Photoelectric conversion elements, imaging elements, optical sensors, compounds

Abstract

The present invention provides a photoelectric conversion element, an imaging element, a photosensor and a compound, wherein the photoelectric conversion element has a photoelectric conversion film with a narrow half-width of an absorption peak and excellent photoelectric conversion efficiency. The photoelectric conversion element of the present invention has a conductive film, a photoelectric conversion film and a transparent conductive film in sequence, wherein the photoelectric conversion film contains a compound represented by formula (1).

Description

Technical Field

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

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

[0003] Regarding a photoelectric conversion element using a photoelectric conversion film, for example, Patent Document 1 discloses a photoelectric conversion element having a photoelectric conversion film containing a specific compound.

[0004] Previous technical literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-167348 Summary of the invention

[0007] Technical issues to be solved by the invention

[0008] As one form of imaging element, a stacked imaging element can be cited, which is formed by stacking a plurality of photoelectric conversion elements of different types of received light. When light is incident on the imaging element, a portion of the incident light is absorbed by the photoelectric conversion element arranged on the incident side, and the transmitted light is further absorbed by the photoelectric conversion element arranged on the inner side. In such an imaging element, the half width of the absorption peak of each photoelectric conversion element is narrow, which makes it easy to separate colors, and is therefore preferred.

[0009] The present inventors have studied the characteristics of the photoelectric conversion element specifically described in the Example section of Patent Document 1 and found that the half width of the absorption peak of the photoelectric conversion film in the photoelectric conversion element is wide and further improvement is required.

[0010] Furthermore, photoelectric conversion elements are also required to have excellent photoelectric conversion efficiency.

[0011] In view of the above-mentioned actual situation, an object of the present invention is to provide a photoelectric conversion element having a photoelectric conversion film with a narrow half-value width of an absorption peak and excellent in photoelectric conversion efficiency.

[0012] Furthermore, another object of the present invention is to provide an imaging element, a photosensor, and a compound.

[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 using a compound having a predetermined structure in a photoelectric conversion film, thereby completing the present invention.

[0015] (1) A photoelectric conversion element comprising, in this order, a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein:

[0016] The photoelectric conversion film contains a compound represented by formula (1) described below.

[0017] In the formula (1) described below, B1 is preferably a group represented by the formula (B-1) described below.

[0018] (2) The photoelectric conversion element according to (1), wherein

[0019] The compound represented by the formula (1) described later is a compound represented by the formula (2) described later or a compound represented by the formula (2b) described later.

[0020] (3) The photoelectric conversion element according to (2), wherein

[0021] The group represented by the formula (B-1-1) described later in the formula (2) described later and the formula (2b) described later is a group represented by the formulas (J-1) to (J-5) described later.

[0022] (4) The photoelectric conversion element according to (3), wherein

[0023] The compound represented by the formula (1) described later is a compound represented by the formula (2) described later or the formula (2b) described later,

[0024] In the compound represented by the formula (2) or the formula (2b) described later, the group represented by the formula (B-1-1) described later is a group represented by the formula (J-1) or a group represented by the formula (J-2) described later.

[0025] (5) The photoelectric conversion element according to any one of (2) to (4), wherein

[0026] The compound represented by the above-mentioned formula (1) is a compound represented by the above-mentioned formula (2b), and Rc1 represents a group represented by the above-mentioned formula (R-2), a group represented by the above-mentioned formula (R-3), a group represented by the above-mentioned formula (R-4), a group represented by the above-mentioned formula (4A), or a polycyclic aromatic ring which may have a substituent.

[0027] (6) The photoelectric conversion element according to (5), wherein

[0028] The compound represented by the formula (1) described later is a compound represented by the formula (2b) described later,

[0029] In the compound represented by the above-mentioned formula (2b), the group represented by the above-mentioned formula (B-1-1) is the group represented by the above-mentioned formula (J-1), and Rc1 represents the group represented by the above-mentioned formula (4A) or a polycyclic aromatic ring which may have a substituent.

[0030] (7) The photoelectric conversion element according to (5) or (6), wherein

[0031] The compound represented by the formula (1) described later is a compound represented by the formula (2b-1) described later or a compound represented by the formula (2b-2) described later.

[0032] (8) The photoelectric conversion element according to (7), wherein

[0033] In the formula (2b-1) and the formula (2b-2) described below, Rc2 represents a group represented by the formula (5A) described below, a group represented by the formula (5B) described below, or a naphthyl group which may have a substituent.

[0034] (9) The photoelectric conversion element according to any one of (1) to (8), wherein

[0035] The photoelectric conversion film further comprises an n-type organic semiconductor.

[0036] The photoelectric conversion film has a bulk heterostructure formed in a state where the compound represented by the formula (1) described later and the n-type organic semiconductor are mixed.

[0037] (10) The photoelectric conversion element according to (9), wherein

[0038] The above-mentioned n-type organic semiconductor includes fullerenes selected from the group consisting of fullerenes and derivatives thereof.

[0039] (11) The photoelectric conversion element according to any one of (1) to (10), wherein

[0040] In addition to the photoelectric conversion film, one or more intermediate layers are provided between the conductive film and the transparent conductive film.

[0041] (12) An imaging element having the photoelectric conversion element according to any one of (1) to (11).

[0042] (13) The imaging element according to (12), further comprising another photoelectric conversion element that receives light of a wavelength different from that of the light received by the photoelectric conversion element.

[0043] (14) The imaging element according to (13), wherein

[0044] The above-mentioned photoelectric conversion element is stacked with the above-mentioned other photoelectric conversion element,

[0045] At least a portion of the incident light is transmitted through the photoelectric conversion element and then received by the other photoelectric conversion element.

[0046] (15) The imaging element according to (13) or (14), wherein

[0047] The above-mentioned photoelectric conversion element is a green photoelectric conversion element.

[0048] The other photoelectric conversion elements include a blue photoelectric conversion element and a red photoelectric conversion element.

[0049] (16) A photosensor having the photoelectric conversion element according to any one of (1) to (11).

[0050] (17) A compound represented by the formula (1) described later.

[0051] (18) The compound according to (17), which is a compound represented by the formula (2) described below or a compound represented by the formula (2b) described below.

[0052] (19) A compound according to (18), which is a compound represented by the above-mentioned formula (2b), and Rc1 represents a group represented by the above-mentioned formula (R-2), a group represented by the above-mentioned formula (R-3), and represents a group represented by the above-mentioned formula (R-4), a group represented by the above-mentioned formula (4A), or a polycyclic aromatic ring that may have a substituent.

[0053] (20) The compound according to (19), which is a compound represented by the formula (2b-1) described below or a compound represented by the formula (2b-2) described below.

[0054] Effects of the Invention

[0055] According to the present invention, it is possible to provide a photoelectric conversion element having a photoelectric conversion film having a narrow half-value width of an absorption peak and having excellent photoelectric conversion efficiency.

[0056] Furthermore, according to the present invention, an imaging element, a photosensor, and a compound can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 It is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element.

[0058] Figure 2 It is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element.

[0059] Figure 3It is a schematic cross-sectional view of one embodiment of an imaging element.

[0060] Figure 4 is compound (D-1) 1 H NMR (Nuclear Magnetic Resonance) spectroscopy.

[0061] Figure 5 is compound (D-2) 1 H NMR spectroscopy.

[0062] Figure 6 Compound (D-3) 1 H NMR spectroscopy.

[0063] Figure 7 Compound (D-4) 1 H NMR spectroscopy.

[0064] Figure 8 Compound (D-5) 1 H NMR spectroscopy.

[0065] Fig. 9 Compound (D-6) 1 H NMR spectroscopy.

[0066] Fig.10 Compound (D-7) 1 H NMR spectroscopy.

[0067] Fig.11 Compound (D-8) 1 H NMR spectroscopy.

[0068] Fig.12 Compound (D-9) 1 H NMR spectroscopy.

[0069] Fig.13 Compound (D-11) 1 H NMR spectroscopy.

[0070] Fig.14 Compound (D-14) 1 H NMR spectroscopy.

[0071] Fig.15 Compound (D-17) 1 H NMR spectroscopy.

[0072] Fig.16 Compound (D-18) 1 H NMR spectroscopy.

[0073] Fig.17 Compound (D-21) 1 H NMR spectroscopy.

[0074] Fig.18 Compound (D-22) 1 H NMR spectroscopy.

[0075] Fig.19 Compound (D-24) 1 H NMR spectroscopy.

[0076] Fig. 20 It is compound (D-25) 1 H NMR spectroscopy.

[0077] Fig.21 Compound (D-26) 1 H NMR spectroscopy. DETAILED DESCRIPTION

[0078] Hereinafter, preferred embodiments of the photoelectric conversion element of the present invention will be described.

[0079] In addition, in the present specification, for a substituent group that is not indicated as substituted or unsubstituted, the group may be further substituted with a substituent group (e.g., a substituent group W described below) within the range that does not impair the intended effect. For example, the symbol "alkyl" means an alkyl group that may be substituted with an unsubstituted alkyl group or a substituent group (e.g., a substituent group W described below).

[0080] In the present specification, examples of the "substituent" include the groups exemplified by the substituent W described later. The "substituent" is preferably an alkyl group, an aryl group or a heteroaryl group.

[0081] In this specification, "aromatic ring" refers to a ring showing aromaticity. The "aromatic ring" may have a substituent or may not have a substituent. Furthermore, the "aromatic ring" may be a "monocyclic aromatic ring" consisting of one ring showing aromaticity, or a "polycyclic aromatic ring" consisting of two or more rings condensed together.

[0082] In addition, a "polycyclic aromatic ring" has two or more rings showing aromaticity.

[0083] The aromatic ring may be any of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

[0084] The substituents possessed by the above-mentioned "aromatic ring (monocyclic aromatic ring or polycyclic aromatic ring)" may be bonded to each other to further form a ring.

[0085] Examples of the monocyclic aromatic ring include a monocyclic aromatic hydrocarbon ring such as a benzene ring, and a monocyclic aromatic heterocyclic ring such as a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, and an oxazole ring.

[0086] Examples of the polycyclic aromatic ring include polycyclic aromatic hydrocarbon rings such as a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring, and polycyclic aromatic heterocyclic rings such as a quinoline ring and a benzothiophene ring.

[0087] In the present specification, a "non-aromatic ring" refers to a ring that does not exhibit aromaticity. A "non-aromatic ring" may or may not have a substituent. Furthermore, a "non-aromatic ring" may be a "monocyclic non-aromatic ring" consisting of one ring that does not exhibit aromaticity, or a "polycyclic non-aromatic ring" that is composed of two or more non-aromatic rings fused together and does not exhibit aromaticity as a whole.

[0088] In this specification, the substituents of the non-aromatic ring may be bonded to each other to form a ring, and the substituents of the non-aromatic ring may be bonded to each other to form an aromatic ring. Furthermore, the non-aromatic ring may have an aromatic ring as a substituent (or a part thereof).

[0089] In addition, the term "non-aromatic ring not including an aromatic structure" does not include an aromatic ring as a part of the non-aromatic ring. For example, in a non-aromatic ring not including an aromatic structure, a substituent (or a part thereof) of the non-aromatic ring is not an aromatic ring, and a ring formed by mutually bonding substituents of the non-aromatic ring is not an aromatic ring.

[0090] Examples of the non-aromatic ring include an aliphatic hydrocarbon ring (cycloalkane ring, etc.) and a cycloolefin ring.

[0091] Furthermore, in the present specification, a numerical range expressed using “to” means a range including the numerical values ​​described before and after “to” as the lower limit and the upper limit.

[0092] In the present specification, the hydrogen atom may be a light hydrogen atom (ordinary hydrogen atom) or a heavy hydrogen atom (such as a dihydrogen atom).

[0093] As a characteristic point of the photoelectric conversion element of the present invention, it can be mentioned that a bulky substituent is introduced into a compound represented by formula (1) described later and contained in the photoelectric conversion film (hereinafter also referred to as a "specific compound"). It is speculated as follows: by introducing a bulky substituent into the specific compound (for example, the positions of R1 to R4 in formula (1) described later), the specific compounds are mutually subjected to steric repulsion to such an extent that excellent photoelectric conversion efficiency can be obtained, and by suppressing the association of the specific compounds in the photoelectric conversion film, the half width of the absorption peak of the photoelectric conversion film is narrowed, and excellent photoelectric conversion efficiency can be obtained.

[0094] Figure 1 Schematic cross-sectional view of one embodiment of the photoelectric conversion element of the present invention is shown in FIG.

[0095] Figure 1 The photoelectric conversion element 10a shown has a structure in which the following films are stacked in sequence: a conductive film (hereinafter also referred to as a lower electrode) 11 functioning 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 functioning as an upper electrode.

[0096] exist Figure 2 Another example of the configuration 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 2 The 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 appropriately according to the application and characteristics.

[0097] In the photoelectric conversion element 10 a (or 10 b ), light is preferably incident on the photoelectric conversion film 12 via the upper electrode 15 .

[0098] When the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and preferably 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.

[0099] In addition, regarding the voltage application method, Figure 1 and Figure 2 In the embodiment, the voltage is preferably applied in such a manner that the electron blocking film 16A side becomes a cathode and the photoelectric conversion film 12 side becomes an anode. When the photoelectric conversion element 10a (or 10b) is used as a photosensor and when incorporated in an imaging element, voltage can be applied by the same method.

[0100] As will be described in detail later, the photoelectric conversion element 10 a (or 10 b ) can be preferably used for imaging element applications.

[0101] Hereinafter, the aspects of each layer constituting the photoelectric conversion element of the present invention will be described in detail.

[0102] <Photoelectric conversion film>

[0103] The photoelectric conversion film is a film containing a specific compound as a photoelectric conversion material. By using the compound, a photoelectric conversion film having a narrow half-width of an absorption peak and a photoelectric conversion element having excellent photoelectric conversion efficiency can be obtained.

[0104] Hereinafter, the specific compounds will be described in detail.

[0105] In formula (1), any geometric isomers distinguishable based on the C=C double bond formed by the carbon atom to which R5 (or R6) is bonded and the carbon atom adjacent thereto are included in formula (1). That is, both the cis-isomer and the trans-isomer distinguishable based on the C=C double bond are included in formula (1).

[0106] The same also applies to the following formula (2), formula (2b), formulas (3) to (7), formula (2b-1), and formula (2b-2).

[0107] [Chemical formula 1]

[0108]

[0109] In formula (1), R1 represents an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a group represented by formula (R-1), a group represented by formula (R-2), a group represented by formula (R-3) or a group represented by formula (R-4).

[0110] [Chemical formula 2]

[0111]

[0112] The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 30, more preferably 6 to 18, and further preferably 6. The aryl group may be a monocyclic structure or a condensed ring structure in which two or more rings are condensed (condensed ring structure).

[0113] As the aryl group, for example, a phenyl group, a naphthyl group or an anthracenyl group is preferred, and a phenyl group is more preferred.

[0114] Examples of the substituent that the aryl group may have include the substituent W described below, and examples thereof include an alkyl group and a halogen atom, and an alkyl group is preferred.

[0115] The aryl group may have various substituents.

[0116] When the aryl group has a substituent, the number of the substituents possessed by the aryl group is not particularly limited, but is preferably 1 to 5, and more preferably 2 to 3.

[0117] In addition, the aryl group is preferably an aryl group substituted with a substituent other than a halogen atom.

[0118] The number of carbon atoms in the heteroaryl group (monovalent aromatic heterocyclic group) is not particularly limited, but is preferably 3 to 30, more preferably 3 to 18.

[0119] The heteroaryl group has a hetero atom other than a carbon atom and a hydrogen atom. Examples of the hetero atom include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom and a boron atom, and a sulfur atom, an oxygen atom or a nitrogen atom is preferred.

[0120] The number of hetero atoms in the heteroaryl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 to 2.

[0121] The number of ring members of the heteroaryl group is not particularly limited, and is preferably 3 to 8, more preferably 5 to 7, and further preferably 5 to 6. In addition, the heteroaryl group may be a monocyclic structure or a fused ring structure formed by condensing two or more rings. When it is a fused ring structure, it may contain an aromatic hydrocarbon ring (e.g., a benzene ring) without a heteroatom.

[0122] Examples of the heteroaryl group include furanyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthidinyl, pteridinyl, pyrazinyl, quinoxalinyl, pyrimidinyl, quinazolinyl, pyridazinyl, cinnolinyl, phthalazinyl, triazinyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, imidazolyl, benzimidazolyl, pyrazolyl, indazolyl, isoxazolyl, benzisoxazolyl, isothiazolyl, benzisothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, pyrrolyl, indolyl, imidazopyridinyl and carbazolyl.

[0123] Among them, a furyl group, a thienyl group, a pyridyl group, a quinolyl group, an isoquinolyl group or a carbazolyl group is preferred.

[0124] Examples of the substituent which the heteroaryl group may have include the same substituents as those which the above aryl group may have.

[0125] When the heteroaryl group has a substituent, the number of the substituents possessed by the heteroaryl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0126] In formula (R-1), Ra1 represents a hydrogen atom or a substituent. The substituent represented by Ra1 is preferably an alkyl group (preferably having 1 to 4 carbon atoms).

[0127] Here, Ra1 is neither an aryl group which may have a substituent nor a heteroaryl group which may have a substituent.

[0128] *Indicates bonding position.

[0129] In formula (R-2), Ra2 and Ra3 each independently represent a substituent. As the substituent represented by Ra2 and Ra3, an alkyl group (preferably having 1 to 4 carbon atoms) or an aryl group is preferred. The definition of the aryl group is the same as the definition of the aryl group described in R1.

[0130] Ra2 and Ra3 may be bonded to each other to form a ring. More specifically, Ra2 and Ra3 may be bonded to each other via a single bond or a linking group to form a ring.

[0131] Examples of the ring formed by mutually bonding Ra2 and Ra3 include an aromatic ring (aromatic hydrocarbon ring or aromatic heterocyclic ring) and a non-aromatic ring.

[0132] *Indicates bonding position.

[0133] In formula (R-3), Ra4 to Ra6 each independently represent a substituent. The substituent represented by Ra4 to Ra6 is preferably an alkyl group (preferably having 1 to 4 carbon atoms) or an aryl group. The definition of the aryl group is the same as the definition of the aryl group described in R1.

[0134] Ra4 to Ra6 may be bonded to each other to form a ring. More specifically, Ra4 and Ra5, Ra5 and Ra6, and Ra4 and Ra6 may be bonded to each other independently via a single bond or a linking group to form a ring.

[0135] The type of the ring to be formed can be exemplified by a ring formed by bonding Ra2 and Ra3 to each other.

[0136] *Indicates bonding position.

[0137] In formula (R-4), Ra 12 The definitions of the aryl group and the heteroaryl group are the same as those of the aryl group and the heteroaryl group explained for R1.

[0138] *Indicates bonding position.

[0139] When R1 is a group other than the group represented by formula (R-1), R1 is preferably a group represented by formula (R-2), a group represented by formula (R-3), a group represented by formula (R-4), a group represented by formula (4A), or a polycyclic aromatic ring that may have a substituent, more preferably a group represented by formula (4A) or a polycyclic aromatic ring that may have a substituent, and further preferably a group represented by formula (5A), a group represented by formula (5B), or a naphthyl group that may have a substituent.

[0140] [Chemical formula 3]

[0141]

[0142] In formula (4A), T 1 ~T 4 Represent CR independently e12 or nitrogen atom. e12 represents a hydrogen atom or a substituent (an alkyl group having 1 to 4 carbon atoms, a halogen atom, etc.). f2 It represents an alkyl group (preferably having 1 to 4 carbon atoms), a cyano group, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

[0143] The definitions of the aryl group and the heteroaryl group are the same as those of the aryl group described in R1.

[0144] In addition, in formula (4A), when R e12 When there are multiple e12 can be the same or different from each other, and R e12 They may be bonded to each other to form a non-aromatic ring having no aromatic ring structure.

[0145] [Chemical formula 4]

[0146]

[0147] In formula (5A), R e1 ~R e4 R each independently represents a hydrogen atom or a substituent (an alkyl group having 1 to 4 carbon atoms, a halogen atom, etc.). e1 ~R e4 They may be bonded to each other to form a non-aromatic ring that does not contain an aromatic ring structure. f1 It represents an alkyl group (preferably having 1 to 4 carbon atoms).

[0148] [Chemical formula 5]

[0149]

[0150] In formula (5B), R e5 ~R e11 and R e13 ~R e14 R each independently represents a hydrogen atom or a substituent (such as an alkyl group having 1 to 4 carbon atoms). e5 ~R e11 and R e13 ~R e14 They may be bonded to each other to form a ring.

[0151] Among them, R e13 and R e14 Preferably, one or two of the groups represent a substituent (such as an alkyl group having 1 to 4 carbon atoms).

[0152] A represents an aromatic ring.

[0153] Among them, from the viewpoint of more excellent effects of the present invention, an aromatic hydrocarbon ring is preferred, and a naphthalene ring or a fluorene ring is more preferred.

[0154] R2 and R3 each independently represent a substituent. As the substituent represented by R2 and R3, an alkyl group (preferably having 1 to 4 carbon atoms) or an aryl group is preferred. The definition of the aryl group is the same as the definition of the aryl group described in R1.

[0155] The total number of carbon atoms contained in R2 and R3 is not particularly limited, and is often 2 or more. From the viewpoint of further excellent effects of the present invention, it is preferably 4 or more. The total number of carbon atoms is not particularly limited, and is preferably 12 or less.

[0156] R2 and R3 may be bonded to each other to form a ring. More specifically, R2 and R3 may be independently bonded to each other via a single bond or a linking group to form a ring.

[0157] The type of the ring to be formed can be exemplified by a ring formed by bonding Ra2 and Ra3 to each other.

[0158] R4 to R6 each independently represent a hydrogen atom or a substituent. The substituent represented by R4 to R6 is preferably an alkyl group (preferably having 1 to 4 carbon atoms) or an aryl group. The definition of the aryl group is the same as the definition of the aryl group described in R1.

[0159] From the viewpoint of achieving more excellent effects of the present invention, it is preferred that R5 and R6 are hydrogen atoms.

[0160] n represents an integer of 0 to 18. Among them, 0 to 5 are preferred, and 0 to 3 are more preferred, from the viewpoint of further improving the effects of the present invention.

[0161] When n is 2 or more, a plurality of R4 may be bonded to each other to form a fluorene ring or a non-aromatic ring not including an aromatic ring structure.

[0162] When A is a benzene ring, n is 1 or more, and at least one of R4 represents a Hammett substituent constant σ p Among them, from the viewpoint of further improving the effect of the present invention, the above-mentioned substituent is preferably a substituent having a Hammett substituent constant σ p The substituent is -0.10 or less. p The lower limit of is preferably -0.80 or more.

[0163] As the Hammett substituent constant σ pThe substituent having a moiety of 0.05 or less may include, for example, an alkyl group, an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heteroaryl group (also referred to as a heterocyclic group), a silyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclicoxy group, an amino group (including an anilino group), a mercapto group, an alkylthio group, an arylthio group, and a heterocyclicthio group. Among them, a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group is preferred.

[0164] Here, the Hammett substituent constant σp is described. Hammett's rule is an empirical rule proposed by LP Hammett in 1935 in order to quantitatively discuss the influence of substituents on the reaction or equilibrium of benzene derivatives. Its rationality is now widely recognized. For example, the substituent constant σp obtained in Hammett's rule is described in detail in Chem. Rev. 1991, 91, 165-195. In addition, in the present invention, although the substituent is limited or described by the Hammett substituent constant σp, this does not mean that the value known in the literature that can be derived in the above-mentioned literature is limited to a certain substituent, but even if its value is unknown in the literature, it also includes substituents that can be included in its range when measured based on Hammett's rule.

[0165] The total number of carbon atoms contained in R1 to R4 is 5 or more. That is, the total number of carbon atoms contained in R1, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and the number of carbon atoms contained in R4 is 5 or more. In addition, when n is 0, the number of carbon atoms contained in R4 is set to 0.

[0166] Furthermore, when n is 2 or more, the total of the number of carbon atoms contained in R1, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and the number of carbon atoms of each of two or more R4 is 5 or more.

[0167] Furthermore, when two R4s are bonded to form a ring, the total number of carbon atoms contained in R1, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and the number of carbon atoms contained in the ring formed by bonding R4s is 5 or more.

[0168] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 7 or more, and more preferably 9 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0169] When R1 represents an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a group represented by the formula (R-2), a group represented by the formula (R-3) or a group represented by the formula (R-4), B1 represents a group represented by the formula (B-1-1) or a group represented by (B-1-2); when R1 represents a group represented by the formula (R-1), B1 represents a group represented by the formula (B-2) or a group represented by the formula (B-3).

[0170] In formula (B-1-1), formula (B-1-2), formula (B-2), and formula (B-3), * represents a connection position.

[0171] [Chemical formula 6]

[0172]

[0173] In formula (B-1-1), E represents a ring which contains at least two carbon atoms and which may have a substituent.

[0174] E represents a ring containing at least two carbon atoms. In addition, the two carbon atoms refer to the carbon atom bonded to Z1 in formula (B-1-1) by a double bond and the carbon atom adjacent to the carbon atom bonded to Z1 by a double bond, and any of the carbon atoms constitute E.

[0175] The number of carbon atoms of E is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 15. The above-mentioned number of carbon atoms is a number including the two carbon atoms indicated in the formula.

[0176] E may have a hetero atom, and examples thereof 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. A nitrogen atom, a sulfur atom, or an oxygen atom is preferred.

[0177] E may have a substituent.

[0178] The number of heteroatoms in E is preferably 0 to 10, more preferably 0 to 5, and still more preferably 0 to 3. The above number of heteroatoms does not include the number of heteroatoms contained in Z1.

[0179] E may or may not be aromatic.

[0180] E may be a monocyclic structure or a condensed ring structure, but is preferably a condensed ring containing a 5-membered ring, a 6-membered ring, or at least one of a 5-membered ring and a 6-membered ring. The number of rings forming the condensed ring is preferably 1 to 4, more preferably 1 to 3.

[0181] Z1 represents an oxygen atom, a sulfur atom, NR Z1 or CR Z2 R Z3 . R Z1represents a hydrogen atom or a substituent, R Z2 and R Z3 Each independently represents a cyano group or a -COOR Z4 . R Z4 It represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

[0182] Z 1 An oxygen atom is preferred.

[0183] In formula (B-1-2), Rb 21 and Rb 22 Each independently represents a cyano group or -COORb 23 . Rb 23 It represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

[0184] In formula (B-2), G represents -CO-, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -NRb1-, -CRb2Rb3- or -SiRb4Rb5-.

[0185] Rb1~Rb5 and Rb7~Rb 10 Each independently represents a hydrogen atom or a substituent.

[0186] Rb7~Rb 10 They can bond to each other to form a ring. For example, Rb7 and Rb8, Rb8 and Rb9, and Rb9 and Rb 10 They may be independently bonded to each other via a single bond or a linking group to form a ring.

[0187] The type of the ring to be formed can be exemplified by a ring formed by bonding Ra2 and Ra3 to each other.

[0188] In formula (B-3), Ch represents =CRa7Ra8, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom.

[0189] Ra7 and Ra8 each independently represent a hydrogen atom or a substituent.

[0190] Ra7 and Ra8 may be bonded to each other to form a ring. More specifically, Ra7 and Ra8 may be bonded to each other via a single bond or a linking group to form a ring.

[0191] The type of the ring to be formed can be exemplified by a ring formed by bonding Ra2 and Ra3 to each other.

[0192] When R1 represents an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a group represented by formula (R-2), a group represented by formula (R-3) or a group represented by formula (R-4), B1 is preferably a group represented by formula (B-1-1).

[0193] From the viewpoint of achieving more excellent effects of the present invention, the group represented by formula (B-1-1) is preferably a group represented by formula (B-1).

[0194] [Chemical formula 7]

[0195]

[0196] In (B-1), D represents -CO-, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -NRb1-, -CRb2Rb3- or -SiRb4Rb5-.

[0197] Rb1 to Rb5 each independently represent a hydrogen atom or a substituent.

[0198] E2 represents a ring containing at least two carbon atoms. In addition, the two carbon atoms refer to the carbon atom in the carbonyl group in formula (B-1) and the carbon atom adjacent to the carbon atom in the carbonyl group, and any of the carbon atoms constitutes E2.

[0199] The number of carbon atoms in E2 is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 15. The above-mentioned number of carbon atoms includes the two carbon atoms indicated in the formula.

[0200] E2 may have a hetero atom, for example, 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, preferably a nitrogen atom, a sulfur atom or an oxygen atom.

[0201] E2 may have a substituent.

[0202] The number of heteroatoms in E2 is preferably 0 to 10, more preferably 0 to 5, and further preferably 0 to 3. The number of heteroatoms is a number excluding the number of oxygen atoms contained in the carbonyl group constituting E2 indicated in formula (B-1).

[0203] E2 may or may not be aromatic.

[0204] E2 may be a monocyclic structure or a condensed ring structure, but is preferably a condensed ring containing at least one of a 5-membered ring, a 6-membered ring, or a 5-membered ring and a 6-membered ring. The number of rings forming the condensed ring is preferably 1 to 4, more preferably 1 to 3.

[0205] From the viewpoint of achieving more excellent effects of the present invention, the group represented by formula (B-1-1) is more preferably a group represented by formulas (J-1) to (J-5), further preferably a group represented by formulas (J-1) to (J-2), and particularly preferably a group represented by formula (J-1).

[0206] [Chemical formula 8]

[0207]

[0208] In formula (J-1), Rg1 to Rg4 each independently represent a hydrogen atom or a substituent.

[0209] Rg1 to Rg4 may be bonded to each other to form a ring. For example, Rg1 and Rg2, Rg2 and Rg3, and Rg3 and Rg4 may be bonded to each other independently via a single bond or a linking group to form a ring.

[0210] The type of the ring to be formed can be exemplified by a ring formed by bonding Ra2 and Ra3 to each other.

[0211] K represents -CO-, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -NRb1-, -CRb2Rb3- or -SiRb4Rb5-. Rb1 to Rb5 each independently represent a hydrogen atom or a substituent.

[0212] In formula (J-2), Rg5 and Rg6 each independently represent a hydrogen atom or a substituent.

[0213] Ch represents =CRa7Ra8, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. Ra7 and Ra8 each independently represent a hydrogen atom or a substituent.

[0214] Ra7 and Ra8 may be bonded to each other to form a ring. More specifically, Ra7 and Ra8 may be bonded to each other via a single bond or a linking group to form a ring.

[0215] The type of the ring to be formed can be exemplified by a ring formed by bonding Ra2 and Ra3 to each other.

[0216] In formula (J-3), Rg7 represents a hydrogen atom or a substituent.

[0217] Ch represents =CRa7Ra8, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. Ra7 and Ra8 each independently represent a hydrogen atom or a substituent.

[0218] Ra7 and Ra8 may bond to each other to form a ring.

[0219] L represents an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom.

[0220] In formula (J-4), Rg8 and Rg9 each independently represent a hydrogen atom or a substituent.

[0221] Rg8 and Rg9 may be bonded to each other to form a ring. More specifically, Rg8 and Rg9 may be independently bonded to each other via a single bond or a linking group to form a ring.

[0222] The type of the ring to be formed can be exemplified by a ring formed by bonding Ra2 and Ra3 to each other.

[0223] K represents -CO-, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -NRb1-, -CRb2Rb3- or -SiRb4Rb5-. Rb1 to Rb5 each independently represent a hydrogen atom or a substituent.

[0224] In formula (J-5), Rg 10 ~Rg 12 Each independently represents a hydrogen atom or a substituent.

[0225] R 10 and Rg 11 They may be bonded to each other to form a ring.

[0226] Ch represents =CRa7Ra8, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. Ra7 and Ra8 each independently represent a hydrogen atom or a substituent. Ra7 and Ra8 may be bonded to each other to form a ring.

[0227] From the viewpoint of optimizing the vapor deposition suitability, the specific compound does not have any of a carboxyl group, a carboxyl salt, a phosphoric acid group, a phosphoric acid salt, a sulfonic acid group, and a sulfonic acid salt.

[0228] From the viewpoint of achieving more excellent effects of the present invention, the specific compound is preferably a compound represented by formula (2), a compound represented by formula (2b), a compound represented by formula (5), a compound represented by formula (6), or a compound represented by formula (7).

[0229] [Chemical formula 9]

[0230]

[0231] In formula (2), R2, R3, R5 and R6 are as defined above.

[0232] Rc1 represents an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a group represented by formula (R-2), a group represented by formula (R-3) or a group represented by formula (R-4). The definitions and preferred embodiments of each group are as described above.

[0233] R7~R 10Each independently represents a hydrogen atom or a substituent. 10 The substituent represented by is preferably an alkyl group (preferably having 1 to 4 carbon atoms) or an aryl group. The definition of the aryl group is the same as the definition of the aryl group explained in R1.

[0234] R7~R 10 They can be bonded to each other to form a non-aromatic ring that does not contain an aromatic ring structure. For example, R7 and R8, R8 and R9, and R9 and R 10 The olefin(e) and olefin(e) rings may be independently bonded to each other via a single bond or a linking group to form a non-aromatic ring having no aromatic ring structure.

[0235] R7~R 10 At least one of them represents a substituent having a Hammett's substituent constant σp of 0.05 or less. The definition and preferred range of the substituent having a Hammett's substituent constant σp of 0.05 or less are as described above.

[0236] Among them, from the viewpoint of further improving the effect of the present invention, R7 to R 10 Only one of them represents a substituent having a Hammett's substituent constant σp of 0.05 or less.

[0237] Rc1, R2, R3 and R7~R 10 The total number of carbon atoms contained in Rc1, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, the number of carbon atoms contained in R7, the number of carbon atoms contained in R8, the number of carbon atoms contained in R9, and R 10 The total number of carbon atoms contained in is 5 or more.

[0238] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 11 or more, and more preferably 15 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0239] B2 represents a group represented by the above-mentioned formula (B-1-1).

[0240] However, the compound represented by formula (2) does not have any of a carboxyl group, a salt of a carboxyl group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.

[0241] [Chemical formula 10]

[0242]

[0243] In formula (2b), Rc1, R2, R3, R4, R5, R6, n and B2 are as defined above.

[0244] Among them, in formula (2b), Rc1 is preferably a group represented by formula (R-2), a group represented by formula (R-3), a group represented by formula (R-4), a group represented by formula (4A), or a polycyclic aromatic ring that may have a substituent, and more preferably a group represented by formula (5A), a group represented by formula (5B), or a naphthyl group that may have a substituent.

[0245] A2 represents a polycyclic aromatic ring which may have a substituent. As the polycyclic aromatic ring, a naphthalene ring or a fluorene ring is preferred.

[0246] The total number of carbon atoms contained in Rc1 and R2 to R4 is 5 or more.

[0247] That is, the total number of carbon atoms contained in Rc1, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and the number of carbon atoms contained in R4 is greater than or equal to 5. When n is 0, the number of carbon atoms contained in R4 is set to 0.

[0248] Furthermore, when n is 2 or more, the total of the number of carbon atoms contained in R1, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and the number of carbon atoms of each of two or more R4s is 5 or more.

[0249] Furthermore, when two R4s are bonded to form a ring, the total number of carbon atoms contained in R1, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and the number of carbon atoms contained in the ring formed by bonding R4s is 5 or more.

[0250] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 7 or more, and more preferably 9 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0251] However, the compound represented by formula (2b) does not have any of a carboxyl group, a salt of a carboxyl group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.

[0252] More specifically, the compound represented by formula (2b) includes a compound represented by formula (3) and a compound represented by formula (4).

[0253] [Chemical formula 11]

[0254]

[0255] In formula (3), Rc1, R2, R3, R5, R6 and B2 are as defined above.

[0256] R 11 ~R 16 Each independently represents a hydrogen atom or a substituent.11 ~R 16 The substituent represented by is preferably an alkyl group (preferably having 1 to 4 carbon atoms) or an aryl group. The definition of the aryl group is the same as the definition of the aryl group explained in R1.

[0257] R 11 ~R 16 They may be bonded to each other to form a fluorene ring or a non-aromatic ring without an aromatic ring structure. 11 With R 12 , R 12 With R 13 , R 13 With R 14 , R 14 With R 15 , and, R 15 With R 16 They may be independently bonded to each other via a single bond or a linking group to form a fluorene ring or a non-aromatic ring not including an aromatic ring structure.

[0258] Rc1, R2, R3 and R 11 ~R 16 The total number of carbon atoms contained in Rc1, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and R 11 The number of carbon atoms contained in R 12 The number of carbon atoms contained in R 13 The number of carbon atoms contained in R 14 The number of carbon atoms contained in R 15 The number of carbon atoms contained in 16 The total number of carbon atoms contained in is 5 or more.

[0259] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 11 or more, and more preferably 15 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0260] However, the compound represented by formula (3) does not have any of a carboxyl group, a salt of a carboxyl group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.

[0261] [Chemical formula 12]

[0262]

[0263] In formula (4), Rc1, R2, R3, R5, R6 and B2 are as defined above.

[0264] R 17 ~R 24 Each independently represents a hydrogen atom or a substituent.17 ~R 24 The substituent represented by is preferably an alkyl group (preferably having 1 to 4 carbon atoms) or an aryl group. The definition of the aryl group is the same as the definition of the aryl group explained in R1.

[0265] R 17 ~R 24 They may be bonded to each other to form a fluorene ring or a non-aromatic ring without an aromatic ring structure. 17 With R 18 , R 18 With R 19 , R 19 With R 20 , R 20 With R 21 , R 21 With R 22 , R 22 With R 23 , and, R 23 With R 23 They may be independently bonded to each other via a single bond or a linking group to form a fluorene ring or a non-aromatic ring without an aromatic ring structure. 18 With R 19 can be bonded to form a fluorene ring. In this case, R 18 With R 19 The directly bonded carbon atom serves as a spiro atom to form a 9,9′-spirobi[9H-fluorene] ring.

[0266] Rc1, R2, R3 and R 17 ~R 24 The total number of carbon atoms contained in Rc1, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and R 11 The number of carbon atoms contained in R 17 The number of carbon atoms contained in R 18 The number of carbon atoms contained in R 19 The number of carbon atoms contained in R 20 The number of carbon atoms contained in R 21 The number of carbon atoms contained in R 22 The number of carbon atoms contained in R 23 The number of carbon atoms and R 24 The total number of carbon atoms contained in is 5 or more.

[0267] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 11 or more, and more preferably 15 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0268] However, the compound represented by formula (4) does not have any of a carboxyl group, a carboxyl salt, a phosphoric acid group, a phosphoric acid salt, a sulfonic acid group, and a sulfonic acid salt.

[0269] [Chemical formula 13]

[0270]

[0271] In formula (5), R2, R3, R5 and R6 are as defined above.

[0272] In formula (5), Rc2 represents a group represented by the above-mentioned formula (R-1).

[0273] R7~R 10 Each independently represents a hydrogen atom or a substituent, R7 to R 10 They may be bonded to each other to form a non-aromatic ring that does not contain an aromatic ring structure. 10 At least one of the following represents the Hammett substituent constant σ p The substituent has a molecular weight of 0.05 or less.

[0274] R7~R 10 The definition and preferred range of are the same as those described in formula (2).

[0275] Rc2, R2, R3 and R7~R 10 The total number of carbon atoms contained in Rc2, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, the number of carbon atoms contained in R7, the number of carbon atoms contained in R8, the number of carbon atoms contained in R9 and R 10 The total number of carbon atoms contained in is 5 or more.

[0276] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 11 or more, and more preferably 15 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0277] B3 represents a group represented by the above-mentioned formula (B-2) or a group represented by the above-mentioned formula (B-3).

[0278] However, the compound represented by formula (5) does not have any of a carboxyl group, a salt of a carboxyl group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.

[0279] [Chemical formula 14]

[0280]

[0281] In formula (6), Rc2, R2, R3, R5, R6 and B3 are as defined above.

[0282] In formula (6), Rc2 represents a group represented by the above-mentioned formula (R-1).

[0283] R 11 ~R 16 Each independently represents a hydrogen atom or a substituent, R 11 ~R 16 They may be bonded to each other to form a fluorene ring or a non-aromatic ring having no aromatic ring structure.

[0284] R 11 ~R 16 The definition and preferred range of are the same as those described in formula (3).

[0285] Rc2, R2, R3 and R 11 ~R 16 The total number of carbon atoms contained in is 5 or more. That is, the number of carbon atoms contained in Rc2, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and R 11 The number of carbon atoms contained in R 12 The number of carbon atoms contained in R 13 The number of carbon atoms contained in R 14 The number of carbon atoms contained in R 15 The number of carbon atoms and R 16 The total number of carbon atoms contained in is 5 or more.

[0286] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 11 or more, and more preferably 15 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0287] The compound represented by formula (6) does not have any of a carboxyl group, a carboxyl salt, a phosphate group, a phosphate salt, a sulfonic acid group, and a sulfonic acid salt.

[0288] [Chemical formula 15]

[0289]

[0290] In formula (7), Rc2, R2, R3, R5, R6 and B3 are as defined above.

[0291] In formula (7), Rc2 represents a group represented by the above-mentioned formula (R-1).

[0292] R 17 ~R 24 Each independently represents a hydrogen atom or a substituent, R 17 ~R 24They may be bonded to each other to form a fluorene ring or a non-aromatic ring having no aromatic ring structure.

[0293] R 17 ~R 24 The definition and preferred range of are the same as those described in formula (4).

[0294] Rc2, R2, R3 and R 17 ~R 24 The total number of carbon atoms contained in is 5 or more. That is, the number of carbon atoms contained in Rc2, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and R 17 The number of carbon atoms contained in R 18 The number of carbon atoms contained in R 19 The number of carbon atoms contained in R 20 The number of carbon atoms contained in R 21 The number of carbon atoms contained in R 22 The number of carbon atoms contained in R 23 The number of carbon atoms and R 24 The total number of carbon atoms contained in is 5 or more.

[0295] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 11 or more, and more preferably 15 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0296] However, the compound represented by formula (7) does not have any of a carboxyl group, a carboxyl salt, a phosphoric acid group, a phosphoric acid salt, a sulfonic acid group, and a sulfonic acid salt.

[0297] Among them, from the viewpoint of further improving the effect of the present invention, it is preferred that the compound represented by formula (1) is at least one selected from the group consisting of a compound represented by formula (3), a compound represented by formula (4), a compound represented by formula (6) and a compound represented by formula (7),

[0298] In the compound represented by the above formula (3), the group represented by the formula (B-1-1) is a group represented by the formula (J-1) or a group represented by the formula (J-2),

[0299] In the compound represented by the above formula (4), the group represented by the formula (B-1-1) is a group represented by the formula (J-1) or a group represented by the formula (J-2).

[0300] Furthermore, it is more preferred that the compound represented by formula (1) is at least one selected from the group consisting of a compound represented by formula (3), a compound represented by formula (4), a compound represented by formula (6), and a compound represented by formula (7).

[0301] In the compound represented by the above formula (3), the group represented by the formula (B-1-1) is a group represented by the formula (J-1) or a group represented by the formula (J-2), and Rc1 represents an aryl group which may be substituted by a substituent other than a halogen atom, a heteroaryl group which may have a substituent, a group represented by the formula (R-2) or a group represented by the formula (R-3),

[0302] In the compound represented by the above formula (4), the group represented by the formula (B-1-1) is a group represented by the formula (J-1) or a group represented by the formula (J-2), and Rc1 represents an aryl group which may be substituted by a substituent other than a halogen atom, a heteroaryl group which may have a substituent, a group represented by the formula (R-2) or a group represented by the formula (R-3),

[0303] In the compound represented by the above formula (6), B3 represents a group represented by the formula (B-2),

[0304] In the compound represented by the above formula (7), B3 represents a group represented by the formula (B-2).

[0305] It is further preferred that the compound represented by formula (1) is at least one selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4).

[0306] In the compound represented by the above formula (3), the group represented by the formula (B-1-1) is a group represented by the formula (J-1), and Rc1 represents an aryl group which may be substituted by a substituent other than a halogen atom or a heteroaryl group which may have a substituent,

[0307] In the compound represented by formula (4), the group represented by formula (B-1-1) is a group represented by formula (J-1), and Rc1 represents an aryl group which may be substituted by a substituent other than a halogen atom or a heteroaryl group which may have a substituent, and the total number of carbon atoms contained in R2 and R3 is 4 or more.

[0308] Furthermore, from the viewpoint of further improving the effects of the present invention, it is also preferred that the compound represented by formula (1) is a compound represented by formula (2b-1) or a compound represented by formula (2b-2).

[0309] [Chemical formula 16]

[0310]

[0311] In formula (2b-1), R2, R3, R5, R6, R 11 ~R 16 and Rg1 to Rg4 are as defined above.

[0312] Rc3 represents a group represented by formula (4A) or a polycyclic aromatic ring which may have a substituent, preferably a group represented by formula (5A), a group represented by formula (5B) or a naphthyl group which may have a substituent.

[0313] Rc3, R2, R3 and R 11 ~R 16 The total number of carbon atoms contained in Rc3, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and R 11 The number of carbon atoms contained in R 12 The number of carbon atoms contained in R 13 The number of carbon atoms contained in R 14 The number of carbon atoms contained in R 15 The number of carbon atoms and R 16 The total number of carbon atoms contained in is 5 or more.

[0314] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 11 or more, and more preferably 15 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0315] The compound represented by formula (2b-1) does not have any of a carboxyl group, a carboxyl salt, a phosphate group, a phosphate salt, a sulfonic acid group, and a sulfonic acid salt.

[0316] [Chemical formula 17]

[0317]

[0318] In formula (2b-2), Rc3, R2, R3, R5, R6, R 17 ~R 24 and Rg1 to Rg4 are as defined above.

[0319] Rc3, R2, R3 and R 17 ~R 24 The total number of carbon atoms contained in Rc3, the number of carbon atoms contained in R2, the number of carbon atoms contained in R3, and R 17 The number of carbon atoms contained in R 18 The number of carbon atoms contained in R 19 The number of carbon atoms contained in R 20 The number of carbon atoms contained in R 21 The number of carbon atoms contained in R 22 The number of carbon atoms contained in R 23 The number of carbon atoms contained in 24The total number of carbon atoms contained in is 5 or more.

[0320] Among them, from the viewpoint of further improving the effect of the present invention, the total number of carbon atoms is preferably 11 or more, and more preferably 15 or more. The total number of carbon atoms is not particularly limited, but is preferably 30 or less.

[0321] Furthermore, in formula (2b-2), the total number of carbon atoms contained in R2 and R3 is 4 or more. That is, the total number of carbon atoms contained in R2 and the total number of carbon atoms contained in R3 is 4 or more.

[0322] However, the compound represented by formula (2b-2) does not have any of a carboxyl group, a salt of a carboxyl group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.

[0323] (Substituent W)

[0324] The substituent W in this specification is described.

[0325] Examples of the substituent W include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heteroaryl group (also referred to as a heteroatom-containing cyclic group), a cyano group, a hydroxyl group, a nitro group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including an anilino group), an ammonium group, an amide group, The invention also includes but is not limited to alkyl, amino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfamoylamino, alkyl or arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclic thio, sulfamoyl, alkyl or arylsulfinyl, alkyl or arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl or heterocyclic azo, imide, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, phosphono, silyl, hydrazine, urea and boronic acid (-B(OH)2).

[0326] Furthermore, the substituent W may be further substituted by a substituent W. For example, the alkyl group may be substituted by a halogen atom.

[0327] Although specific compounds are exemplified below, the specific compounds in the present invention are not limited thereto.

[0328] [Chemical formula 18]

[0329]

[0330] [Chemical formula 19]

[0331]

[0332] [Chemical formula 20]

[0333]

[0334] [Chemical formula 21]

[0335]

[0336] [Chemical formula 22]

[0337]

[0338] [Chemical formula 23]

[0339]

[0340] The specific compound is particularly useful as a material for a photoelectric conversion film used in an imaging element, a light sensor or a photocell. In addition, in general, the specific compound functions as a p-type organic semiconductor in the photoelectric conversion film. In addition, 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 drug material.

[0341] From the viewpoint of stability when used as a p-type organic semiconductor and the degree of matching with the energy level of an n-type organic semiconductor, the specific compound is preferably a compound having an ionization potential of -5.0 to -6.0 eV in a single film.

[0342] The maximum absorption wavelength of a specific compound is not particularly limited. From the perspective that the photoelectric conversion film in the photoelectric conversion element of the present invention receives (absorbs) green light and is preferably used as an organic photoelectric conversion film for photoelectric conversion, it is preferably in the range of 500 nm to less than 590 nm, more preferably in the range of 520 nm to less than 580 nm, and further preferably in the range of 540 nm to less than 570 nm.

[0343] The maximum absorption wavelength is a value obtained by adjusting the absorbance to a concentration of about 0.5 to 1 and measuring the absorption spectrum of a specific compound in a solution state (solvent: chloroform).

[0344] The maximum absorption wavelength of the photoelectric conversion film is not particularly limited. From the perspective that the photoelectric conversion film in the photoelectric conversion element of the present invention receives (absorbs) green light and is preferably used as an organic photoelectric conversion film for photoelectric conversion, it is preferably in the range of 500 nm to less than 590 nm, more preferably in the range of 520 nm to less than 580 nm, and further preferably in the range of 540 nm to less than 570 nm.

[0345] <n-type organic semiconductor>

[0346] The photoelectric conversion film preferably contains an n-type organic semiconductor as a component other than the above-mentioned specific compound.

[0347] An n-type organic semiconductor is an acceptor organic semiconductor material (compound), which refers to an organic compound having the property of easily accepting electrons. In further detail, an n-type organic semiconductor refers to an organic compound having a large electron affinity when two organic compounds are brought into contact and used. Therefore, as an acceptor organic semiconductor, any organic compound can be used as long as it is an organic compound having electron accepting properties.

[0348] Examples of the n-type organic semiconductor 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 having 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, phenanthrazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives and oxadiazole derivatives; anthraquinone dimethane derivatives; diphenyl quinone (diphenyl quinone) derivatives; quinone derivatives; bathocuproine, bathophenanthroline, and derivatives thereof; triazole compounds; distyrylarylene derivatives; metal complexes having nitrogen-containing heterocyclic compounds as ligands; silylene compounds; and compounds described in paragraphs

[0056] to

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

[0349] Among them, as the n-type organic semiconductor (compound), it is preferable to contain fullerenes selected from the group consisting of fullerene and derivatives thereof.

[0350] Examples of the fullerene 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.

[0351] As for the fullerene derivative, for example, there can be mentioned compounds in which a substituent is added to the above-mentioned fullerene. As the substituent, an alkyl group, an aryl group or a heterocyclic group is preferred. As the fullerene derivative, the compound described in Japanese Patent Application Laid-Open No. 2007-123707 is preferred.

[0352] Alternatively, an organic dye may be used as an n-type organic semiconductor. For example, cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zero methine merocyanine (simple merocyanine)), rhodamine cyanine dyes, alopolar dyes, oxonol dyes, hemicyanine dyes, squarylium dyes, crotonium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, methine azo dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenathiazine dyes, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, acridone dyes, diphenylamine dyes, quinophthalocyanine dyes, phenoxazine dyes, phthaloperyl dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, and metal complex dyes.

[0353] The molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, more preferably 200 to 900.

[0354] From the viewpoint that the photoelectric conversion film in the photoelectric conversion element of the present invention receives (absorbs) green light and is preferably used as an organic photoelectric conversion film for photoelectric conversion, the n-type organic semiconductor is preferably colorless or has an absorption maximum wavelength and / or absorption waveform close to that of a specific compound. As a specific numerical value, the absorption maximum wavelength of the n-type organic semiconductor is preferably below 400 nm or in the range of 500 to 600 nm.

[0355] The photoelectric conversion film preferably has a bulk heterostructure formed in a state where a specific compound and an n-type organic semiconductor are mixed. The bulk heterostructure is a structure in which a layer of a specific compound and an n-type organic semiconductor are mixed and dispersed in the photoelectric conversion film. A photoelectric conversion film having a bulk heterostructure can be formed by any of a wet method and a dry method. In addition, the bulk heterostructure is described in detail in paragraphs

[0013] to

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

[0356] From the viewpoint of the responsiveness of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor (=film thickness of the specific compound converted in monolayer / (film thickness of the specific compound converted in monolayer + film thickness of the n-type organic semiconductor converted in monolayer) × 100) is preferably 15 to 75 volume %, and more preferably 35 to 75 volume %.

[0357] Furthermore, when the photoelectric conversion film contains a p-type organic semiconductor described later, the content of the specific compound (=film thickness when converted as a single layer of the specific compound / (film thickness when converted as a single layer of the specific compound + film thickness when converted as a single layer of the n-type organic semiconductor + film thickness when converted as a single layer of the p-type organic semiconductor) × 100) is preferably 15 to 75 volume %, and more preferably 35 to 75 volume %.

[0358] In addition, the photoelectric conversion film is preferably composed essentially of a specific compound and an n-type organic semiconductor.

[0359] Substantially, it means that the total content of the specific compound and the n-type organic semiconductor is 95% by mass or more based on the total mass of the photoelectric conversion film.

[0360] The n-type organic semiconductor contained in the photoelectric conversion film may be used alone or in combination of two or more.

[0361] Furthermore, the photoelectric conversion film may further contain a p-type organic semiconductor in addition to the specific compound and the n-type organic semiconductor. Examples of the p-type organic semiconductor include the following compounds.

[0362] The p-type organic semiconductor referred to herein refers to a p-type organic semiconductor that is a compound other than the specific compound. When the photoelectric conversion film contains a p-type organic semiconductor, the p-type organic semiconductor may be used alone or in combination of two or more.

[0363] <p-type organic semiconductor>

[0364] The p-type organic semiconductor refers to a donor organic semiconductor material (compound), and refers to an organic compound having a property of easily donating electrons. More specifically, the p-type organic semiconductor refers to an organic compound having a small ionization potential when two organic compounds are used in contact with each other.

[0365] 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, compounds described in paragraphs

[0119] to

[0148] of JP-A-2011-225544).

[0158] , the compounds described in

[0044] to

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

[0086] to

[0090] of JP-A-2012-094660, etc.), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (for example, thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b]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. 2018-014474, 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 paragraphs

[0029] to

[0034] of Japanese Patent Application Laid-Open No. 2017-076766, etc.), cyanine compounds, oxonocyanine compounds , polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (for example, 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, polyaryl alkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having nitrogen-containing heterocyclic compounds as ligands.

[0366] Examples of the p-type organic semiconductor include compounds having a lower ionization potential than that of the n-type organic semiconductor. As long as this condition is satisfied, the organic dyes exemplified as the n-type organic semiconductor can be used.

[0367] Compounds that can be used as the p-type semiconductor compound are exemplified below.

[0368] [Chemical formula 24]

[0369]

[0370] [Chemical formula 25]

[0371]

[0372] [Chemical formula 26]

[0373]

[0374] The photoelectric conversion film containing the specific compound is a non-luminescent film and has characteristics different from an organic electroluminescent element (OLED: Organic Light Emitting Diode). A non-luminescent film refers to a film with a luminescent quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less.

[0375] <Film Formation Method>

[0376] The photoelectric conversion film can be mainly formed by a dry film forming method. As a dry film forming method, for example, physical vapor deposition methods such as evaporation (especially vacuum evaporation), sputtering, ion plating, and MBE (Molecular Beam Epitaxy) and CVD (Chemical Vapor Deposition) methods such as plasma polymerization can be cited. Among them, vacuum evaporation is preferred. When the photoelectric conversion film is formed by vacuum evaporation, the manufacturing conditions such as vacuum degree and evaporation temperature can be set according to the conventional method.

[0377] 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 300 nm.

[0378] <Electrode>

[0379] 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.

[0380] Since light is incident from the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected. As materials constituting the upper electrode 15, for example, 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; and organic conductive materials such as polyaniline, polythiophene and polypyrrole. Among them, conductive metal oxides are preferred from the viewpoints of high conductivity and transparency.

[0381] 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 imaging element equipped with the photoelectric conversion element of this embodiment, the sheet resistance is preferably 100 to 10000Ω / □, and the film thickness range that can be thinned is relatively free. In addition, the thinner the thickness of the upper electrode (transparent conductive film) 15, the less light is absorbed, and generally speaking, the transmittance will increase. The increase in transmittance increases the light absorption in the photoelectric conversion film, thereby increasing the photoelectric conversion energy, so it is preferred. Considering the suppression of leakage current, the increase in resistance value of the film, and the increase in transmittance that accompanies thinning, the film thickness of the upper electrode 15 is preferably 5 to 100nm, and more preferably 5 to 20nm.

[0382] The lower electrode 11 may be transparent or may not be transparent and reflect light depending on the application. Examples of the material 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; 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; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.

[0383] The method for forming the electrode is not particularly limited and can be appropriately selected according to the electrode material. Specifically, there can be cited wet methods such as printing and coating methods; physical methods such as vacuum evaporation, sputtering and ion plating methods; and chemical methods such as CVD and plasma CVD methods.

[0384] When the material of the electrode is ITO, examples of the method include an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (sol-gel method, etc.), and coating of a dispersion of indium tin oxide.

[0385] <Charge blocking film: electron blocking film, hole blocking film>

[0386] The photoelectric conversion element of the present invention preferably has one or more intermediate layers between the conductive film and the transparent conductive film in addition to the photoelectric conversion film. As the above-mentioned intermediate layer, a charge blocking film can be cited. By having the film in the photoelectric conversion element, the characteristics (photoelectric conversion efficiency and responsiveness, etc.) of the obtained photoelectric conversion element are more excellent. As the charge blocking film, an electron blocking film and a hole blocking film can be cited. Below, each film is described in detail.

[0387] (Electron blocking film)

[0388] The electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used.

[0389] Furthermore, a polymer material can also be used as the electron blocking film.

[0390] Examples of the polymer material include polymers of phenylacetylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and the like, and derivatives thereof.

[0391] In addition, the electron blocking film may be composed of a plurality of films.

[0392] The electron blocking film can be made of an inorganic material. Generally speaking, the dielectric constant of an inorganic material is greater than that of an organic material. Therefore, when an inorganic material is used for an electron blocking film, a larger voltage is applied to the photoelectric conversion film, thereby increasing the photoelectric conversion efficiency. Examples of inorganic materials that can be used as 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.

[0393] (Hole Blocking Film)

[0394] The hole blocking film is an acceptor organic semiconductor material (compound), and the above-mentioned n-type semiconductor can be used.

[0395] The manufacturing method of the charge blocking film is not particularly limited, and dry film forming method and wet film forming method can be cited. As dry film forming method, evaporation method and sputtering method can be cited. The evaporation method can be any of physical vapor deposition (PVD: physical vapor deposition (Physical Vapor Deposition)) method and chemical vapor deposition (CVD) method, preferably physical vapor deposition method such as vacuum evaporation method. As wet film forming method, for example, inkjet method, spray method, nozzle printing method, spin coating method, dip coating method, casting method, die coating method, roller coating method, rod coating method and gravure coating method can be cited. From the viewpoint of high-precision patterning, inkjet method is preferred.

[0396] The thickness of each of the charge blocking film (the electron blocking film and the hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and further preferably 5 to 30 nm.

[0397] <Substrate>

[0398] The photoelectric conversion element may further include a substrate. The type of substrate used is not particularly limited, and examples thereof include a semiconductor substrate, a glass substrate, and a plastic substrate.

[0399] In addition, the position of the substrate is not particularly limited, but generally, a conductive film, a photoelectric conversion film, and a transparent conductive film are sequentially stacked on the substrate.

[0400] <Sealing layer>

[0401] The photoelectric conversion element may also have a sealing layer. Sometimes the performance of the photoelectric conversion material is significantly degraded due to the presence of degradation factors such as water molecules. Therefore, the photoelectric conversion film is entirely covered and sealed with a sealing layer such as a dense ceramic such as a metal oxide, metal nitride or metal nitride oxide that does not allow water molecules to penetrate, or diamond-like carbon (DLC: Diamond-like Carbon), thereby preventing the above-mentioned degradation.

[0402] The sealing layer may be selected and manufactured according to the description in paragraphs

[0210] to

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

[0403] <Imaging element>

[0404] As a use of the photoelectric conversion element, for example, an imaging element can be cited. An imaging element is an element that converts the optical information of an image into an electrical signal. It usually means that a plurality of photoelectric conversion elements are arranged in a matrix in the same plane, and the optical information can be converted into an electrical signal in each photoelectric conversion element (pixel), and the electrical signal is output to the outside of the imaging element one by one for each pixel. Therefore, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.

[0405] Figure 3 The schematic cross-sectional view shows a schematic structure of an imaging element for explaining one embodiment of the present invention. The imaging element is mounted in an imaging element such as a digital camera or a digital video camera, an electronic endoscope, and an imaging module such as a mobile phone.

[0406] Figure 3 The imaging element 20a shown includes the photoelectric conversion element 10a of the present invention, a blue photoelectric conversion element 22, and a red photoelectric conversion element 24, which are stacked along the direction in which light is incident. As described above, the photoelectric conversion element 10a can function as a green photoelectric conversion element that can mainly receive green light.

[0407] The imaging element 20a is a so-called laminated color separation imaging element. The wavelength spectra detected by the photoelectric conversion element 10a, the blue photoelectric conversion element 22, and the red photoelectric conversion element 24 are different. That is, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 are equivalent to photoelectric conversion elements that receive light of a different wavelength from the light received (absorbed) by the photoelectric conversion element 10a. The photoelectric conversion element 10a can mainly receive green light, the blue photoelectric conversion element 22 can mainly receive blue light, and the red photoelectric conversion element can mainly receive red light.

[0408] In addition, green light refers to light within a wavelength range of 500 to 600 nm, blue light refers to light within a wavelength range of 400 to 500 nm, and red light refers to light within a wavelength range of 600 to 700 nm.

[0409] When light enters the imaging element 20a from the direction of the arrow, first, the green light is mainly absorbed in the photoelectric conversion element 10a, but the blue light and the red light pass through the photoelectric conversion element 10a. When the light that passes through the photoelectric conversion element 10a enters the blue photoelectric conversion element 22, the blue light is mainly absorbed, but the red light passes through the blue photoelectric conversion element 22. Then, the light that passes through the blue photoelectric conversion element 22 is absorbed by the red photoelectric conversion element 24. In this way, in the imaging element 20a which is a stacked color separation imaging element, one pixel can be composed of three light receiving parts of green, blue and red, and a large area of ​​the light receiving part can be used.

[0410] In particular, in the photoelectric conversion element 10 a of the present invention, since the half width of the absorption peak is narrow, the absorption of blue light and red light hardly occurs, and the detectability in the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 is hardly affected.

[0411] The structures of the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 are not particularly limited.

[0412] For example, it can be a photoelectric conversion element that uses silicon and has a structure that separates colors by the difference in light absorption length. As a more specific example, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 can both be made of silicon. In this case, with respect to the light including blue light, green light and red light incident on the imaging element 20a in the direction of the arrow, the green light, which is the light of the intermediate wavelength, is mainly received by the photoelectric conversion element 10a, and the remaining blue light and red light become easy to separate colors. There is a difference in the light absorption length of blue light and red light to silicon (the wavelength dependence of the absorption coefficient of silicon), and blue light is easily absorbed near the surface of silicon, and red light can invade a relatively deep position of silicon. Based on this difference in light absorption length, blue light is mainly received by the blue photoelectric conversion element 22 present in a shallower position, and red light is mainly received by the red photoelectric conversion element 24 present in a deeper position.

[0413] Furthermore, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 may be photoelectric conversion elements (blue photoelectric conversion element 22 or red photoelectric conversion element 24) having a structure including a conductive film, an organic photoelectric conversion film having maximum absorption of blue light or red light, and a transparent conductive film in sequence.

[0414] exist Figure 3 In the embodiment, the photoelectric conversion element of the present invention, the blue photoelectric conversion element, and the red photoelectric conversion element are sequentially arranged from the light incident side, but it is not limited to this mode, and other arrangement orders are also possible. For example, the blue photoelectric conversion element, the photoelectric conversion element of the present invention, and the red photoelectric conversion element may also be sequentially arranged from the light incident side.

[0415] As described above, as an imaging element, a structure in which photoelectric conversion elements of three primary colors of blue, green and red are stacked is described, but it may be two layers (2 colors) or four layers (4 colors) or more.

[0416] For example, the photoelectric conversion element 10a of the present invention may be disposed on the arranged blue photoelectric conversion element 22 and the red photoelectric conversion element 24. Furthermore, a color filter that absorbs light of a specific wavelength may be further disposed on the light incident side as needed.

[0417] The form of the imaging element is not limited to Figure 3 As well as the above forms, other forms are also possible.

[0418] For example, a mode in which the photoelectric conversion element of the present invention, a blue photoelectric conversion element, and a red photoelectric conversion element are arranged at positions within the same plane may be adopted.

[0419] Furthermore, a structure in which the photoelectric conversion element is used in a single layer may be used. For example, a structure in which blue, red, and green color filters are arranged on the photoelectric conversion element 10a of the present invention to separate colors may be used.

[0420] As other uses of the photoelectric conversion element, for example, photocells and optical sensors can be cited, but the photoelectric conversion element of the present invention is preferably used as a photo sensor. As a photo sensor, the above-mentioned photoelectric conversion element can be used alone, or it can be used as a line sensor in which the above-mentioned photoelectric conversion element is arranged in a straight line or a two-dimensional sensor arranged on a plane.

[0421] Example

[0422] Below, based on embodiment, the present invention is described in further detail.As long as the material, usage amount, ratio, processing content and processing step etc. shown in the following embodiment do not depart from the purpose of the present invention, then can be changed appropriately.Therefore, the scope of the present invention should not be interpreted restrictively by the embodiment shown below.

[0423] <Synthesis of Compound (D-1)>

[0424] Compound (D-1) was synthesized according to the following scheme.

[0425] [Chemical formula 27]

[0426]

[0427] 4-tert-Butylphenylhydrazine hydrochloride (5.00 g, 24.9 mmol) and 3-methyl-2-butanone (2.58 g, 29.9 mmol) were added to acetic acid (62.5 mL), and the obtained solution was heated to reflux under a nitrogen atmosphere and reacted for 3 hours. After the obtained solution was cooled to room temperature, the organic layer was extracted with methyl tert-butyl ether (MTBE), and the obtained extract was washed with physiological saline, and the washed extract was concentrated under reduced pressure to obtain a concentrated residue containing compound 1.

[0428] Acetonitrile (40 mL) and methyl trifluoromethanesulfonate (7.14 g, 43.5 mmol) were added to the concentrated residue, and the obtained solution was heated to reflux under a nitrogen atmosphere and reacted for 3 hours. If MTBE (80 mL) was added to the obtained solution, the obtained solution was separated into a solid containing compound 2 and an MTBE solution, and the MTBE solution was removed by decantation. MTBE (80 mL) was added to the solid containing compound 2 for dispersion and washing, and MTBE was removed by decantation to obtain compound 2 (3.54 g, 9.33 mmol, yield 37%) as an orange solid.

[0429] Compound 2 (1.70 g, 4.48 mmol), Ac1 (1.22 g, 4.07 g) (synthesized according to paragraphs

[0080] to

[0084] of Japanese Patent No. 5337381) and piperidine (0.8 mL) were added to butyronitrile (62.5 mL), and the obtained solution was heated to reflux under a nitrogen atmosphere and reacted for 48 hours. After the obtained solution was cooled to room temperature, the precipitated solid was recovered by filtration, and the obtained solid was washed with acetonitrile to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (chloroform: ethyl acetate = 9:1), and the obtained compound was recrystallized from a chloroform-acetonitrile mixed solvent and washed with acetonitrile to obtain compound (D-1) (1.20 g, 2.76 mmol, yield 61%).

[0430] The obtained compound (D-1) was identified by NMR (Nuclear Magnetic Resonance) and MS (Mass Spectrometry).

[0431] exist Figure 4 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0432] MS (ESI + )m / z:436.6([M+H] + )

[0433] <Synthesis of Compound (D-2)>

[0434] Compound (D-2) was synthesized according to the following scheme.

[0435] [Chemical formula 28]

[0436]

[0437] Acetonitrile (77 mL) and 2-iodopropane (25.0 g, 147 mmol) were added to 1,1,2-trimethyl-1H-benzo[e]indole (7.69 g, 36.8 mmol), and the obtained solution was heated to reflux under a nitrogen atmosphere and reacted for 48 hours. After the obtained solution was cooled to room temperature, the precipitated powder was recovered by filtration. The obtained powder was dispersed and washed with toluene, the powder was recovered by filtration, and the recovered powder was washed with MTBE to obtain compound 3 (4.00 g, 10.5 mmol, yield 29%) as a white powder.

[0438] Compound 3 (4.00 g, 11.3 mmol), Ac1 (2.87 g, 9.59 mmol) and piperidine (2.66 mL) were added to butyronitrile (80 mL), and the obtained solution was heated to reflux under a nitrogen atmosphere and reacted for 48 hours. After the obtained solution was cooled to room temperature, the precipitated solid was recovered by filtration, and the recovered solid was washed with acetonitrile to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (chloroform: ethyl acetate = 9: 1), and the obtained compound was recrystallized from a chloroform-acetonitrile mixed solvent and washed with acetonitrile to obtain compound (D-2) (0.99 g, 2.16 mmol, yield 23%).

[0439] The obtained compound (D-2) was identified by NMR and MS.

[0440] exist Figure 5 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0441] MS (ESI + )m / z:458.7([M+H] + )

[0442] <Synthesis of Compound (D-3)>

[0443] Compound (D-3) was synthesized according to the following scheme.

[0444] [Chemical formula 29]

[0445]

[0446] 2,6-difluoroaniline (46.7 g, 362 mmol), 2-bromonaphthalene (50.0 g, 241 mmol), palladium (II) acetate (1.62 g, 7.23 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (S-Phos) (5.94 g, 14.5 mmol), cesium carbonate (157 g, 481 mmol) and toluene (500 mL) were added to a 2L three-necked flask, and degassed and replaced with nitrogen. Under a nitrogen atmosphere, the solution in the flask was heated to 110°C and stirred for 12 hours. Moreover, after the solution was cooled to room temperature, the solution was added to water. The obtained organic layer was extracted with ethyl acetate, and the obtained extract was washed with physiological saline, and the washed extract was concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (toluene:hexane=1:1) to obtain Compound 4 (49.3 g, 193 mmol, yield 80%) as a pale yellow solid.

[0447] Compound 4 (40 g, 178 mmol) was added to a mixed solvent of tetrahydrofuran (200 mL) and acetic acid (200 mL), and an aqueous sodium nitrite solution (87.8 mL, 356 mmol) was added dropwise to the obtained solution at room temperature, and the solution was reacted for 20 minutes. The obtained solution was extracted with toluene (434 mL), and the obtained extract was washed with water (434 mL) to remove the water layer. After adding water (88 mL) and ethanol (88 mL) to the organic layer containing the obtained compound 5, the obtained solution was cooled to 0°C in an ice bath, and zinc powder (81.5 g, 1.25 mmol) was added. Acetic acid (88 mL) was added dropwise to the obtained solution so that it did not exceed 10°C, and then the obtained solution was reacted for 2 hours at room temperature. Insoluble matter was filtered out from the solution, and the filtrate was recovered. After adding physiological saline (434 mL) to the filtrate to wash the organic layer, the recovered organic layer was concentrated to about 150 mL under reduced pressure. MTBE (400 mL) and 30% hydrochloric acid (43.3 g, 356 mmol) were added to the concentrated solution and stirred. The powder precipitated in the solution was filtered to recover the solid, which was washed with MTBE and isopropanol and then dried by heating to obtain Compound 6 (21.8 g, 71.1 mmol, yield 36%).

[0448] Compound 6 (8.00 g, 26.1 mmol), cyclohexyl methyl ketone (3.62 g, 28.7 mmol) and 60% hexafluorophosphoric acid (7.23 mL) were added to ethanol (80 mL), and the obtained solution was heated under reflux under a nitrogen atmosphere to react for 2 hours. After the obtained solution was cooled to room temperature, a 10 M sodium hydroxide aqueous solution (100 mL) was added to the solution to neutralize it, and the organic layer was extracted with MTBE, and the obtained extract was washed with physiological saline, and the washed extract was concentrated under reduced pressure to about 20 mL.

[0449] MTBE (150 mL) and 60% hexafluorophosphoric acid (7.23 mL, 52.2 mmol) were added to the concentrated solution and stirred. The salt of compound 7 precipitated in the solution was recovered by filtration, and the recovered solid was washed with MTBE. The salt of compound 7 obtained was added to dichloromethane (200 mL), and 2M aqueous sodium hydroxide solution (200 mL) was further added dropwise to the solution for neutralization and dissolved in dichloromethane. Dichloromethane was concentrated under reduced pressure to obtain compound 7 (1.13 g, 3.13 mmol, yield 12%).

[0450] Under a nitrogen atmosphere, (chloromethylene) dimethyliminium (Iminium) (800 mg, 6.25 mmol) was added to dichloromethane (11 mL) and cooled to 0 ° C in an ice bath. A dichloromethane solution (11 mL) of compound 7 (1.13 g, 3.13 mmol) was added dropwise to the obtained solution, and it was reacted at room temperature for 2 hours. A 2M aqueous sodium hydroxide solution (100 mL) was added dropwise to the obtained solution and hydrolyzed. The obtained organic layer was extracted with dichloromethane, and the obtained extract was washed with physiological saline, and the washed extract was concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (chloroform: ethyl acetate = 99: 1), thereby obtaining compound 8 (900 mg, 2.31 mmol, yield 74%) as a light yellow solid.

[0451] Compound 8 (900 mg, 2.31 mmol) and Ac3 (453 mg, 2.31 mmol) were added to acetic anhydride (16 mL), and the obtained solution was reacted at 110° C. for 2 hours under a nitrogen atmosphere. After the obtained solution was cooled to room temperature and the solvent was removed under reduced pressure concentration, the obtained crude product was purified by silica gel column chromatography (chloroform: ethyl acetate = 9: 1), and the obtained compound was recrystallized from a chloroform-acetonitrile mixed solvent and washed with acetonitrile to obtain compound (D-3) (1.00 g, 1.76 mmol, yield 76%).

[0452] The obtained compound (D-3) was identified by NMR and MS.

[0453] exist Figure 6 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0454] MS (ESI + )m / z:568.5([M+H] + )

[0455] <Synthesis of Compound (D-4)>

[0456] Compound (D-4) was synthesized according to the following scheme.

[0457] [Chemical formula 30]

[0458]

[0459] Compound 6 (3.00 g, 9.83 mmol), 3-methyl-2-butanone (1.27 g, 14.7 mmol) and 60% hexafluorophosphoric acid (2.71 mL) were added to ethanol (30 mL), and the obtained solution was heated to reflux under a nitrogen atmosphere and reacted for 2 hours. After the obtained solution was cooled to room temperature, 10 M sodium hydroxide aqueous solution (50 mL) was added to the solution and neutralized, and then the organic layer was extracted with MTBE, and the obtained extract was washed with physiological saline, and the washed extract was concentrated under reduced pressure. MTBE (150 mL) and 60% hexafluorophosphoric acid (2.71 mL, 19.7 mmol) were added to the concentrated solution and stirred. The salt of compound 9 precipitated in the solution was recovered by filtration, and the recovered solid was washed with MTBE. Next, the obtained salt of Compound 9 was added to dichloromethane (100 mL), neutralized by dropwise addition of 2M sodium hydroxide aqueous solution (100 mL), and dissolved in dichloromethane. The obtained dichloromethane was concentrated under reduced pressure to obtain Compound 9 (2.30 g, 7.16 mmol, yield 49%).

[0460] Under a nitrogen atmosphere, (chloromethylene) dimethyliminium (Iminium) (1.37 g, 10.7 mmol) was added to dichloromethane (23 mL), and the obtained solution was cooled to 0 ° C in an ice bath. A dichloromethane solution (23 mL) of compound 9 (2.30 g, 7.16 mmol) was added dropwise to the solution, and the mixture was reacted at room temperature for 2 hours. A 2M aqueous sodium hydroxide solution (100 mL) was added dropwise to the obtained solution and hydrolyzed. The organic layer was extracted with dichloromethane, and the obtained extract was washed with physiological saline, and the washed extract was concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (chloroform: ethyl acetate = 99: 1), thereby obtaining compound 10 (1.28 g, 3.66 mmol, yield 51%) as a light yellow solid.

[0461] Compound 10 (1.28 g, 3.66 mmol) and Ac3 (719 mg, 3.66 mmol) were added to acetic anhydride (26 mL), and the obtained solution was reacted at 110° C. for 2 hours under a nitrogen atmosphere. After the obtained solution was cooled to room temperature and the solvent was removed under reduced pressure concentration, the obtained crude product was purified by silica gel column chromatography (chloroform: ethyl acetate = 9: 1), and the obtained compound was recrystallized from a chloroform-acetonitrile mixed solvent and washed with acetonitrile to obtain compound (D-4) (1.15 g, 2.18 mmol, yield 60%).

[0462] The obtained compound (D-4) was identified by NMR and MS.

[0463] exist Figure 7 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0464] MS (ESI + )m / z:528.3([M+H] + )

[0465] <Synthesis of Compound (D-5)>

[0466] Compound (D-5) was synthesized in the same manner as compound (D-4) according to the following scheme.

[0467] [Chemical formula 31]

[0468]

[0469] exist Figure 8 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0470] MS (ESI + )m / z:556.6([M+H] + )

[0471] <Synthesis of Compound (D-6)>

[0472] Compound (D-6) was synthesized in the same manner as compound (D-4) according to the following scheme.

[0473] [Chemical formula 32]

[0474]

[0475] exist Fig. 9 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0476] MS (ESI + )m / z:534.8([M+H] + )

[0477] <Synthesis of Compound (D-7)>

[0478] Compound (D-7) was synthesized in the same manner as compound (D-4) according to the following scheme.

[0479] [Chemical formula 33]

[0480]

[0481] exist Fig.10 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0482] MS (ESI + )m / z:582.5([M+H] + )

[0483] <Synthesis of Compound (D-8)>

[0484] Compound (D-8) was synthesized according to the following scheme.

[0485] [Chemical formula 34]

[0486]

[0487] Compound 27 (1.50 g, 4.75 mmol) was added to acetonitrile (15 mL), benzyl bromide (5.61 g, 23.8 mmol) was added dropwise in the obtained solution, and the solution was heated to reflux and reacted for 8 hours under a nitrogen atmosphere. After acetonitrile was removed from the solution by concentrating under reduced pressure, toluene was added to separate it into a solid and a toluene solution containing compound 29, and the toluene solution was removed by decantation. MTBE was added to the solid containing the obtained compound 29 for dispersion and cleaning, and MTBE was removed by decantation to obtain an orange solid containing compound 29. The solid was not further purified and used in the next reaction.

[0488] An orange solid, Ac1 (1.28 g, 4.28 mmol) and piperidine (1.00 mL) were added to butyronitrile (30 mL), and the obtained solution was heated to reflux under a nitrogen atmosphere to react for 48 hours. After the obtained solution was cooled to room temperature, the precipitated solid was recovered by filtration, and the recovered solid was washed with acetonitrile to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (chloroform: ethyl acetate = 9:1), and the obtained compound was recrystallized from a chloroform-acetonitrile mixed solvent and washed with acetonitrile to obtain compound (D-8) (710 mg, 1.16 mmol, yield 24% (2 steps)). Fig.11 Shown in 1 H-NMR spectrum (400 MHz, CDCl3).

[0489] MS (ESI + )m / z:512.9([M+H] + )

[0490] <Synthesis of Compound (D-9)>

[0491] Compound (D-9) was synthesized in the same manner as compound (D-4) according to the following scheme.

[0492] [Chemical formula 35]

[0493]

[0494] exist Fig.12 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0495] MS (ESI + )m / z:534.8([M+H] + )

[0496] <Synthesis of Compound (D-10)>

[0497] Referring to the synthesis of compound (D-4), compound (D-10) was synthesized according to the following scheme.

[0498] [Chemical formula 36]

[0499]

[0500] MS (ESI + )m / z:795.8([M+H] + ).

[0501] <Synthesis of Compound (D-11)>

[0502] Compound (D-11) was synthesized according to the following scheme.

[0503] [Chemical formula 37]

[0504]

[0505] Compound 34 (480 mg, 0.968 mmol) and 2-thiobarbituric acid (140 mg, 0.968 mmol) were added to acetic anhydride (7 mL), and the obtained solution was reacted at 110° C. for 2 hours under a nitrogen atmosphere. After the obtained solution was cooled to room temperature and concentrated under reduced pressure to remove the solvent, the obtained crude product was purified by silica gel column chromatography (chloroform: ethyl acetate = 9:1), and the obtained compound was recrystallized from a chloroform-acetonitrile mixed solvent and washed with acetonitrile to obtain compound (D-11) (283 mg, 0.455 mmol, yield 47%).

[0506] exist Fig.13 Shown in 1 H NMR spectroscopy (400 MHz, DMSO).

[0507] MS (ESI + )m / z:622.5([M+H] + )

[0508] <Synthesis of Compound (D-12)>

[0509] Referring to the synthesis of compound (D-11), compound (D-12) was synthesized according to the following scheme.

[0510] [Chemical formula 38]

[0511]

[0512] MS (ESI + )m / z:650.6([M+H] + )

[0513] <Synthesis of Compound (D-13)>

[0514] Referring to the syntheses of compound (D-11) and compound (D-12), compound (D-13) was synthesized according to the following scheme.

[0515] [Chemical formula 39]

[0516]

[0517] MS (ESI + )m / z:639.7([M+H] + )

[0518] <Synthesis of Compound (D-14)>

[0519] Compound (D-14) was synthesized according to the following scheme.

[0520] [Chemical formula 40]

[0521]

[0522] Compound 34 (480 mg, 0.968 mmol) and 1,2-diphenylpyrazolidine-3,5-dione (244 mg, 0.968 mmol) were added to acetic anhydride (7 mL), and the obtained solution was reacted at 110° C. for 2 hours under a nitrogen atmosphere. After the obtained solution was cooled to room temperature and concentrated under reduced pressure to remove the solvent, the obtained crude product was purified by silica gel column chromatography (chloroform: ethyl acetate = 9:1), and the obtained compound was recrystallized from a chloroform-acetonitrile mixed solvent and washed with acetonitrile to obtain compound (D-14) (311 mg, 0.426 mmol, yield 44%).

[0523] exist Fig.14 Shown in 1 H NMR spectroscopy (400 MHz, DMSO).

[0524] MS (ESI + )m / z:730.0([M+H] + )

[0525] Synthesis of Compound (D-15)>

[0526] Compound (D-15) was synthesized according to the following scheme with reference to the syntheses of compound (D-2) and compound (D-11).

[0527] [Chemical formula 41]

[0528]

[0529] MS (ESI + )m / z:428.4([M+H] + )

[0530] <Synthesis of Compound (D-16)>

[0531] Referring to the synthesis of compound (D-2), compound (D-16) was synthesized according to the following scheme.

[0532] [Chemical formula 42]

[0533]

[0534] MS (ESI + )m / z:408.2([M+H] + )

[0535] <Synthesis of Compound (D-17)>

[0536] Compound (D-17) was synthesized in the same manner as in the synthesis of compound (D-6) and according to the following scheme.

[0537] [Chemical formula 43]

[0538]

[0539] exist Fig.15 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0540] MS (ESI + )m / z:545.8([M+H] + )

[0541] <Synthesis of Compound (D-18)>

[0542] Compound (D-18) was synthesized according to the following scheme with reference to the syntheses of compound (D-6) and compound (D-3).

[0543] [Chemical formula 44]

[0544]

[0545] exist Fig.16 Shown in 1 H NMR spectrum (400 MHz, CDCl3).

[0546] MS (ESI + )m / z:574.9([M+H] + )

[0547] <Synthesis of Compound (D-19)>

[0548] Compound (D-19) was synthesized according to the following scheme with reference to the syntheses of compound (D-1) and compound (D-2).

[0549] [Chemical formula 45]

[0550]

[0551] MS (ESI + )m / z:434.5([M+H] + )

[0552] <Synthesis of Compound (D-20)>

[0553] Compound (D-20) was synthesized according to the following scheme by referring to the syntheses of compound (D-2) and compound (D-8).

[0554] [Chemical formula 46]

[0555]

[0556] MS (ESI + )m / z:505.6([M+H] + )

[0557] <Synthesis of Compound (D-21)>

[0558] Compound (D-21) was synthesized according to the following scheme.

[0559] [Chemical formula 47]

[0560]

[0561] Compound 34 (480 mg, 0.968 mmol) and 3-cyano-1-ethyl-6-hydroxy-4-methyl-2-pyridone (172 mg, 0.968 mmol) were added to acetic anhydride (7 mL), and the obtained solution was reacted at 110° C. for 2 hours under a nitrogen atmosphere. After the obtained solution was cooled to room temperature and the solvent was removed under reduced pressure concentration, the obtained crude product was purified by silica gel column chromatography (chloroform: ethyl acetate = 9: 1), and the obtained compound was recrystallized from a chloroform-acetonitrile mixed solvent and washed with acetonitrile to obtain compound (D-21) (456 mg, 0.695 mmol, yield 72%).

[0562] exist Fig.17 Shown in 1 H NMR spectroscopy (400 MHz, DMSO).

[0563] MS (ESI + )m / z:656.5([M+H] + )

[0564] Referring to the synthesis of compounds (D-1) to (D-21), compounds (D-22) to (D-32) were further synthesized.

[0565] exist Figures 18 to 21 The compounds (D-22), (D-24) to (D-26) are shown in 1 H NMR spectroscopy (400 MHz, DMSO).

[0566] Comparative compounds (R-1), (R-2), (R-3) and (R-4) were synthesized with reference to Japanese Patent Publication No. 2009-167348, comparative compound (R-5) was synthesized with reference to J. Am. Chem. Soc. 73, 1951, 5326-5330, and comparative compound (R-6) was synthesized with reference to Japanese Patent Publication No. 2016-188363.

[0567] [Chemical formula 48]

[0568]

[0569] [Chemical formula 49]

[0570]

[0571] [Chemical formula 50]

[0572]

[0573] <Example and Comparative Example: Preparation of Photoelectric Conversion Element>

[0574] Using the obtained compound, Figure 1 Here, the photoelectric conversion element includes a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, and an upper electrode 15.

[0575] Specifically, amorphous ITO was deposited on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and the following compound (EB-1) was deposited on the lower electrode 11 by vacuum heating evaporation to form an electron blocking film 16A (thickness: 30 nm).

[0576] Furthermore, while the temperature of the substrate is controlled at 25°C, the compound (D-1) and fullerene (C60) are co-evaporated on the electron blocking film 16A by vacuum evaporation to form a film so that their thicknesses are 100nm and 100nm respectively when converted to a single layer, thereby forming a photoelectric conversion film 12 with a bulk heterostructure of 200nm.

[0577] Furthermore, amorphous ITO was formed by sputtering on the photoelectric conversion film 12 to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm). After a SiO film as a sealing layer was formed on the upper electrode 15 by vacuum evaporation, an aluminum oxide (Al2O3) layer was formed thereon by ALCVD (Atomic Layer Chemical Vapor Deposition) to produce a photoelectric conversion element.

[0578] [Chemical formula 51]

[0579]

[0580] Similarly, photoelectric conversion elements were produced using compounds (D-2) to (D-32) and comparative compounds (R-1) to (R-6). However, comparative compound (R-6) was thermally decomposed during vapor deposition, and a photoelectric conversion element could not be produced.

[0581] <Photoelectric conversion efficiency evaluation>

[0582] With respect to the photoelectric conversion elements prepared in the examples and comparative examples, voltage was applied until the electric field intensity reached 1.0×10 5 V / cm.

[0583] Then, light was irradiated from the upper electrode (transparent conductive film) side and the external quantum efficiency at 580 nm was measured. The external quantum efficiency was measured using a constant energy quantum efficiency measurement device (manufactured by NIHON OPTEL CORPORATION). The irradiated light amount was 50 μW / cm2 And, in order to exclude the influence of reflected light on the surface of the photoelectric conversion element, the external quantum efficiency was obtained by dividing the measured value of the external quantum efficiency at 580 nm by the light absorption rate at 580 nm.

[0584] The photoelectric conversion efficiency of each photoelectric conversion element corresponding to the photoelectric conversion element formed using the compound (D-1) was evaluated as a relative value.

[0585] The relative value of the photoelectric conversion efficiency relative to the photoelectric conversion element formed using the compound (D-1) was 1.05 or more, and was designated as "AA", 1.00 or more and less than 1.05 was designated as "A", 0.95 or more and less than 1.00 was designated as "B", 0.90 or more and less than 0.95 was designated as "C", and less than 0.90 was designated as "D". The results are shown in Table 1.

[0586] In practical applications, "AA", "A" or "B" are preferred, and "AA" or "A" are more preferred.

[0587] <Measurement of half width and maximum absorption wavelength>

[0588] While the temperature of the glass substrate was controlled at 25° C., the compound (D-1) and the fullerene (C-1) were co-deposited by vacuum heating evaporation. 60 ) are formed so that the thicknesses are 100 nm and 100 nm respectively in terms of a single layer, thereby forming a photoelectric conversion film having a bulk heterostructure of 200 nm.

[0589] The maximum absorption wavelength and the half-width of absorption of the photoelectric conversion film were measured using a spectrophotometer U3310 manufactured by Hitachi High-Technologies Corporation. The half-width of absorption represents the difference between two wavelengths showing 0.5 times the absorbance relative to the absorbance of the maximum absorption wavelength (points showing 0.5 times the absorbance of the maximum absorption at two points on the long wavelength side and the short wavelength side relative to the maximum absorption wavelength).

[0590] The maximum absorption wavelength was evaluated based on the following criteria. The results are summarized in Table 1.

[0591] "A": When the maximum absorption wavelength is 540nm or more and less than 570nm

[0592] "B": When the maximum absorption wavelength is 520nm or more and less than 540nm or 570nm or more and less than 580nm

[0593] "C": When the maximum absorption wavelength is 500nm or more and less than 520nm or 580nm or more and less than 590nm

[0594] "D": Maximum absorption wavelength is less than 500nm or above 590nm

[0595] The absorption half width was evaluated based on the following criteria. The results are summarized in Table 1.

[0596] "AA": Absorption half width is less than 86nm

[0597] "A": When the absorption half width is 86 nm or more and less than 92 nm

[0598] "B": Absorption half width is 92 nm or more and less than 98 nm

[0599] "C": Absorption half width is 98 nm or more and less than 100 nm

[0600] "D": Absorption half width is less than 100nm

[0601] Regarding the absorption half width, in practical use, "AA", "A" or "B" is preferred, and "AA" or "A" is more preferred.

[0602] The same evaluation as above was carried out except that compound (D-1) was replaced with compounds (D-2) to (D-32) and comparative compounds (R-1) to (R-5).

[0603] In Table 1, the "A" column represents a ring corresponding to A in formula (1), "B ring" represents a benzene ring, "N ring" represents a naphthalene ring, "F ring" represents a fluorene ring, "P ring" represents a phenanthrene ring, "Q ring" represents a quinoline ring, and "BT ring" represents a benzothiophene ring.

[0604] The column "n" indicates a number corresponding to n in formula (1).

[0605] The "R1" column represents a group corresponding to R1 in formula (1), "R-1" represents a group represented by formula (R-1), "R-2" represents a group represented by formula (R-2), "R-4" represents a group represented by formula (R-4), "Ar" represents an aryl group (which may be substituted with a substituent), "4A" represents a group represented by formula (4A), "5A" represents a group represented by formula (5A), "5B" represents a group represented by formula (5B), and "Nap" represents a naphthalene ring (which may be substituted with a substituent). In addition, when a group corresponding to R1 corresponds to multiple conditions in the above groups, it is recorded as the following group. For example, the groups corresponding to R1 in compound (D-6) all correspond to "Ar", "4A" and "5A", but only "5A" is shown in the table.

[0606] The "B1" column represents a group corresponding to B1 in formula (1), "B-2" represents a group represented by formula (B-2), and "J-1" to "J-5" represent groups represented by formula (J-1) to formula (J-5), respectively.

[0607] The "total number" indicates the total number of carbon atoms contained in R1 to R4 in formula (1).

[0608] The "Formula" column indicates that each compound is equivalent to a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (2b), a compound represented by formula (2b-1), and a compound represented by formula (2b-2). "1" refers to the compound represented by formula (1), "2" refers to the compound represented by formula (2), "2b" refers to the compound represented by formula (2b), "2b-1" refers to the compound represented by formula (2b-1), and "2b-2" refers to the compound represented by formula (2b-2). In addition, when a compound is equivalent to multiple of the above formulas, it is recorded as the following formula. For example, the compounds represented by formula (2b-1) and formula (2b-2) are equivalent to the compounds represented by formula (1) and formula (2b) at the same time, but only "2b-1" and "2b-2" are shown in the table respectively.

[0609] Furthermore, the Hammett substituent constant σ of the butyl group substituted on the benzene ring in compounds (D-1) and (D-19) is p is -0.20.

[0610] [Table 1]

[0611]

[0612] [Table 2]

[0613]

[0614] As shown in Table 1, in the photoelectric conversion element of the present invention, the half width of the absorption peak of the photoelectric conversion film is narrow.

[0615] It was confirmed that when the specific compound is a compound represented by formula (2) or formula (2b), and B1 (B2) is represented by formula (J-1) or formula (J-2), the performance of the photoelectric conversion element of the present invention is further improved.

[0616] (Results of Examples 2 to 12, 16 to 20, and 22 to 32, etc. (all evaluation items were rated "B" at one or less))

[0617] It was confirmed that when the specific compound is a compound represented by formula (2b), B1 (B2) is represented by formula (J-1), and R1 (Rc1) is a group represented by formula (R-2), a group represented by formula (R-4), a group represented by formula (4A), or a polycyclic aromatic ring that may have a substituent, the performance of the photoelectric conversion element of the present invention is further excellent.

[0618] (Results of Examples 2, 5 to 10, 16 to 18, 20, 22 to 31, etc. (all evaluation items were rated "A" or higher))

[0619] It was confirmed that when the specific compound is a compound represented by formula (2b-1) or formula (2b-2), and R1 (Rc3) is a group represented by formula (5A), a group represented by formula (5B), or a naphthyl group which may have a substituent, the performance of the photoelectric conversion element of the present invention is particularly excellent.

[0620] (Results of Examples 5 to 7, 10, 17, 18, 22, 24 to 27, and 30, etc. (All evaluation items were rated "A" or higher, and there was an item rated "AA"))

[0621] <Production of imaging elements>

[0622] Compounds (D-1) to (D-32) were used to prepare Figure 3 The imaging elements are of the same form as shown.

[0623] The above-mentioned photoelectric conversion element functioning as a green photoelectric conversion element was produced by the above-mentioned method.

[0624] In addition, a blue photoelectric conversion element and a red photoelectric conversion element were produced with reference to the description in Japanese Patent Application Laid-Open No. 2005-303266.

[0625] In the obtained imaging element, since the half width of the absorption peak of the photoelectric conversion film in the photoelectric conversion element of the present invention is narrow, light is easily received by the blue photoelectric conversion element and the red photoelectric conversion element, and the color separation performance is excellent.

[0626] Explanation of symbols

[0627] 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, 20a-imaging element, 22-blue photoelectric conversion element, 24-red photoelectric conversion element.

Claims

1. A photoelectric conversion element, comprising a conductive film, a photoelectric conversion film and a transparent conductive film in this order, wherein: The photoelectric conversion film comprises a compound represented by formula (1), [Chemical formula 1] In formula (1), R1 represents an aryl group which may have a halogen atom or an alkyl group, a heteroaryl group which may have a halogen atom or an alkyl group, a group represented by formula (R-2) or a group represented by formula (R-4), [Chemical formula 2] In formula (R-2), Ra2 and Ra3 each independently represent an alkyl group or an aryl group, Ra2 and Ra3 may be bonded to each other to form an aromatic ring or a non-aromatic ring, and * represents a bonding position. In formula (R-4), Ra 12 represents an aryl or heteroaryl group, * represents a bonding position, A represents a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, a quinoline ring or a benzothiophene ring, R2 and R3 each independently represent an alkyl group or an aryl group, R2 and R3 may be bonded to each other to form an aromatic ring or a non-aromatic ring, R4 represents a halogen atom, an alkoxy group, an alkyl group or an aryl group, R5 and R6 each independently represent a hydrogen atom, n represents an integer of 0 to 5, and when n is 2 or more, a plurality of R4 may be bonded to each other to form a fluorene ring, When A is a benzene ring, n is 1 or more, at least one of R4 represents an alkoxy group, an alkyl group or an aryl group, The total number of carbon atoms contained in R1 to R4 is 5 to 30, The total number of carbon atoms contained in R2 and R3 is 2 to 12, In R1 to R4, the number of carbon atoms of the aryl group is 6 to 30, the number of carbon atoms of the heteroaryl group is 3 to 30, and the number of heteroatoms of the heteroaryl group is 1 to 4. In Ra2 and Ra3, the number of carbon atoms of the alkyl group is 1 to 4, and the number of carbon atoms of the aryl group is 6 to 30. Ra 12 In the formula (a), the number of carbon atoms of the aryl group is 6 to 30, the number of carbon atoms of the heteroaryl group is 3 to 30, and the number of heteroatoms of the heteroaryl group is 1 to 4. When R1 represents an aryl group which may have a halogen atom or an alkyl group, a heteroaryl group which may have a halogen atom or an alkyl group, a group represented by the formula (R-2) or a group represented by the formula (R-4), B1 represents a group represented by the formula (B-1-1), [Chemical formula 3] In formula (B-1-1), E represents an aromatic ring or non-aromatic ring which may have a substituent selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a cyano group, a nitro group and an alkoxy group, the number of carbon atoms of E is 2 to 30, the number of heteroatoms in E is 0 to 5, E is a monocyclic structure or a condensed ring structure, the condensed ring structure is a condensed ring containing at least any one of a 5-membered ring, a 6-membered ring or a 5-membered ring and a 6-membered ring, the number of rings forming the condensed ring is 1 to 4 but not 1, Z1 represents an oxygen atom, * represents a connection position, However, the compound represented by formula (1) does not have any of a carboxyl group, a salt of a carboxyl group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.

2. The photoelectric conversion element according to claim 1, wherein The compound represented by the formula (1) is a compound represented by the formula (2) or a compound represented by the formula (2b), [Chemical formula 4] In formula (2), Rc1 has the same meaning as R1 in formula (1), R2 and R3 have the same meanings as R2 and R3 in formula (1), R5 and R6 have the same meanings as R5 and R6 in formula (1), R7 to R 10 Each independently represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group or an aryl group, and R7 to R 10 At least one of them represents an alkoxy group, an alkyl group or an aryl group, and Rc1, R2, R3 and R7 to R 10 The total number of carbon atoms contained in is 5 to 30, R7~R 10 In the formula (A), the alkyl group has 1 to 4 carbon atoms, the aryl group has 6 to 30 carbon atoms, B2 has the same meaning as B1 in formula (1), The compound represented by formula (2) does not have any of a carboxyl group, a carboxyl salt, a phosphate group, a phosphate salt, a sulfonic acid group, and a sulfonic acid salt. [Chemical formula 5] In formula (2b), Rc1 has the same meaning as R1 in formula (1), R2 to R6, n have the same meanings as R2 to R6, n in formula (1), respectively. A2 represents a naphthalene ring, a fluorene ring, a phenanthrene ring, a quinoline ring or a benzothiophene ring, The total number of carbon atoms contained in Rc1 and R2 to R4 is 5 to 30, B2 has the same meaning as B1 in formula (1), However, the compound represented by formula (2b) does not have any of a carboxyl group, a salt of a carboxyl group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.

3. The photoelectric conversion element according to claim 2, wherein The group represented by the formula (B-1-1) in the formula (2) and the formula (2b) is a group represented by the formulas (J-1) to (J-5), [Chemical formula 6] In formula (J-1), Rg1 to Rg4 each independently represent a hydrogen atom or a substituent, Rg1 to Rg4 may be bonded to each other to form an aromatic ring or a non-aromatic ring, K represents -CO-, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -NRb1-, -CRb2Rb3- or -SiRb4Rb5-, Rb1 to Rb5 each independently represent a hydrogen atom or a substituent, In formula (J-2), Rg5 and Rg6 each independently represent a hydrogen atom or a substituent, Ch represents =CRa7Ra8, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, Ra7 and Ra8 each independently represent a hydrogen atom or a substituent, Ra7 and Ra8 may be bonded to each other to form an aromatic ring or a non-aromatic ring, In formula (J-3), Rg7 represents a hydrogen atom or a substituent, Ch represents =CRa7Ra8, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, Ra7 and Ra8 each independently represent a hydrogen atom or a substituent, Ra7 and Ra8 may be bonded to each other to form an aromatic ring or a non-aromatic ring, L represents an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, In formula (J-4), Rg8 and Rg9 each independently represent a hydrogen atom or a substituent, Rg8 and Rg9 may be bonded to each other to form an aromatic ring or a non-aromatic ring, K represents -CO-, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -NRb1-, -CRb2Rb3- or -SiRb4Rb5-, and Rb1 to Rb5 each independently represent a hydrogen atom or a substituent, In formula (J-5), Rg 10 ~Rg 12 Each independently represents a hydrogen atom or a substituent, Rg 10 With Rg 11 can be bonded to each other to form an aromatic ring or a non-aromatic ring, Ch represents =CRa7Ra8, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, Ra7 and Ra8 each independently represent a hydrogen atom or a substituent, Ra7 and Ra8 can be bonded to each other to form an aromatic ring or a non-aromatic ring, The "substituent" has the same meaning as the "substituent" in formula (1).

4. The photoelectric conversion element according to claim 3, wherein The compound represented by the formula (1) is a compound represented by the formula (2) or the formula (2b), In the compound represented by the formula (2) or the formula (2b), the group represented by the formula (B-1-1) is the group represented by the formula (J-1) or the group represented by the formula (J-2).

5. The photoelectric conversion element according to claim 2, wherein The compound represented by the formula (1) is a compound represented by the formula (2b), and Rc1 represents a group represented by the formula (R-2), a group represented by the formula (R-4), a group represented by the formula (4A), a naphthyl group which may have an alkyl group, or a fluorenyl group which may have an alkyl group, [Chemical formula 7] In formula (4A), T 1 ~T 4 Represent CRe independently 12 or nitrogen atom, Re 12 represents a hydrogen atom, a halogen atom or an alkyl group, Rf 2 represents an alkyl group, Re 12 and Rf 2 In the formula, the number of carbon atoms in the alkyl group is 1 to 4. The total number of carbon atoms contained in Rc1 and R2 to R4 is 5 to 30, In addition, in formula (4A), when Re 12 When there are multiple 12 They may be the same as or different from each other.

6. The photoelectric conversion element according to claim 3, wherein The compound represented by the formula (1) is a compound represented by the formula (2b), and Rc1 represents a group represented by the formula (R-2), a group represented by the formula (R-4), a group represented by the formula (4A), a naphthyl group which may have an alkyl group, or a fluorenyl group which may have an alkyl group, [Chemical formula 7] In formula (4A), T 1 ~T 4 Represent CRe independently 12 or nitrogen atom, Re 12 represents a hydrogen atom, a halogen atom or an alkyl group, Rf 2 represents an alkyl group, Re 12 and Rf 2 In the formula, the number of carbon atoms in the alkyl group is 1 to 4. The total number of carbon atoms contained in Rc1 and R2 to R4 is 5 to 30, In addition, in formula (4A), when Re 12 When there are multiple 12 They may be the same as or different from each other.

7. The photoelectric conversion element according to claim 6, wherein The compound represented by the formula (1) is a compound represented by the formula (2b), In the compound represented by the formula (2b), the group represented by the formula (B-1-1) is the group represented by the formula (J-1), and Rc1 represents the group represented by the formula (4A), a naphthyl group which may have an alkyl group, or a fluorenyl group which may have an alkyl group.

8. The photoelectric conversion element according to claim 5 or 6, wherein The compound represented by the formula (1) is a compound represented by the formula (2b-1) or a compound represented by the formula (2b-2), [Chemical formula 8] In formula (2b-1), Rc3 represents a group represented by formula (4A), a naphthyl group which may have an alkyl group, or a fluorenyl group which may have an alkyl group, R2 and R3 have the same meanings as R2 and R3 in formula (1), R5 and R6 have the same meanings as R5 and R6 in formula (1), R 11 ~R 16 Rg1 to Rg4 independently represent a hydrogen atom or a substituent, and Rg1 to Rg4 may be bonded to each other to form an aromatic ring or a non-aromatic ring. Rc3, R2, R3 and R 11 ~R 16 The total number of carbon atoms contained in is 5 to 30, R 11 ~R 16 In the formula, the number of carbon atoms in the alkyl group is 1 to 4. The compound represented by formula (2b-1) does not have any of a carboxyl group, a carboxyl salt, a phosphate group, a phosphate salt, a sulfonic acid group, and a sulfonic acid salt. [Chemical formula 9] In formula (2b-2), Rc3 represents a group represented by formula (4A), a naphthyl group which may have an alkyl group, or a fluorenyl group which may have an alkyl group, R2 and R3 have the same meanings as R2 and R3 in formula (1), except that the total number of carbon atoms contained in R2 and R3 is 4 to 12, R5 and R6 have the same meanings as R5 and R6 in formula (1), and R 17 ~R 24 Each independently represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group or an aryl group, and R 17 ~R 24 may be bonded to each other to form a fluorene ring, Rg1 to Rg4 each independently represent a hydrogen atom or a substituent, and Rg1 to Rg4 may be bonded to each other to form an aromatic ring or a non-aromatic ring, Rc3, R2, R3 and R 17 ~R 24 The total number of carbon atoms contained in is 5 to 30, R 17 ~R 24 In the formula, the number of carbon atoms in the alkyl group is 1 to 4. The compound represented by formula (2b-2) does not have any of a carboxyl group, a carboxyl salt, a phosphate group, a phosphate salt, a sulfonic acid group, and a sulfonic acid salt. The "substituent" has the same meaning as the "substituent" in formula (1).

9. The photoelectric conversion element according to claim 8, wherein Rc3 represents a group represented by formula (5A), a group represented by formula (5B), or a naphthyl group which may have an alkyl group, [Chemical formula 10] In formula (5A), Re 1 ~Re 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group, and Rf 1 represents an alkyl group, Re 1 ~Re 4 and Rf 1 In the formula, the number of carbon atoms in the alkyl group is 1 to 4. [Chemical formula 11] In formula (5B), Re 5 ~Re 11 and Re 13 ~Re 14 each independently represents a hydrogen atom or an alkyl group, Re 5 ~Re 11 and Re 13 ~Re 14 In the above, the alkyl group has 1 to 4 carbon atoms.

10. The photoelectric conversion element according to any one of claims 1 to 4, wherein The photoelectric conversion film further comprises an n-type organic semiconductor, The photoelectric conversion film has a bulk heterostructure formed in a state where the compound represented by the formula (1) and the n-type organic semiconductor are mixed.

11. The photoelectric conversion element according to claim 10, wherein The n-type organic semiconductor comprises: fullerenes selected from the group consisting of fullerenes and derivatives thereof.

12. The photoelectric conversion element according to any one of claims 1 to 4, wherein In addition to the photoelectric conversion film, one or more intermediate layers are provided between the conductive film and the transparent conductive film. 13 . An imaging element comprising the photoelectric conversion element according to claim 1 . 14 . The imaging element according to claim 13 , further comprising another photoelectric conversion element that receives light having a wavelength different from that of the light received by the photoelectric conversion element.

15. The imaging element according to claim 14, wherein The photoelectric conversion element is stacked with the other photoelectric conversion element, After at least a portion of the incident light is transmitted through the photoelectric conversion element, the light is received by the other photoelectric conversion element.

16. The imaging element according to claim 14 or 15, wherein: The photoelectric conversion element is a green photoelectric conversion element. The other photoelectric conversion elements include a blue photoelectric conversion element and a red photoelectric conversion element.

17. A photosensor comprising the photoelectric conversion element according to any one of claims 1 to 12.

18. A compound represented by formula (1), wherein [Chemical formula 12] In formula (1), R1 represents an aryl group which may have a halogen atom or an alkyl group, a heteroaryl group which may have a halogen atom or an alkyl group, a group represented by formula (R-2) or a group represented by formula (R-4), [Chemical formula 13] In formula (R-2), Ra2 and Ra3 each independently represent an alkyl group or an aryl group, Ra2 and Ra3 may be bonded to each other to form an aromatic ring or a non-aromatic ring, and * represents a bonding position. In formula (R-4), Ra 12 represents an aryl or heteroaryl group, * represents a bonding position, A represents a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, a quinoline ring or a benzothiophene ring, R2 and R3 each independently represent an alkyl group or an aryl group, R2 and R3 may be bonded to each other to form an aromatic ring or a non-aromatic ring, R4 represents a halogen atom, an alkoxy group, an alkyl group or an aryl group, R5 and R6 each independently represent a hydrogen atom, n represents an integer of 0 to 5, and when n is 2 or more, a plurality of R4 may be bonded to each other to form a fluorene ring, When A is a benzene ring, n is 1 or more, at least one of R4 represents an alkoxy group, an alkyl group or an aryl group, The total number of carbon atoms contained in R1 to R4 is 5 to 30, The total number of carbon atoms contained in R2 and R3 is 2 to 12, In R1 to R4, the number of carbon atoms of the aryl group is 6 to 30, the number of carbon atoms of the heteroaryl group is 3 to 30, and the number of heteroatoms of the heteroaryl group is 1 to 4. In Ra2 and Ra3, the number of carbon atoms of the alkyl group is 1 to 4, and the number of carbon atoms of the aryl group is 6 to 30. Ra 12 In the formula (a), the number of carbon atoms of the aryl group is 6 to 30, the number of carbon atoms of the heteroaryl group is 3 to 30, and the number of heteroatoms of the heteroaryl group is 1 to 4. When R1 represents an aryl group which may have a halogen atom or an alkyl group, a heteroaryl group which may have a halogen atom or an alkyl group, a group represented by the formula (R-2) or a group represented by the formula (R-4), B1 represents a group represented by the formula (B-1-1); [Chemical formula 14] In formula (B-1-1), E represents an aromatic ring or non-aromatic ring which may have a substituent selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a cyano group, a nitro group and an alkoxy group, the number of carbon atoms of E is 2 to 30, the number of heteroatoms in E is 0 to 5, E is a monocyclic structure or a condensed ring structure, the condensed ring structure is a condensed ring containing at least any one of a 5-membered ring, a 6-membered ring or a 5-membered ring and a 6-membered ring, the number of rings forming the condensed ring is 1 to 4 but not 1, Z1 represents an oxygen atom, * represents a connection position, However, the compound represented by formula (1) does not have any of a carboxyl group, a salt of a carboxyl group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.

19. The compound according to claim 18, which is a compound represented by formula (2) or a compound represented by formula (2b), [Chemical formula 15] In formula (2), Rc1 has the same meaning as R1 in formula (1), R2 and R3 have the same meanings as R2 and R3 in formula (1), R5 and R6 have the same meanings as R5 and R6 in formula (1), R7 to R 10 Each independently represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group or an aryl group, and R7 to R 10 At least one of them represents an alkoxy group, an alkyl group or an aryl group, and Rc1, R2, R3 and R7 to R 10 The total number of carbon atoms contained in is 5 to 30, B2 has the same meaning as B1 in formula (1), in, The compound represented by formula (2) does not have any of a carboxyl group, a carboxyl salt, a phosphoric acid group, a phosphoric acid salt, a sulfonic acid group, and a sulfonic acid salt. [Chemical formula 16] In formula (2b), Rc1 has the same meaning as R1 in formula (1), R2 to R6, n have the same meanings as R2 to R6, n in formula (1), respectively. A2 represents a naphthalene ring, a fluorene ring, a phenanthrene ring, a quinoline ring or a benzothiophene ring, The total number of carbon atoms contained in Rc1 and R2 to R4 is 5 to 30, B2 has the same meaning as B1 in formula (1), However, the compound represented by formula (2b) does not have any of a carboxyl group, a salt of a carboxyl group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group.

20. The compound according to claim 19, which is a compound represented by the formula (2b), and Rc1 represents a group represented by the formula (R-2), a group represented by the formula (R-4), a group represented by the formula (4A), a naphthyl group which may have an alkyl group, or a fluorenyl group which may have an alkyl group, [Chemical formula 17] In formula (4A), T 1 ~T 4 Represent CRe independently 12 or nitrogen atom, Re 12 represents a hydrogen atom, a halogen atom or an alkyl group, Rf 2 represents an alkyl group, Re 12 and Rf 2 In the formula, the number of carbon atoms in the alkyl group is 1 to 4. The total number of carbon atoms contained in Rc1 and R2 to R4 is 5 to 30, In addition, in formula (4A), when Re 12 When there are multiple 12 They may be the same as or different from each other.

21. The compound according to claim 20, which is a compound represented by formula (2b-1) or a compound represented by formula (2b-2), [Chemical formula 18] In formula (2b-1), Rc3 represents a group represented by formula (4A), a naphthyl group which may have an alkyl group, or a fluorenyl group which may have an alkyl group, R2 and R3 have the same meanings as R2 and R3 in formula (1), R5 and R6 have the same meanings as R5 and R6 in formula (1), R 11 ~R 16 Rg1 to Rg4 independently represent a hydrogen atom or a substituent, and Rg1 to Rg4 may be bonded to each other to form an aromatic ring or a non-aromatic ring. Rc3, R2, R3 and R 11 ~R 16 The total number of carbon atoms contained in is 5 to 30, R 11 ~R 16 In the formula, the number of carbon atoms in the alkyl group is 1 to 4. in, The compound represented by formula (2b-1) does not have any of a carboxyl group, a carboxyl salt, a phosphoric acid group, a phosphoric acid salt, a sulfonic acid group, and a sulfonic acid salt. [Chemical formula 19] In formula (2b-2), Rc3 represents a group represented by formula (4A), a naphthyl group which may have an alkyl group, or a fluorenyl group which may have an alkyl group, R2 and R3 have the same meanings as R2 and R3 in formula (1), except that the total number of carbon atoms contained in R2 and R3 is 4 to 12, R5 and R6 have the same meanings as R5 and R6 in formula (1), and R 17 ~R 24 Each independently represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group or an aryl group, and R 17 ~R 24 may be bonded to each other to form a fluorene ring, Rg1 to Rg4 each independently represent a hydrogen atom or a substituent, and Rg1 to Rg4 may be bonded to each other to form an aromatic ring or a non-aromatic ring, Rc3, R2, R3 and R 17 ~R 24 The total number of carbon atoms contained in is 5 to 30, R 17 ~R 24 In the formula, the number of carbon atoms in the alkyl group is 1 to 4. The compound represented by formula (2b-2) does not have any of a carboxyl group, a carboxyl salt, a phosphate group, a phosphate salt, a sulfonic acid group, and a sulfonic acid salt. The "substituent" has the same meaning as the "substituent" in formula (1).

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