds

Abstract

The present invention provides a photoelectric conversion element, an imaging element, a photosensor, and a compound having excellent photoelectric conversion efficiency. The photoelectric conversion element of the present invention comprises, in order, a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein the photoelectric conversion film comprises a compound represented by formula (1).

Description

Technical Field

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

[0002] In recent years, development of devices (for example, imaging devices) having a photoelectric conversion film has been underway.

[0003] For example, Patent Document 1 discloses a photoelectric conversion element for an imaging element including a photoelectric conversion section having one or more organic thin film layers containing a predetermined compound.

[0004] Previous technical literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application No. 2018-170487 Summary of the Invention

[0007] Technical issues to be solved by the invention

[0008] In recent years, as there has been a demand for improved performance of image pickup elements, optical sensors, and the like, there has been a demand for further improvement in various characteristics required of photoelectric conversion elements used therein.

[0009] For example, it is required to further improve the photoelectric conversion efficiency of the photoelectric conversion element.

[0010] The present inventors have studied a photoelectric conversion element using the compound disclosed in Patent Document 1 and have confirmed that the photoelectric conversion efficiency of this photoelectric conversion element (for example, the photoelectric conversion efficiency for light with a wavelength of 400 to 550 nm) can be improved.

[0011] In view of the above-mentioned actual situation, an object of the present invention is to provide a photoelectric conversion element having excellent photoelectric conversion efficiency.

[0012] Furthermore, another object of the present invention is to provide an imaging element, a photosensor, and a compound related to the above-mentioned photoelectric conversion element.

[0013] Means for solving technical problems

[0014] The present inventors have conducted intensive studies on the above-mentioned problems and, as a result, have found that the above-mentioned problems can be solved by the following structure, thereby completing the present invention.

[0015] [1]

[0016] A photoelectric conversion element comprises a conductive film, a photoelectric conversion film and a transparent conductive film in this order, wherein:

[0017] The above-mentioned photoelectric conversion film contains the compound represented by formula (1).

[0018] [Chemical Formula 1]

[0019]

[0020] In formula (1), n11 represents 1 or 2.

[0021] n12 and n13 each independently represent 0 or 1. However, at least one of n12 and n13 represents 1.

[0022] Ar 11 It represents a fused polycyclic aromatic ring group composed of a combination of one or more aromatic rings selected from the group consisting of a thiophene ring, a benzene ring, a furan ring, and a selenophene ring, wherein the number of rings in the fused polycyclic aromatic ring group is 3 to 4. The fused polycyclic aromatic ring group may have a substituent.

[0023] Ar 14 and Ar 15 Each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent.

[0024] Ar 12 and Ar 13 Each independently represents any one of the groups represented by formula (2) to formula (4).

[0025] [Chemical Formula 2]

[0026]

[0027] In formula (2) to formula (4), * A and* B Indicates the bonding position.

[0028] In formula (2), X 21 and X 22 Each independently represents a sulfur atom, an oxygen atom or a selenium atom. 21 and Y 22 Each independently represents a nitrogen atom or -CR=. R represents a hydrogen atom or a substituent, wherein Y 21 and Y 22 At least one of represents a nitrogen atom.

[0029] In formula (3), X 31 represents a sulfur atom, an oxygen atom or a selenium atom. 31 ~Y 34 Each independently represents a nitrogen atom or -CR=. R represents a hydrogen atom or a substituent.

[0030] In formula (4), X 41represents a sulfur atom, an oxygen atom or a selenium atom. 41 ~Y 43 Each independently represents a nitrogen atom or -CR=. R represents a hydrogen atom or a substituent.

[0031] [2]

[0032] The photoelectric conversion element according to [1], wherein in the above formula (1), Ar 11 The group represented is any one of the groups represented by formula (A1) to formula (A6).

[0033] [Chemical Formula 3]

[0034]

[0035] In formulae (A1) to (A6), * represents a bonding position.

[0036] In formula (A1), Z 11 and Z 12 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 11 and Z 12 The other one in Z represents -CR=. 13 and Z 14 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 13 and Z 14 The other one in represents -CR=. R and R A Each independently represents a hydrogen atom or a substituent.

[0037] In formula (A2), Z 21 ~Z 23 R each independently represents a sulfur atom, an oxygen atom or a selenium atom. A represents a hydrogen atom or a substituent.

[0038] In formula (A3), Z 31 and Z 32 R each independently represents a sulfur atom, an oxygen atom or a selenium atom. A represents a hydrogen atom or a substituent.

[0039] In formula (A4), Z 41 and Z 42 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 41 and Z 42 The other one in Z represents -CR=. 43 and Z 44 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 43 and Z 44 The other one in represents -CR=. R and R AEach independently represents a hydrogen atom or a substituent.

[0040] In formula (A5), Z 51 and Z 52 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 51 and Z 52 The other one in Z represents -CR=. 53 and Z 54 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 53 and Z 54 The other one in represents -CR=. R and R A Each independently represents a hydrogen atom or a substituent.

[0041] In formula (A6), Z 61 ~Z 64 R each independently represents a sulfur atom, an oxygen atom or a selenium atom. A represents a hydrogen atom or a substituent.

[0042] 〔3〕

[0043] The photoelectric conversion element according to [2], wherein in the above formula (A1), Z 11 and Z 12 One of them represents a sulfur atom or an oxygen atom, Z 11 and Z 12 The other one in represents -CR=,

[0044] Z 13 and Z 14 One of them represents a sulfur atom or an oxygen atom, Z 13 and Z 14 The other one in represents -CR=,

[0045] In the above formula (A2), Z 21 ~Z 23 each independently represents a sulfur atom or an oxygen atom,

[0046] In the above formula (A3), Z 31 and Z 32 each independently represents a sulfur atom or an oxygen atom,

[0047] In the above formula (A4), Z 41 and Z 42 One of them represents a sulfur atom or an oxygen atom, Z 41 and Z 42 The other one in represents -CR=,

[0048] Z 43 and Z 44 One of them represents a sulfur atom or an oxygen atom, Z 43 and Z44 The other one in represents -CR=,

[0049] In the above formula (A5), Z 51 and Z 52 One of them represents a sulfur atom or an oxygen atom, Z 51 and Z 52 The other one in represents -CR=,

[0050] Z 53 and Z 54 One of them represents a sulfur atom or an oxygen atom, Z 53 and Z 54 The other one in represents -CR=,

[0051] In the above formula (A6), Z 61 ~Z 64 Each independently represents a sulfur atom or an oxygen atom.

[0052] [4]

[0053] The photoelectric conversion element according to [2] or [3], wherein in the above formula (1), n11 is 1, Ar 11 It is a group represented by the above-mentioned formula (A5).

[0054] 〔5〕

[0055] The photoelectric conversion element according to any one of [1] to [4], wherein in the above formula (2), X 21 and X 22 each independently represents a sulfur atom or an oxygen atom,

[0056] In the above formula (3), X 31 represents a sulfur atom or an oxygen atom,

[0057] In the above formula (4), X 41 represents a sulfur atom or an oxygen atom.

[0058] [6]

[0059] The photoelectric conversion element according to any one of [1] to [5], wherein in the above formula (1), Ar 12 and Ar 13 Each independently represents any one of the groups represented by formula (5) to formula (13).

[0060] [Chemical Formula 4]

[0061]

[0062] In formulas (5) to (13), * A and* B Indicates the bonding position.

[0063] R A represents a hydrogen atom or a substituent.

[0064] [7]

[0065] The photoelectric conversion element according to any one of [1] to [6], wherein the compound represented by the above formula (1) has a molecular weight of 550 to 1200.

[0066] 〔8〕

[0067] The photoelectric conversion element according to any one of [1] to [7], wherein the photoelectric conversion film further contains a pigment.

[0068] The photoelectric conversion film is a mixed layer formed in a state where the compound represented by the above formula (1) and the above dye are mixed.

[0069] 〔9〕

[0070] The photoelectric conversion element according to any one of [1] to [8], wherein the photoelectric conversion film further contains an n-type semiconductor material.

[0071]

[10]

[0072] The photoelectric conversion element according to [9], wherein the n-type semiconductor material contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.

[0073]

[11]

[0074] The photoelectric conversion element according to any one of [1] to

[10] further comprises one or more intermediate layers between the conductive film and the transparent conductive film in addition to the photoelectric conversion film.

[0075]

[12]

[0076] An imaging element comprising the photoelectric conversion element according to any one of [1] to

[11] .

[0077]

[13]

[0078] A photosensor having the photoelectric conversion element described in any one of [1] to

[11] .

[0079]

[14]

[0080] A compound represented by formula (1).

[0081] [Chemical Formula 5]

[0082]

[0083] In formula (1), n11 represents 1 or 2.

[0084] n12 and n13 each independently represent 0 or 1. However, at least one of n12 and n13 represents 1.

[0085] Ar 11 It represents a fused polycyclic aromatic ring group composed of a combination of one or more aromatic rings selected from the group consisting of a thiophene ring, a benzene ring, a furan ring, and a selenophene ring, wherein the number of rings in the fused polycyclic aromatic ring group is 3 to 4. The fused polycyclic aromatic ring group may have a substituent.

[0086] Ar 14 and Ar 15 Each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent.

[0087] Ar 12 and Ar 13 Each independently represents any one of the groups represented by formula (2) to formula (4).

[0088] [Chemical Formula 6]

[0089]

[0090] In formulas (2) to (4), * A and* B Indicates the bonding position.

[0091] In formula (2), X 21 and X 22 Each independently represents a sulfur atom, an oxygen atom or a selenium atom. 21 and Y 22 Each independently represents a nitrogen atom or -CR=. R represents a hydrogen atom or a substituent. 21 and Y 22 At least one of represents a nitrogen atom.

[0092] In formula (3), X 31 represents a sulfur atom, an oxygen atom or a selenium atom. 31 ~Y 34 Each independently represents a nitrogen atom or -CR=. R represents a hydrogen atom or a substituent.

[0093] In formula (4), X 41 represents a sulfur atom, an oxygen atom or a selenium atom. 41 ~Y 43 Each independently represents a nitrogen atom or -CR=. R represents a hydrogen atom or a substituent.

[0094]

[15]

[0095] The compound according to

[14] , wherein in the above formula (1), Ar 11 The group represented is any one of the groups represented by formula (A1) to formula (A6).

[0096] [Chemical Formula 7]

[0097]

[0098] In formulae (A1) to (A6), * represents a bonding position.

[0099] In formula (A1), Z 11 and Z 12 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 11 and Z 12 The other one in Z represents -CR=. 13 and Z 14 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 13 and Z 14 The other one in represents -CR=. R and R A Each independently represents a hydrogen atom or a substituent.

[0100] In formula (A2), Z 21 ~Z 23 R each independently represents a sulfur atom, an oxygen atom or a selenium atom. A represents a hydrogen atom or a substituent.

[0101] In formula (A3), Z 31 and Z 32 R each independently represents a sulfur atom, an oxygen atom or a selenium atom. A represents a hydrogen atom or a substituent.

[0102] In formula (A4), Z 41 and Z 42 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 41 and Z 42 The other one in Z represents -CR=. 43 and Z 44 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 43 and Z 44 The other one in represents -CR=. R and R A Each independently represents a hydrogen atom or a substituent.

[0103] In formula (A5), Z 51 and Z 52 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 51 and Z 52 The other one in Z represents -CR=.53 and Z 54 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 53 and Z 54 The other one in represents -CR=. R and R A Each independently represents a hydrogen atom or a substituent.

[0104] In formula (A6), Z 61 ~Z 64 R each independently represents a sulfur atom, an oxygen atom or a selenium atom. A represents a hydrogen atom or a substituent.

[0105]

[16]

[0106] The compound according to

[15] , wherein in the above formula (A1), Z 11 and Z 12 One of them represents a sulfur atom or an oxygen atom, Z 11 and Z 12 The other one in represents -CR=,

[0107] Z 13 and Z 14 One of them represents a sulfur atom or an oxygen atom, Z 13 and Z 14 The other one in represents -CR=,

[0108] In the above formula (A2), Z 21 ~Z 23 each independently represents a sulfur atom or an oxygen atom,

[0109] In the above formula (A3), Z 31 and Z 32 each independently represents a sulfur atom or an oxygen atom,

[0110] In the above formula (A4), Z 41 and Z 42 One of them represents a sulfur atom or an oxygen atom, Z 41 and Z 42 The other one in represents -CR=,

[0111] Z 43 and Z 44 One of them represents a sulfur atom or an oxygen atom, Z 43 and Z 44 The other one in represents -CR=,

[0112] In the above formula (A5), Z 51 and Z 52 One of them represents a sulfur atom or an oxygen atom, Z 51 and Z 52The other one in represents -CR=,

[0113] Z 53 and Z 54 One of them represents a sulfur atom or an oxygen atom, Z 53 and Z 54 The other one in represents -CR=,

[0114] In the above formula (A6), Z 61 ~Z 64 Each independently represents a sulfur atom or an oxygen atom.

[0115]

[17]

[0116] The compound according to

[15] or

[16] , wherein in the above formula (1), n11 is 1, Ar 11 It is a group represented by the above-mentioned formula (A5).

[0117]

[18]

[0118] The compound according to any one of

[14] to

[17] , wherein in the above formula (2), X 21 and X 22 each independently represents a sulfur atom or an oxygen atom,

[0119] In the above formula (3), X 31 represents a sulfur atom or an oxygen atom,

[0120] In the above formula (4), X 41 represents a sulfur atom or an oxygen atom.

[0121]

[19]

[0122] The compound according to any one of

[14] to

[18] , wherein in the above formula (1), Ar 12 and Ar 13 Each independently represents any one of the groups represented by formula (5) to formula (13).

[0123] [Chemical Formula 8]

[0124]

[0125] In formulas (5) to (13), * A and* B Indicates the bonding position.

[0126] R A represents a hydrogen atom or a substituent.

[0127] 〔20〕

[0128] The compound according to any one of

[14] to

[19] , wherein the molecular weight of the compound represented by the above formula (1) is 550 to 1200.

[0129] Effects of the Invention

[0130] According to the present invention, a photoelectric conversion element having excellent photoelectric conversion efficiency can be provided.

[0131] Furthermore, according to the present invention, an imaging element, a photosensor, and a compound related to the above-mentioned photoelectric conversion element can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0132] Figure 1 It is a schematic cross-sectional view showing a structural example of a photoelectric conversion element.

[0133] Figure 2 It is a schematic cross-sectional view showing a structural example of a photoelectric conversion element. DETAILED DESCRIPTION

[0134] Hereinafter, preferred embodiments of the photoelectric conversion element of the present invention will be described.

[0135] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0136] In this specification, when there are multiple identical symbols representing the type or number of groups in a formula (general formula) representing a chemical structure, unless otherwise specified, the contents of these multiple identical symbols are independent of each other, and the contents of the identical symbols may be the same or different.

[0137] Furthermore, in this specification, a numerical range expressed with “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit.

[0138] In the present specification, the hydrogen atom may be a light hydrogen atom (normal hydrogen atom) or a heavy hydrogen atom (such as a dihydrogen atom).

[0139] [Photoelectric conversion element]

[0140] The photoelectric conversion element of the present invention comprises 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) (hereinafter also referred to as "specific compound").

[0141] The mechanism by which the photoelectric conversion element of the present invention can solve the above-mentioned problems by adopting such a structure is not clear, but the present inventors speculate as follows.

[0142] That is, the specific compound has a condensed polycyclic aromatic ring group (Ar 11) that is, the parent nucleus and the aromatic or heteroaromatic group (Ar 14 and / or Ar 15 ) have a specified linking group (Ar 12 and / or Ar 13 The linking group is a fused polycyclic aromatic heterocyclic group having a structure in which predetermined 5-membered rings are fused together, or a 5-membered ring and a 6-membered ring are fused together, and the bonding position with the donor and / or acceptor is also a predetermined position.

[0143] In this manner, the donor is sandwiched between the acceptor, and by having the aforementioned predetermined linking group between the donor and the acceptor, the specific compound exhibits particularly good absorption of light with a wavelength of 400 to 550 nm. Furthermore, it is speculated that the specific compound having the aforementioned structure improves charge transport within the specific compound, between specific compounds, or between the specific compound and other components, thereby improving the photoelectric conversion efficiency of the photoelectric conversion element (particularly the photoelectric conversion efficiency for light with a wavelength of 400 to 550 nm).

[0144] Furthermore, the photoelectric conversion element of the present invention suppresses the electric field intensity dependence of the photoelectric conversion efficiency. This is presumably because the specific compound, having the aforementioned linking group, creates a packing structure within the photoelectric conversion film that facilitates charge transport, maintaining excellent charge transport even at low voltages.

[0145] Hereinafter, a case where the photoelectric conversion efficiency of the photoelectric conversion element is further improved and / or a case where the electric field intensity dependency of the photoelectric conversion efficiency is further suppressed will also be referred to as “a further improved effect of the present invention”.

[0146] Figure 1 Schematic cross-sectional view of one embodiment of the photoelectric conversion element of the present invention is shown in FIG.

[0147] Figure 1 The photoelectric conversion element 10a shown has the following structure, namely, a conductive film (hereinafter also referred to as the lower electrode) 11 serving 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 the upper electrode) 15 serving as an upper electrode are stacked in sequence.

[0148] Figure 2 Another structural example of a photoelectric conversion element is shown in FIG. Figure 2 The photoelectric conversion element 10b shown 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 sequentially stacked on a lower electrode 11. Figure 1 and Figure 2The stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in the embodiment may be changed as appropriate depending on the application and characteristics.

[0149] In the photoelectric conversion element 10 a (or 10 b ), light preferably enters the photoelectric conversion film 12 via the upper electrode 15 .

[0150] Furthermore, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1×10 -5 ~1×10 7 From the perspective of performance and power consumption, the applied voltage is more preferably 1×10 -4 ~1×10 7 V / cm, more preferably 1×10 -3 ~5×10 6 V / cm.

[0151] In addition, regarding the voltage application method, Figure 1 and Figure 2 In the embodiment, the electron blocking film 16A side is preferably used as a cathode and the photoelectric conversion film 12 side is used as an anode. When the photoelectric conversion element 10a (or 10b) is used as a photosensor or incorporated into an imaging element, voltage can be applied by the same method.

[0152] As will be described in detail later, the photoelectric conversion element 10 a (or 10 b ) can be preferably used in an imaging element application.

[0153] Hereinafter, the configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail.

[0154] [Photoelectric conversion film]

[0155] The photoelectric conversion film is a film containing a specific compound.

[0156] Hereinafter, the specific compounds will be described in detail.

[0157] <Compound represented by formula (1) (specific compound)>

[0158] The specific compound is a compound represented by the following formula (1).

[0159] [Chemical Formula 9]

[0160]

[0161] In formula (1), n11 represents 1 or 2.

[0162] Among them, from the viewpoint of more excellent effect of the present invention, in Ar 11 In the case of a condensed polycyclic aromatic ring group consisting of four rings (for example, Ar 11 In the case of a group represented by formula (A3) to formula (A6) described later), n11 is preferably 1.

[0163] In formula (1), n12 and n13 each independently represent 0 or 1. However, at least one of n12 and n13 represents 1.

[0164] Preferably, both n12 and n13 are 1.

[0165] In formula (1), Ar 11 It represents a condensed polycyclic aromatic ring group composed of a combination of one or more (for example, one to four) aromatic rings selected from the group consisting of a thiophene ring, a benzene ring, a furan ring, and a selenophene ring.

[0166] Among them, Ar 11 It is preferably a condensed polycyclic aromatic ring group composed of a combination of one or more (eg, one to three) aromatic rings selected from the group consisting of a thiophene ring, a benzene ring, and a furan ring.

[0167] The fused polycyclic aromatic ring group has 3 to 4 rings.

[0168] Among the three to four rings constituting the condensed polycyclic aromatic ring group, it is preferred that at least one ring is not a benzene ring, and it is preferred that at least two rings are not a benzene ring.

[0169] The fused polycyclic aromatic ring group also preferably contains at least one (eg, 1 to 4, preferably 2) thiophene ring or furan ring, and more preferably contains a thiophene ring.

[0170] The fused polycyclic aromatic ring group may or may not have a substituent. As the substituent, a halogen atom (such as a fluorine atom) is preferred.

[0171] The number of substituents that the fused polycyclic aromatic ring group has is, for example, 1 to 6.

[0172] When n11 represents 2, 2 Ar 11 same.

[0173] Among them, Ar in formula (1) 11 It is preferably any of the groups represented by the following formulae (A1) to (A6), more preferably any of the groups represented by any of formulae (A3) to (A6), and still more preferably a group represented by formula (A5).

[0174] Among them, in formula (1), it is particularly preferred that n11 is 1, Ar 11 It is a group represented by formula (A5).

[0175] Furthermore, (Ar 11 ) n11 A group in which groups represented by the same formula among formulae (A1) to (A6) are linked to each other is also preferred. For example, a group in which two groups represented by formula (A1) are linked to each other is also preferred.

[0176] [Chemical Formula 10]

[0177]

[0178] In formulae (A1) to (A6), * represents a bonding position.

[0179] In formula (A1), Z 11 and Z 12 One of them represents a sulfur atom (-S-), an oxygen atom (-O-) or a selenium atom (-Se-), and Z 11 and Z 12 The other of represents -CR=. Preferably Z 11 and Z 12 One of them represents a sulfur atom or an oxygen atom, Z 11 and Z 12 The other one in represents -CR=.

[0180] Z 13 and Z 14 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 13 and Z 14 The other of represents -CR=. Preferably Z 13 and Z 14 One of them represents a sulfur atom or an oxygen atom, Z 13 and Z 14 The other one in represents -CR=.

[0181] R and R A Each independently represents a hydrogen atom or a substituent, preferably a hydrogen atom.

[0182] Can be made by R and R A The substituent represented by is preferably a halogen atom (fluorine atom, etc.) or an alkyl group (for example, having 1 to 2 carbon atoms) which may further have a halogen atom, and more preferably a halogen atom (fluorine atom, etc.).

[0183] In formula (A2), Z 21 ~Z 23 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and preferably represents a sulfur atom or an oxygen atom.

[0184] R A represents a hydrogen atom or a substituent, preferably a hydrogen atom.

[0185] Can be made by R A The substituent represented by is preferably a halogen atom (fluorine atom etc.).

[0186] In formula (A3), Z 31 and Z 32 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and preferably represents a sulfur atom or an oxygen atom.

[0187] R A represents a hydrogen atom or a substituent, preferably a hydrogen atom.

[0188] Can be made by R A The substituent represented by is preferably a halogen atom (fluorine atom etc.).

[0189] In formula (A4), Z 41 and Z 42 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 41 and Z 42 The other of represents -CR=. Preferably Z 41 and Z 42 One of them represents a sulfur atom or an oxygen atom, Z 41 and Z 42 The other one in represents -CR=.

[0190] Z 43 and Z 44 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 43 and Z 44 The other of represents -CR=. Preferably Z 43 and Z 44 One of them represents a sulfur atom or an oxygen atom, Z 43 and Z 44 The other one in represents -CR=.

[0191] R and R A Each independently represents a hydrogen atom or a substituent, preferably a hydrogen atom.

[0192] Can be made by R and R A The substituent represented by is preferably a halogen atom (fluorine atom etc.).

[0193] In formula (A5), Z 51 and Z 52 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 51 and Z 52 The other of represents -CR=. Preferably Z 51 and Z 52 One of them represents a sulfur atom or an oxygen atom, Z 51 and Z 52The other one in represents -CR=.

[0194] Z 53 and Z 54 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 53 and Z 54 The other of represents -CR=. Preferably Z 53 and Z 54 One of them represents a sulfur atom or an oxygen atom, Z 53 and Z 54 The other one in represents -CR=.

[0195] R and R A Each independently represents a hydrogen atom or a substituent, preferably a hydrogen atom.

[0196] Can be made by R and R A The substituent represented by is preferably a halogen atom (fluorine atom etc.).

[0197] In formula (A6), Z 61 ~Z 64 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and preferably represents a sulfur atom or an oxygen atom.

[0198] R A represents a hydrogen atom or a substituent.

[0199] Can be made by R A The substituent represented by is preferably a halogen atom (fluorine atom etc.).

[0200] In formula (1), Ar 14 and Ar 15 Each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent.

[0201] The aryl group may be monocyclic or polycyclic, and the number of ring members is preferably 6 to 15. The aryl group is preferably phenyl, naphthyl or anthracenyl, and more preferably phenyl.

[0202] The heteroaryl group may be monocyclic or polycyclic, and the number of ring atoms is preferably 5 to 15. The number of heteroatoms possessed by the aryl group is preferably 1 to 5, more preferably 1. Examples of the heteroatoms include nitrogen, oxygen, sulfur, and selenium atoms. The heteroaryl group is preferably pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolyl, quinoxalinyl, quinazolyl, phthalazinyl, cinnolyl, isoquinolyl, pteridyl, acridinyl, phenazinyl, phenanthrolyl, tetrazolyl, pyrazolyl, imidazolyl, or thiazolyl.

[0203] As the substituent that the aryl group and the heteroaryl group may have, an alkyl group or a halogen atom (such as a fluorine atom) which may further have a substituent is preferable.

[0204] The alkyl group may be linear or branched, and preferably has 1 to 3 carbon atoms. Examples of substituents that the alkyl group may further have include halogen atoms (such as fluorine atoms). For example, the alkyl group is preferably a haloalkyl group (such as a fluoroalkyl group), and more preferably a perhaloalkyl group (such as a perfluoroalkyl group).

[0205] Among them, Ar 14 and Ar 15 Each independently preferably is an aryl group having a halogenated alkyl group or a halogen atom as a substituent, or a heteroaryl group which may have a substituent.

[0206] Ar 14 and Ar 15 They may be the same or different, but are preferably the same.

[0207] In formula (1), Ar 12 and Ar 13 Each independently represents any one of the groups represented by formula (2) to formula (4).

[0208] Ar 12 and Ar 13 They may be the same or different, but are preferably the same.

[0209] [Chemical Formula 11]

[0210]

[0211] In formula (2) to formula (4), * A and* B Indicates the bonding position.

[0212] In formulas (2) to (4), * A and* B Can be* A is (Ar 11 ) n11 The bonding position on the side can also be * B is (Ar 11 ) n11 side bonding position.

[0213] Among them, in formula (3), preferably * A is (Ar 11 ) n11 side bonding position.

[0214] In formula (2), X 21 and X22 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, preferably a sulfur atom or an oxygen atom.

[0215] Y 21 and Y 22 Each independently represents a nitrogen atom (-N=) or -CR=. R represents a hydrogen atom or a substituent.

[0216] Y 21 and Y 22 Each independently preferably is a nitrogen atom or -CH=.

[0217] The substituent that may be represented by R is preferably a halogen atom (fluorine atom etc.).

[0218] Among them, Y 21 and Y 22 At least one of represents a nitrogen atom.

[0219] Y 21 and Y 22 In the 21 It can be a nitrogen atom or only Y 22 It may be a nitrogen atom, or both may be nitrogen atoms.

[0220] In formula (3), X 31 represents an oxygen atom, a sulfur atom or a selenium atom, preferably a sulfur atom or an oxygen atom.

[0221] Y 31 ~Y 34 Each independently represents a nitrogen atom or -CR=. R represents a hydrogen atom or a substituent.

[0222] Y 31 ~Y 34 Each independently preferably is a nitrogen atom or -CH=.

[0223] The substituent that may be represented by R is preferably a halogen atom (fluorine atom etc.).

[0224] Y 31 ~Y 34 Among them, 0 to 4 may be nitrogen atoms, preferably 0 or 1 may be a nitrogen atom, and more preferably 1 may be a nitrogen atom.

[0225] In formula (4), X 41 represents an oxygen atom, a sulfur atom or a selenium atom, preferably a sulfur atom or an oxygen atom.

[0226] Y 41 ~Y 43 Each independently represents a nitrogen atom or -CR=. R represents a hydrogen atom or a substituent.

[0227] Y 41 ~Y 43Each independently preferably is a nitrogen atom or -CH=.

[0228] The substituent that may be represented by R is preferably a halogen atom (fluorine atom etc.).

[0229] Y 41 ~Y 43 Among them, 0 to 3 may be nitrogen atoms, preferably 1 or 2 may be nitrogen atoms.

[0230] Ar 12 and Ar 13 Preferably, each independently represents any one of the groups represented by formula (5) to formula (13), and more preferably represents any one of the groups represented by formula (5), formula (6), and formula (8) to formula (13).

[0231] Among them, Ar 11 is a group represented by formula (A5), and Ar 12 and Ar 13 Each independently preferably represents any one of the groups represented by formula (5), formula (6), and formula (8) to formula (13).

[0232] In addition, the groups represented by formulae (5) to (6) are preferred embodiments of the group represented by formula (2), the groups represented by formulae (7) to (11) are preferred embodiments of the group represented by formula (3), and the groups represented by formulae (12) to (13) are preferred embodiments of the group represented by formula (4).

[0233] [Chemical Formula 12]

[0234]

[0235] In formulas (5) to (13), * A and* B Indicates the bonding position.

[0236] In formulas (5) to (13), * A and* B Can be* A is (Ar 11 ) n11 The bonding position on the side can also be * B is (Ar 11 ) n11 side bonding position.

[0237] Among them, in formula (7) to formula (11), * A is (Ar 11 ) n11 side bonding position.

[0238] R Arepresents a hydrogen atom or a substituent, preferably a hydrogen atom.

[0239] Can be made by R A The substituent represented by is preferably a halogen atom (fluorine atom etc.).

[0240] Specific examples of the specific compounds are shown below.

[0241] In the following structural formulas showing specific examples of specific compounds, Ar 14 ~Ar 15 Examples of combinations of possible forms of each group of n1, n12, and n13 are shown in the table in the following section.

[0242] [Chemical Formula 13]

[0243]

[0244] [Chemical Formula 14]

[0245]

[0246] [Chemical Formula 15]

[0247]

[0248] [Chemical Formula 16]

[0249]

[0250] In the above structural formulas, Ar 14 ~Ar 15 Examples of combinations of possible forms of each group or each value of n12, n13 are shown in the following table.

[0251] In the following tables, * represents a bonding position, and Ph represents a phenyl group.

[0252] In the following table, “Ar 12 The left bonding position (*) of the group shown in the "" column is Ar 14 The bonding position on the side is the bonding position, and the bonding position on the right side (*) is the center side (equivalent to (Ar 11 ) n11 The bonding position of the group on the side of the “Ar 13 The right bonding position (*) of the group shown in the "" column is Ar 15 The bonding position on the left side is the center side (equivalent to (Ar 11 ) n11 The bonding position of the group on the side of the molecule.

[0253] [Table 1]

[0254]

[0255] [Table 2]

[0256]

[0257] [Table 3]

[0258]

[0259] [Table 4]

[0260]

[0261] The molecular weight of the specific compound is not particularly limited, but is preferably 550 to 1200, more preferably 600 to 900. A molecular weight of 1200 or less prevents high vapor deposition temperatures and reduces decomposition of the compound. A molecular weight of 550 or greater prevents a decrease in the glass transition point of the vapor-deposited film, improving the heat resistance of the photoelectric conversion element.

[0262] The specific compound is particularly useful as a material for photoelectric conversion films used in imaging devices, photosensors, or photocells. Furthermore, the specific compound can be used as a coloring material, liquid crystal material, organic semiconductor material, charge transport material, pharmaceutical material, and fluorescent diagnostic drug material.

[0263] From the viewpoint of energy level matching with an n-type semiconductor material described later, the specific compound is preferably a compound having an ionization potential of -5.0 to -6.0 eV in a single film.

[0264] The maximum absorption wavelength of the specific compound is not particularly limited, but is preferably within the wavelength range of 350 to 550 nm, and more preferably within the wavelength range of 400 to 550 nm.

[0265] The maximum absorption wavelength is the value measured in a solution state (solvent: chloroform) after adjusting the absorption spectrum of the specific compound to a concentration where the absorbance is approximately 0.5 to 1. However, if the specific compound is not soluble in chloroform, the maximum absorption wavelength of the specific compound is the value measured using the specific compound in a film state by vapor deposition.

[0266] The maximum absorption wavelength of the photoelectric conversion film is not particularly limited, but is preferably within a wavelength range of 300 to 700 nm, and more preferably within a wavelength range of 400 to 700 nm.

[0267] From the viewpoint of the responsiveness of the photoelectric conversion element, the content of the specific compound in the photoelectric conversion film (=film thickness of the specific compound converted to a single layer / film thickness of the photoelectric conversion film × 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 25 to 40% by volume.

[0268] The specific compound may be used alone or in combination of two or more.

[0269] Pigment

[0270] The photoelectric conversion film preferably further contains a dye as a component other than the above-mentioned specific compound.

[0271] The above-mentioned pigment is preferably an organic pigment.

[0272] Examples of the pigment include cyanine pigments, styryl pigments, hemicyanine pigments, merocyanine pigments (including zero methine merocyanine (simple merocyanine)), rhodanine pigments, allopolar pigments, oxonol pigments, hemicyanine pigments, squarylium pigments, crotonium pigments, azamethine pigments, coumarin pigments, arylide pigments, anthraquinone pigments, triphenylmethane pigments, azo pigments, methine azo pigments, metallocene pigments, fluorenone pigments, fulgide pigments, perylene pigments, phenazine pigments, phenanthene pigments, and phenanthene pigments. Thiazine pigments, quinone pigments, diphenylmethane pigments, polyene pigments, acridine pigments, acridone pigments, quinoxaline pigments, diphenylamine pigments, quinophthalone pigments, phenoxazine pigments, phthaloperyl pigments, dioxane pigments, porphyrin pigments, chlorophyll pigments, phthalocyanine pigments, subphthalocyanine pigments, metal complex pigments, compounds described in paragraphs

[0083] to

[0089] of JP-A-2014-82483, compounds described in paragraphs

[0029] to

[0033] of JP-A-2009-167348, The compounds described in paragraphs

[0197] to

[0227] of Japanese Patent Application Laid-Open No. 2012-77064, the compounds described in paragraphs

[0035] to

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

[0041] to

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

[0059] to

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

[0063] to

[0064] of WO2019-009249,

[0078] to

[0083] , the compounds described in paragraphs

[0054] to

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

[0059] to

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

[0086] to

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

[0085] to

[0114] of WO2020-013246.

[0273] Relative to the total content of the specific compound and the pigment in the photoelectric conversion film, the content of the pigment (= (film thickness of the pigment converted to a single layer / (film thickness of the specific compound converted to a single layer + film thickness of the pigment converted to a single layer) × 100)) is preferably 15 to 75 volume %, more preferably 20 to 60 volume %, and further preferably 25 to 50 volume %.

[0274] In addition, the pigment may be used alone or in combination of two or more.

[0275] <n-type semiconductor materials>

[0276] The photoelectric conversion film preferably further contains an n-type semiconductor material as a component other than the above-mentioned specific compound and the dye.

[0277] The n-type semiconductor material is an acceptor organic semiconductor material (compound), and refers to an organic compound having a property of readily accepting electrons.

[0278] More specifically, the n-type semiconductor material is preferably an organic compound having an electron affinity greater than that of the specific compound when used in contact with the specific compound.

[0279] In this specification, the inverse value of the LUMO value (value multiplied by minus 1) obtained by calculating B3LYP / 6-31G(d) using Gaussian'09 (software manufactured by Gaussian Corporation) is used as the value of the electron affinity.

[0280] Furthermore, the n-type semiconductor material is preferably an organic compound having an electron affinity greater than that of the dye when used in contact with the dye.

[0281] The electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV.

[0282] As n-type semiconductor materials, examples thereof include fullerenes selected from the group consisting of fullerenes and their derivatives, fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); heterocyclic compounds having a 5- to 7-membered ring containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole); polyarylene compounds; fluorene compounds; cyclic Pentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives, oxadiazole derivatives; anthraquinone dimethane derivatives; dibenzoquinone derivatives; bathocuproine, bathophenanthroline, and their derivatives; triazole compounds; distyrylarylene derivatives; metal complexes having nitrogen-containing heterocyclic compounds as ligands; silole compounds; and compounds described in paragraphs

[0056] to

[0057] of Japanese Patent Application Laid-Open No. 2006-100767.

[0283] Among them, the n-type semiconductor material preferably includes fullerenes selected from the group consisting of fullerenes and derivatives thereof.

[0284] 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.

[0285] Examples of fullerene derivatives include compounds obtained by adding a substituent to the above-mentioned fullerene. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. Fullerene derivatives are preferably compounds described in Japanese Patent Application Laid-Open No. 2007-123707.

[0286] In the case where the photoelectric conversion film contains an n-type semiconductor material, the content of the n-type semiconductor material (=(film thickness of the n-type semiconductor material converted to a single layer / (film thickness of the specific compound converted to a single layer + film thickness of the pigment converted to a single layer + film thickness of the n-type semiconductor material converted to a single layer) × 100)) is preferably 15 to 75 volume %, more preferably 20 to 60 volume %, and even more preferably 25 to 50 volume % relative to the total content of the specific compound, the pigment and the n-type semiconductor material.

[0287] In addition, the n-type semiconductor material may be used alone or in combination of two or more.

[0288] Furthermore, when the n-type semiconductor material contains fullerenes, the content of fullerenes relative to the total content of the n-type semiconductor material (= (film thickness of fullerenes converted in a single layer / total film thickness of each n-type semiconductor material converted in a single layer) × 100) is preferably 50 to 100 volume %, and more preferably 80 to 100 volume %.

[0289] Furthermore, the fullerenes may be used alone or in combination of two or more.

[0290] The molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.

[0291] The photoelectric conversion film preferably consists essentially only of a specific compound, a pigment, and an n-type semiconductor material. "The photoelectric conversion film consists essentially only of 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 relative to the total mass of the photoelectric conversion film.

[0292] When the photoelectric conversion film contains a dye, the photoelectric conversion film is preferably a mixed layer formed in a state where a specific compound and the dye are mixed.

[0293] Furthermore, when the photoelectric conversion film includes an n-type semiconductor material, the photoelectric conversion film is preferably a mixed layer formed in a state where a specific compound and the n-type semiconductor material are mixed.

[0294] When the photoelectric conversion film contains a dye and an n-type semiconductor material, the photoelectric conversion film is preferably a mixed layer formed in a state where a specific compound, a dye, and an n-type semiconductor material are mixed.

[0295] A mixed layer is a layer in which two or more materials are mixed in a single layer.

[0296] Photoelectric conversion films containing specific compounds are non-luminescent films, which have characteristics different from organic light emitting diodes (OLEDs). Non-luminescent films have a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less.

[0297] <Film Formation Method>

[0298] The photoelectric conversion film is mainly formed by a dry film-forming method. Examples of dry film-forming methods include physical vapor deposition methods such as vapor deposition (especially vacuum vapor deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), as well as CVD (Chemical Vapor Deposition) methods such as plasma polymerization. Among them, vacuum vapor deposition is preferred. When forming a photoelectric conversion film by vacuum vapor deposition, manufacturing conditions such as the degree of vacuum and the vapor deposition temperature can be set according to conventional methods.

[0299] The thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, further preferably 50 to 500 nm, and particularly preferably 50 to 400 nm.

[0300] [Electrode (conductive film)]

[0301] The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of the conductive material include metals, alloys, metal oxides, conductive compounds, and mixtures thereof.

[0302] Since light enters from the upper electrode 15 , it is preferable that the upper electrode 15 be transparent to the light to be detected. Examples of materials constituting the upper electrode 15 include 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); thin films of metals such as gold, silver, chromium, and nickel; mixtures or laminates of these metals with 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 due to their high conductivity and transparency.

[0303] Generally, if the conductive film is made thinner than a certain range, it will lead to a sharp increase in resistance value. However, in the solid-state imaging element assembled with the photoelectric conversion element of this embodiment, the thin film resistance can be, for example, 100 to 10,000 Ω / □, and the film thickness range that can be thinned is large. In addition, the thinner the thickness of the upper electrode (transparent conductive film) 15, the less light is absorbed, and the transmittance generally increases. The increase in transmittance increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion energy, so it is preferred. Considering the suppression of leakage current, the increase in thin film resistance value and the increase in transmittance associated with thin filming, the film thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0304] The lower electrode 11 may be transparent or non-transparent and reflect light, depending on its intended use. Examples of materials constituting the lower electrode 11 include 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 (for example, titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as graphene and carbon nanotubes.

[0305] The method for forming the electrodes is not particularly limited and can be appropriately selected depending on the electrode material. Specifically, examples include wet methods such as printing and coating; physical methods such as vacuum deposition, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD.

[0306] When the electrode material is ITO, examples of methods include an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), and coating of an indium tin oxide dispersion.

[0307] [Charge blocking film: electron blocking film, hole blocking film]

[0308] The photoelectric conversion element of the present invention also preferably has one or more intermediate layers other than the photoelectric conversion film between the conductive film and the transparent conductive film. Examples of the intermediate layer include a charge blocking film. By including such a film in the photoelectric conversion element, the characteristics of the resulting photoelectric conversion element (photoelectric conversion efficiency and responsiveness, etc.) are further improved. Examples of the charge blocking film include an electron blocking film and a hole blocking film. Each film is described in detail below.

[0309] <Electron blocking film>

[0310] The electron blocking film is made of a donor organic semiconductor material (compound), and for example, the following p-type organic semiconductors can be used: The p-type organic semiconductors can be used alone or in combination of two or more.

[0311] Examples of p-type organic semiconductors include triarylamine compounds (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), compounds described in paragraphs

[0128] to

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

[0052] to

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

[0119] of JP-A-2011-225544). to

[0158] , compounds described in

[0044] to

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

[0086] to

[0090] of JP-A-2012-94660, etc.), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (for example, thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b]thiophene (BTBT) derivatives, thieno[3,2-f:4,5-f′] bis[1]benzothiophene (TBBT) derivatives, compounds described in paragraphs

[0031] to

[0036] of Japanese Patent Application Laid-Open No. 2018-14474, compounds described in paragraphs

[0043] to

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

[0025] to

[0037] and

[0099] to

[0109] of WO2017-159684, compounds described in Japanese Patent Application Laid-Open No. 2017-07676 The compounds described in paragraphs

[0029] to

[0034] of WO 6, the compounds described in paragraphs

[0015] to

[0025] of WO 2018-207722, the compounds described in paragraphs

[0045] to

[0053] of JP 2019-54228, the compounds described in paragraphs

[0045] to

[0055] of WO 2019-058995, the compounds described in paragraphs

[0063] to

[0071] of WO 2019-081416 89], compounds described in paragraphs

[0033] to

[0036] of Japanese Patent Application Laid-Open No. 2019-80052, compounds described in paragraphs

[0044] to

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

[0041] to

[0046] of WO2019-093188, etc.), cyanine compounds, oxocyanine compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylenes compounds, fused 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 nitrogen-containing heterocyclic compounds as ligands.

[0312] As the p-type organic semiconductor, compounds having a lower ionization potential than that of n-type semiconductor materials can be mentioned. As long as this condition is satisfied, the above-mentioned dyes can also be used.

[0313] Furthermore, a polymer material may be used as the electron blocking film.

[0314] Examples of the polymer material include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.

[0315] In addition, the electron blocking film may be composed of a plurality of films.

[0316] The electron-blocking film can be made of an inorganic material. Generally, the dielectric constant of inorganic materials is greater than that of organic materials. Therefore, when inorganic materials are used in the electron-blocking film, a higher voltage is applied to the photoelectric conversion film, resulting in higher photoelectric conversion efficiency. Examples of inorganic materials that can form the electron-blocking film include calcium oxide, chromium oxide, chromium copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, indium silver oxide, and iridium oxide.

[0317] Hole-blocking film

[0318] The hole blocking film is an acceptor organic semiconductor material (compound), and the above-mentioned n-type semiconductor material or the like can be used.

[0319] 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. As for the dry film forming method, examples thereof include a vapor deposition method and a sputtering method. The vapor deposition method may be any of a physical vapor deposition (PVD: Physical Vapor Deposition (physical vapor deposition)) method and a chemical vapor deposition (CVD) method, and preferably a physical vapor deposition method such as a vacuum vapor deposition method. As for the wet film forming method, examples thereof include an inkjet method, a spray coating method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roller coating method, a rod coating method, and a gravure coating method. From the viewpoint of high-precision patterning, an inkjet method is preferred.

[0320] The thickness of each of the charge blocking films (electron blocking film and hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm.

[0321] [Substrate]

[0322] The photoelectric conversion element may further include a substrate. The type of substrate used is not particularly limited, and examples thereof include semiconductor substrates, glass substrates, and plastic substrates.

[0323] The position of the substrate is not particularly limited, but generally, a conductive film, a photoelectric conversion film, and a transparent conductive film are stacked in this order on the substrate.

[0324] Sealing layer

[0325] The photoelectric conversion element may also have a sealing layer. The performance of the photoelectric conversion material can sometimes degrade significantly due to the presence of degradation factors such as water molecules. Therefore, by encapsulating and sealing the entire photoelectric conversion film with a sealing layer, such as a dense ceramic material (such as a metal oxide, metal nitride, or metal oxynitride) that is impermeable to water molecules, or a sealing layer made of diamond-like carbon (DLC), the above degradation can be prevented.

[0326] In addition, regarding the sealing layer, the material selection and production can be carried out according to the description in paragraphs

[0210] to

[0215] of Japanese Patent Application Laid-Open No. 2011-082508.

[0327] [Image sensor, optical sensor]

[0328] An example of a use for photoelectric conversion elements is an imaging element. An imaging element is an element that converts the optical information of an image into an electrical signal. Typically, multiple photoelectric conversion elements are arranged in a matrix on the same plane. Each photoelectric conversion element (pixel) converts the optical signal into an electrical signal, and each pixel can sequentially output this electrical signal to the outside of the imaging element. Therefore, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.

[0329] The imaging element is mounted on imaging elements such as digital cameras and digital video cameras, and imaging modules of electronic endoscopes and mobile phones.

[0330] The photoelectric conversion element of the present invention is also preferably used in a photosensor having the photoelectric conversion element of the present invention. The photosensor may be used alone or as a line sensor in which the photoelectric conversion elements are arranged in a straight line or as a two-dimensional sensor in which the photoelectric conversion elements are arranged in a plane.

[0331] [Compound]

[0332] The present invention also relates to compounds.

[0333] The compound of the present invention is the same as the above-mentioned specific compound (the compound represented by formula (1)), and the preferred conditions are also the same.

[0334] Example

[0335] Below, based on embodiment, the present invention is described in further detail.As long as do not depart from the purpose of the present invention, then can suitably change the material, usage amount, ratio, processing content and processing step etc. shown in following embodiment.Therefore, the scope of the present invention should not be interpreted restrictively by the embodiment shown below.

[0336] [Compound (Evaluation Compound)]

[0337] <Synthesis of Compound (1-1)>

[0338] A specific compound, compound (1-1), was synthesized according to the following scheme.

[0339] [Chemical Formula 17]

[0340]

[0341] Compound (1-1-1) (1 mmol), compound (1-1-2) (2.4 mmol), XPhos Pd G3 (0.03 mmol) and 4-methyltetrahydrofuran 16 mL were added to a glass reaction vessel to obtain a mixed solution. After nitrogen substitution in the reaction vessel, the mixed solution was reacted at 100 ° C for 5 hours. After the mixed solution was naturally cooled to room temperature (25 ° C), the precipitate precipitated in the mixed solution was filtered out. The obtained solid (filtered material) was suspended in chlorobenzene and filtered after heating at 140 ° C for 1 hour. After drying the obtained solid (filtered material) under reduced pressure, 0.4 mmol of compound (1-1) was obtained by sublimation purification.

[0342] The measurement results of the obtained compound (1-1) by LDI-MS (soft laser desorption ionization mass-spectrometric method) are as follows.

[0343] LDI-MS: 620.9(M + +H)

[0344] In addition, XPhos Pd G3 is (2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate.

[0345] <Synthesis of Compound (1-24)>

[0346] The specific compound, Compound (1-24), was synthesized according to the following scheme.

[0347] [Chemical Formula 18]

[0348]

[0349] Compound (1-24-1) (1 mmol), compound (1-24-2) (2.4 mmol), XPhos Pd G3 (0.03 mmol) and 4-methyltetrahydrofuran (16 mL) were added to a glass reaction vessel to obtain a mixed solution. After nitrogen substitution in the reaction vessel, the mixed solution was reacted at 100 ° C for 5 hours. After the mixed solution was naturally cooled to room temperature (25 ° C), the precipitate precipitated in the mixed solution was filtered out. The obtained solid (filtered material) was suspended in chlorobenzene and filtered after heating at 140 ° C for 1 hour. After drying the obtained solid (filtered material) under reduced pressure, 0.5 mmol of compound (1-24) was obtained by sublimation purification.

[0350] The measurement results of the obtained compound (1-24) by LDI-MS are as follows. LDI-MS: 636.9 (M + +H)

[0351] Other specific compounds were also synthesized with reference to the above synthesis methods.

[0352] The specific compounds and comparative compounds used in the tests are shown below.

[0353] Hereinafter, compounds (1-1) to (1-27) are specific compounds.

[0354] Hereinafter, specific compounds and comparative compounds are also collectively referred to as evaluation compounds.

[0355] [Chemical Formula 19]

[0356]

[0357] [Chemical Formula 20]

[0358]

[0359] [Pigment (Evaluation Pigment)]

[0360] The dyes shown below were used as dyes for evaluation in Examples and were used to produce photoelectric conversion elements described later.

[0361] [Chemical Formula 21]

[0362]

[0363] [Chemical Formula 22]

[0364]

[0365] [n-type semiconductor materials]

[0366] Fullerene C60 was used as an n-type semiconductor material for evaluation and was used to produce a photoelectric conversion element described later.

[0367] [test]

[0368] <Examples and Comparative Examples: Preparation of Photoelectric Conversion Elements>

[0369] The obtained compound was used to prepare Figure 2 Here, the photoelectric conversion element includes a lower electrode 11 , an electron blocking film 16A, a photoelectric conversion film 12 , a hole blocking film 16B, and an upper electrode 15 .

[0370] Specifically, a lower electrode 11 (thickness: 30 nm) was formed by sputtering amorphous ITO on a glass substrate. Furthermore, an electron-blocking film 16A (thickness: 30 nm) was formed by vacuum-heating evaporation of the following compound (C-1) on the lower electrode 11. Furthermore, the evaluation compound, n-type semiconductor material, and pigment listed in Table 1 were co-evaporated on the electron-blocking film 16A to form a photoelectric conversion film 12 as a mixed layer. The ratio of the deposition rates of the evaluation compound, n-type semiconductor material, and pigment was adjusted so that the film thickness of these components in the photoelectric conversion film, calculated as a single layer, was the ratio shown in the "Component Ratio" column of Table 1.

[0371] The following compound (C-2) was then vapor-deposited onto the photoelectric conversion film 12 to form a hole-blocking film 16B (thickness: 10 nm). An amorphous ITO film was then deposited onto the hole-blocking film 16B by sputtering to form the upper electrode 15 (transparent conductive film) (thickness: 10 nm). A SiO film was then formed as a sealing layer on the upper electrode 15 by vacuum evaporation, and then an aluminum oxide (Al2O3) layer was formed thereon by ALCVD (Atomic Layer Chemical Vapor Deposition) to fabricate the photoelectric conversion elements of each Example or Comparative Example.

[0372] [Chemical Formula 23]

[0373]

[0374] <Evaluation of Dark Current>

[0375] The dark current of each of the obtained photoelectric conversion elements was measured by the following method.

[0376] The electric field strength becomes 2.5×10 5 A voltage was applied to the lower and upper electrodes of each photoelectric conversion element at 100 V / cm, and the current value (dark current) in the dark was measured. The results confirmed that the dark current was 50 nA / cm in all photoelectric conversion elements. 2 Below, a sufficiently low dark current is shown.

[0377] <Evaluation of Photoelectric Conversion Efficiency (Quantum Efficiency)>

[0378] The driving of each obtained photoelectric conversion element was confirmed by the following method.

[0379] A voltage was applied to each photoelectric conversion element so that the electric field strength was 2.0×10 5 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 (light with a wavelength of 400 to 700 nm) was evaluated.

[0380] The relative ratio of the integrated value of the photoelectric conversion efficiency in light with a wavelength of 400 to 550 nm was calculated according to Formula (S) and evaluated according to the following criteria.

[0381] The larger the relative ratio, the better the photoelectric conversion efficiency (particularly the photoelectric conversion efficiency for light with a wavelength of 400 to 550 nm), which is more preferable.

[0382] Formula (S):

[0383] Relative contrast =

[0384] (Integrated value of the photoelectric conversion efficiency of the photoelectric conversion element to be evaluated for light with a wavelength of 400 to 550 nm) / (Integrated value of the photoelectric conversion efficiency of the photoelectric conversion element of Example 1-1 for light with a wavelength of 400 to 550 nm)

[0385] A: The relative ratio of the integrated value of the photoelectric conversion efficiency is 1.4 or more

[0386] B: The relative ratio of the integrated value of the photoelectric conversion efficiency is 1.2 or more and less than 1.4

[0387] C: The relative ratio of the integrated value of the photoelectric conversion efficiency is 1.0 or more and less than 1.2

[0388] D: The relative ratio of the integrated value of the photoelectric conversion efficiency is 0.8 or more and less than 1.0

[0389] E: The relative ratio of the integrated value of the photoelectric conversion efficiency is less than 0.8

[0390] <Evaluation of the Electric Field Intensity Dependence of Photoelectric Conversion Efficiency>

[0391] The electric field intensity dependence of the quantum efficiency of each of the obtained photoelectric conversion elements was confirmed by the following method.

[0392] A voltage was applied to each photoelectric conversion element so that the electric field strength was 1.5×10 5 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 (light with a wavelength of 400 to 700 nm) was evaluated.

[0393] Furthermore, a voltage was applied to each photoelectric conversion element so that the electric field strength was 2.0×10 5 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 (light with a wavelength of 400 to 700 nm) was evaluated.

[0394] The photoelectric conversion efficiency ratio was calculated using the integrated value of the photoelectric conversion efficiency in light with a wavelength of 400 to 550 nm measured at each electric field strength using the following formula, and the electric field strength dependency of the photoelectric conversion efficiency was evaluated according to the following criteria.

[0395] The closer the photoelectric conversion efficiency ratio is to 1, the smaller the electric field intensity dependency of the photoelectric conversion efficiency becomes, which is more preferable.

[0396] Photoelectric conversion efficiency ratio

[0397] = (When a voltage of 1.5×10 5 V / cm) / (the integral value of the photoelectric conversion efficiency in the case of light with a wavelength of 400 to 550 nm under the condition of an electric field strength of 2.0 × 10 5 The integrated value of the photoelectric conversion efficiency for light with a wavelength of 400 to 550 nm under the condition of an electric field intensity of 100 V / cm

[0398] A: Photoelectric conversion efficiency ratio is 0.9 or more and 1.0 or less

[0399] B: Photoelectric conversion efficiency ratio is 0.8 or more and less than 0.9

[0400] C: Photoelectric conversion efficiency ratio is 0.7 or more and less than 0.8

[0401] D: Photoelectric conversion efficiency ratio is less than 0.7

[0402] The characteristics of the photoelectric conversion element of each example or comparative example and the results of tests conducted using the photoelectric conversion element of each example or comparative example are shown in Table 1 below.

[0403] In the table, the "Type" column in the "Evaluation Compound" column, the "n-Type Semiconductor Material" column, and the "Dye" column indicates the types of components used in the production of the photoelectric conversion element.

[0404] The column "Ar11" indicates the number of Ar11 in the specific compound used. 11 The group represented is any one of the groups represented by formula (A1) to formula (A6).

[0405] [Table 5]

[0406]

[0407] From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention using a specific compound in the photoelectric conversion film exhibits excellent effects of the present invention.

[0408] On the other hand, it was confirmed that when a compound different from the specific compound was used, the photoelectric conversion efficiency of the obtained photoelectric conversion element was poor and the dependence of the photoelectric conversion efficiency on electric field intensity was also large.

[0409] In the 11 When the group represented by the formula (A5) is a specific compound, the photoelectric conversion efficiency and / or the electric field intensity dependence of the photoelectric conversion efficiency becomes better. Therefore, it is confirmed that in the specific compound, the group represented by Ar 11 When the group represented is a group represented by formula (A5), the effects of the present invention are more excellent.

[0410] Explanation of symbols

[0411] 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 comprising, in this order, a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein: The photoelectric conversion film includes a compound represented by formula (1), In formula (1), n11 represents 1 or 2, n12 and n13 are both 1, By Ar 11 The group represented is any one of the groups represented by formula (A1) to formula (A6), In formulas (A1) to (A6), * represents a bonding position, In formula (A1), Z 11 and Z 12 One of them represents a sulfur atom, Z 11 and Z 12 The other one in represents -CR=, Z 13 and Z 14 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 13 and Z 14 The other one represents -CR=, R and R A Each independently represents a hydrogen atom or a substituent, In formula (A2), Z 21 ~Z 23 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and Z 21 ~Z 23 At least one of represents a sulfur atom, R A represents a hydrogen atom or a substituent, In formula (A3), Z 31 and Z 32 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and Z 31 and Z 32 At least one of represents a sulfur atom, R A represents a hydrogen atom or a substituent, In formula (A4), Z 41 and Z 42 One of them represents a sulfur atom, Z 41 and Z 42 The other one in represents -CR=, Z 43 and Z 44 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 43 and Z 44 The other one represents -CR=, R and R A Each independently represents a hydrogen atom or a substituent, In formula (A5), Z 51 and Z 52 One of them represents a sulfur atom, Z 51 and Z 52 The other one in represents -CR=, Z 53 and Z 54 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 53 and Z 54 The other one represents -CR=, R and R A Each independently represents a hydrogen atom or a substituent, In formula (A6), Z 61 ~Z 64 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and Z 61 ~Z 64 At least one of represents a sulfur atom, R A represents a hydrogen atom or a substituent, Ar 14 and Ar 15 Each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, Ar 12 and Ar 13 Each independently represents any one of the groups represented by formula (2) to formula (4), In formula (2) to formula (4), * A and* B represents the bonding position, In formula (2), X 21 and X 22 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and Y 21 and Y 22 Each independently represents a nitrogen atom or -CR=, R represents a hydrogen atom or a substituent, wherein Y 21 and Y 22 At least one of represents a nitrogen atom, In formula (3), X 31 represents a sulfur atom, an oxygen atom, or a selenium atom, Y 31 ~Y 34 Each independently represents a nitrogen atom or -CR= and Y 31 ~Y 34 represents a nitrogen atom, R represents a hydrogen atom or a substituent, In formula (4), X 41 represents a sulfur atom, an oxygen atom, or a selenium atom, Y 41 ~Y 43 Each independently represents a nitrogen atom or -CR=, and R represents a hydrogen atom or a substituent.

2. The photoelectric conversion element according to claim 1, wherein In the formula (A1), Z 11 and Z 12 One of them represents a sulfur atom, Z 11 and Z 12 The other one in represents -CR=, Z 13 and Z 14 One of them represents a sulfur atom or an oxygen atom, Z 13 and Z 14 The other one in represents -CR=, In the formula (A2), Z 21 ~Z 23 Each independently represents a sulfur atom or an oxygen atom, Z 21 ~Z 23 At least one of represents a sulfur atom, In the formula (A3), Z 31 and Z 32 Each independently represents a sulfur atom or an oxygen atom, Z 31 ~Z 32 At least one of represents a sulfur atom, In the formula (A4), Z 41 and Z 42 One of them represents a sulfur atom, Z 41 and Z 42 The other one in represents -CR=, Z 43 and Z 44 One of them represents a sulfur atom or an oxygen atom, Z 43 and Z 44 The other one in represents -CR=, In the formula (A5), Z 51 and Z 52 One of them represents a sulfur atom, Z 51 and Z 52 The other one in represents -CR=, Z 53 and Z 54 One of them represents a sulfur atom or an oxygen atom, Z 53 and Z 54 The other one in represents -CR=, In the formula (A6), Z 61 ~Z 64 Each independently represents a sulfur atom or an oxygen atom, Z 61 ~Z 64 At least one of represents a sulfur atom.

3. The photoelectric conversion element according to claim 1 or 2, wherein In the formula (1), n11 is 1, Ar 11 It is a group represented by the above formula (A5).

4. The photoelectric conversion element according to claim 1 or 2, wherein In the formula (2), X 21 and X 22 each independently represents a sulfur atom or an oxygen atom, In the formula (3), X 31 represents a sulfur atom or an oxygen atom, In the formula (4), X 41 represents a sulfur atom or an oxygen atom.

5. The photoelectric conversion element according to claim 1 or 2, wherein In the formula (1), Ar 12 and Ar 13 Each independently represents any one of the groups represented by formula (5), formula (6), and formula (8) to formula (13), In formulas (5) to (13), * A and* B represents the bonding position, R A represents a hydrogen atom or a substituent.

6. The photoelectric conversion element according to claim 1 or 2, wherein The molecular weight of the compound represented by the formula (1) is 550 to 1200.

7. The photoelectric conversion element according to claim 1 or 2, wherein The photoelectric conversion film further comprises a pigment, The photoelectric conversion film is a mixed layer formed in a state where the compound represented by the formula (1) and the pigment are mixed.

8. The photoelectric conversion element according to claim 1 or 2, wherein The photoelectric conversion film further includes an n-type semiconductor material.

9. The photoelectric conversion element according to claim 8, wherein The n-type semiconductor material contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.

10. The photoelectric conversion element according to claim 1 or 2, wherein Between the conductive film and the transparent conductive film, one or more intermediate layers are provided in addition to the photoelectric conversion film. An imaging element comprising the photoelectric conversion element according to any one of claims 1 to 10. 12 . A photosensor comprising the photoelectric conversion element according to claim 1 .

13. A compound represented by formula (1), In formula (1), n11 represents 1 or 2, n12 and n13 are both 1, By Ar 11 The group represented is any one of the groups represented by formula (A1) to formula (A6), In formulas (A1) to (A6), * represents a bonding position, In formula (A1), Z 11 and Z 12 One of them represents a sulfur atom, Z 11 and Z 12 The other one in represents -CR=, Z 13 and Z 14 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 13 and Z 14 The other one represents -CR=, R and R A Each independently represents a hydrogen atom or a substituent, In formula (A2), Z 21 ~Z 23 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and Z 21 ~Z 23 At least one of represents a sulfur atom, R A represents a hydrogen atom or a substituent, In formula (A3), Z 31 and Z 32 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and Z 31 and Z 32 At least one of represents a sulfur atom, R A represents a hydrogen atom or a substituent, In formula (A4), Z 41 and Z 42 One of them represents a sulfur atom, Z 41 and Z 42 The other one in represents -CR=, Z 43 and Z 44 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 43 and Z 44 The other one represents -CR=, R and R A Each independently represents a hydrogen atom or a substituent, In formula (A5), Z 51 and Z 52 One of them represents a sulfur atom, Z 51 and Z 52 The other one in represents -CR=, Z 53 and Z 54 One of them represents a sulfur atom, an oxygen atom or a selenium atom, and Z 53 and Z 54 The other one represents -CR=, R and R A Each independently represents a hydrogen atom or a substituent, In formula (A6), Z 61 ~Z 64 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and Z 61 ~Z 64 At least one of represents a sulfur atom, R A represents a hydrogen atom or a substituent, Ar 14 and Ar 15 Each independently represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, Ar 12 and Ar 13 Each independently represents any one of the groups represented by formula (2) to formula (4), In formulas (2) to (4), * A and* B represents the bonding position, In formula (2), X 21 and X 22 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and Y 21 and Y 22 Each independently represents a nitrogen atom or -CR=, R represents a hydrogen atom or a substituent, wherein, Y 21 and Y 22 At least one of represents a nitrogen atom, In formula (3), X 31 represents a sulfur atom, an oxygen atom, or a selenium atom, Y 31 ~Y 34 Each independently represents a nitrogen atom or -CR= and Y 31 ~Y 34 represents a nitrogen atom, R represents a hydrogen atom or a substituent, In formula (4), X 41 represents a sulfur atom, an oxygen atom, or a selenium atom, Y 41 ~Y 43 Each independently represents a nitrogen atom or -CR=, R represents a hydrogen atom or a substituent, However, the compound does not include a compound represented by the following formula:

14. The compound according to claim 13, wherein In the formula (A1), Z 11 and Z 12 One of them represents a sulfur atom, Z 11 and Z 12 The other one in represents -CR=, Z 13 and Z 14 One of them represents a sulfur atom or an oxygen atom, Z 13 and Z 14 The other one in represents -CR=, In the formula (A2), Z 21 ~Z 23 Each independently represents a sulfur atom or an oxygen atom, Z 21 ~Z 23 At least one of represents a sulfur atom, In the formula (A3), Z 31 and Z 32 Each independently represents a sulfur atom or an oxygen atom, Z 31 ~Z 32 At least one of represents a sulfur atom, In the formula (A4), Z 41 and Z 42 One of them represents a sulfur atom, Z 41 and Z 42 The other one in represents -CR=, Z 43 and Z 44 One of them represents a sulfur atom or an oxygen atom, Z 43 and Z 44 The other one in represents -CR=, In the formula (A5), Z 51 and Z 52 One of them represents a sulfur atom, Z 51 and Z 52 The other one in represents -CR=, Z 53 and Z 54 One of them represents a sulfur atom or an oxygen atom, Z 53 and Z 54 The other one in represents -CR=, In the formula (A6), Z 61 ~Z 64 Each independently represents a sulfur atom or an oxygen atom, Z 61 ~Z 64 At least one of represents a sulfur atom.

15. The compound according to claim 13 or 14, wherein In the formula (1), n11 is 1, Ar 11 It is a group represented by the above formula (A5).

16. The compound according to claim 13 or 14, wherein In the formula (2), X 21 and X 22 each independently represents a sulfur atom or an oxygen atom, In the formula (3), X 31 represents a sulfur atom or an oxygen atom, In the formula (4), X 41 represents a sulfur atom or an oxygen atom.

17. The compound according to claim 13 or 14, wherein In the formula (1), Ar 12 and Ar 13 Each independently represents any one of the groups represented by formula (5), formula (6), and formula (8) to formula (13), In formulas (5) to (13), * A and* B represents the bonding position, R A represents a hydrogen atom or a substituent.

18. The compound according to claim 13 or 14, wherein The molecular weight of the compound represented by the formula (1) is 550 to 1200.

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