Photoelectric conversion element, imaging element, photosensor, and compound

Abstract

Provided is a photoelectric conversion element in which the dependence of photoelectric conversion efficiency on electric field strength is suppressed. Also provided are an imaging element, a light sensor, and a compound. The photoelectric conversion element of the present invention has, in order, a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein the photoelectric conversion film contains a compound represented by formula (1).

Description

Technical Field

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

[0002] In recent years, the development of components with photoelectric conversion films (e.g., imaging elements) has been underway.

[0003] For example, Patent Document 1 discloses the following organic semiconductor material as a material related to the optoelectronic field. Furthermore, in the following structural formula, R is a specified alkyl group.

[0004] [Chemical Formula 1]

[0005]

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: Chinese Patent Application Publication No. 104177380 Summary of the Invention

[0009] The technical problem to be solved by the invention

[0010] In recent years, with the increasing demands for improved performance of imaging elements and optical sensors, there is a growing need to further enhance the various characteristics required for the photoelectric conversion elements used in them.

[0011] For example, even with voltage variations applied to the photoelectric conversion element, a stable photoelectric conversion efficiency must be achieved.

[0012] The inventors conducted research on a photoelectric conversion element using the materials disclosed in Patent Document 1, and confirmed that it is difficult to suppress the dependence of the photoelectric conversion efficiency on the applied voltage.

[0013] In view of the above-mentioned actual situation, the objective of the present invention is to provide a photoelectric conversion element that suppresses the dependence of electric field strength on photoelectric conversion efficiency.

[0014] Furthermore, the present invention also aims to provide an imaging element, a light sensor, and a compound related to the above-mentioned photoelectric conversion element.

[0015] means for solving technical problems

[0016] The inventors conducted in-depth research on the above-mentioned problems and found that the above-mentioned problems could be solved by the following structure, thereby completing the present invention.

[0017] [1]

[0018] A photoelectric conversion element comprises, in sequence, a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein,

[0019] The aforementioned photoelectric conversion film comprises the compound represented by formula (1) described later.

[0020] [2]

[0021] According to the photoelectric conversion element described in [1], Ar 11 ~Ar 14 Each of the groups represented by any one of the formulas (2) to (7) described later can be used independently.

[0022] [3]

[0023] According to the photoelectric conversion element described in [1] or [2], wherein Ar 15 ~Ar 16 Each of the following formulas (8) to (15) and (47) to (53) represents a group independently.

[0024] [4]

[0025] According to any one of [1] to [3], n11 to n12 represent 1, n13 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

[0026] [5]

[0027] According to any one of [1] to [3], n11 to n14 represent 1, n15 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

[0028] [6]

[0029] According to any one of [1] to [3], the photoelectric conversion element, wherein n11 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

[0030] [7]

[0031] According to any one of [1] to [3], n11 to n12 represent 1, n13 to n14 represent 0, n15 to n16 represent 1, n17 represents 1, and n18 represents 1 or 2.

[0032] [8]

[0033] According to any one of [1] to [3], in the photoelectric conversion element, n11 to n14 represent 0, n15 to n16 represent 0 or 1 independently, n17 represents 2, and n18 represents 1.

[0034] [9]

[0035] The photoelectric conversion element according to any one of [1] to [3], wherein the compound represented by the above formula (1) is any one of the compounds represented by formulas (16) to (46) and (54) to (60) described later.

[0036]

[10]

[0037] According to the photoelectric conversion element described in [9], the compound represented by the above formula (1) is Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (16) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 111 ~Y 115 The compound represented by the above formula (17) with -CR= and R being a hydrogen atom, Y 21 ~Y 24 and Y 111 ~Y 115 The compound represented by the above formula (21) with -CR = and R being a hydrogen atom, Y 21 ~Y 24 and Y 151 ~Y 157 The compound represented by the above formula (22) with -CR= and R being a hydrogen atom, Y 61 ~Y 62 and Y 81 ~Y 85 The compound represented by the above formula (24) with -CR= and R being a hydrogen atom, Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (27) with -CR= and R being a hydrogen atom, Y 151 ~Y 157 The compound represented by the above formula (28) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (29) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 91 ~Y 97 For -CR= and R is a hydrogen atom, the above formula (44) and Y 51 ~Y 54 and Y 81 ~Y 85The compound represented by the above formula (45) with -CR= and R being a hydrogen atom, Y 21 ~Y 24 Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (46) with -CR= and R being a hydrogen atom, Y 471 ~Y 475 The compound represented by the above formula (54) with -CR= and R being a hydrogen atom, Y 481 ~Y 485 The compound represented by the above formula (55) with -CR= and R being a hydrogen atom, Y 491 ~Y 497 The compound represented by the above formula (56) with -CR= and R being a hydrogen atom, Y 501 ~Y 505 The compound represented by the above formula (57) with -CR= and R being a hydrogen atom, Y 511 ~Y 515 The compound represented by the above formula (58) with -CR= and R being a hydrogen atom, Y 521 ~Y 528 The compound represented by the above formula (59) with -CR= and R being a hydrogen atom, or Y 531 ~Y 539 The compound represented by the above formula (59) is -CR= and R is a hydrogen atom.

[0038]

[11]

[0039] According to the photoelectric conversion element described in [9], the compound represented by the above formula (1) is any one of the above formulas (16), (31), (32), (35), (37), (39) and (42).

[0040]

[12]

[0041] According to any one of [1] to

[11] , the photoelectric conversion element, wherein X 11 and X 12 It represents a sulfur atom.

[0042]

[13]

[0043] The photoelectric conversion element according to any one of [1] to

[12] , wherein the photoelectric conversion film further contains an n-type semiconductor material.

[0044]

[14]

[0045] According to the photoelectric conversion element described in

[13] , the above-mentioned n-type semiconductor material contains fullerenes selected from the group consisting of fullerenes and their derivatives.

[0046]

[15]

[0047] The photoelectric conversion element according to any one of [1] to

[14] , wherein the photoelectric conversion film further contains a p-type semiconductor material.

[0048]

[16]

[0049] The photoelectric conversion element according to any one of [1] to

[15] , wherein the photoelectric conversion film contains two compounds represented by the above formula (1).

[0050]

[17]

[0051] The photoelectric conversion element according to any one of [1] to

[16] , wherein the photoelectric conversion film further contains pigment.

[0052]

[18]

[0053] The photoelectric conversion element according to any one of [1] to

[17] , wherein, between the conductive film and the transparent conductive film, there is one or more intermediate layers in addition to the photoelectric conversion film.

[0054]

[19]

[0055] An imaging element having a photoelectric conversion element as described in any one of [1] to

[18] .

[0056]

[20]

[0057] An optical sensor having a photoelectric conversion element as described in any one of [1] to

[18] .

[0058] 〔twenty one〕

[0059] A compound represented by formula (1) as described below.

[0060] 〔twenty two〕

[0061] According to the compound described in

[21] , wherein Ar 11 ~Ar 14 Each of the groups represented by any one of the formulas (2) to (7) described later can be used independently.

[0062] 〔twenty three〕

[0063] According to the compound described in

[21] or

[22] , wherein Ar 15 ~Ar 16Each of the following formulas (8) to (15) and (47) to (53) represents a group independently.

[0064] 〔twenty four〕

[0065] The compound according to any one of

[21] to

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

[0066]

[25]

[0067] The compound according to any one of

[21] to

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

[0068]

[26]

[0069] The compound according to any one of

[21] to

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

[0070]

[27]

[0071] The compound according to any one of

[21] to

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

[0072]

[28]

[0073] The compound according to any one of

[21] to

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

[0074]

[29]

[0075] The compound according to any one of

[21] to

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

[0076]

[30]

[0077] According to the compound described in

[29] , wherein the compound represented by the above formula (1) is Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (16) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 111 ~Y115 The compound represented by the above formula (17) with -CR= and R being a hydrogen atom, Y 21 ~Y 24 and Y 111 ~Y 115 The compound represented by the above formula (21) with -CR = and R being a hydrogen atom, Y 21 ~Y 24 and Y 151 ~Y 157 The compound represented by the above formula (22) with -CR= and R being a hydrogen atom, Y 61 ~Y 62 and Y 81 ~Y 85 The compound represented by the above formula (24) with -CR= and R being a hydrogen atom, Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (27) with -CR= and R being a hydrogen atom, Y 151 ~Y 157 The compound represented by the above formula (28) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (29) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 91 ~Y 97 For -CR= and R is a hydrogen atom, the above formula (44) and Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (45) with -CR= and R being a hydrogen atom, Y 21 ~Y 24 Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (46) with -CR= and R being a hydrogen atom, Y 471 ~Y 475 The compound represented by the above formula (54) with -CR= and R being a hydrogen atom, Y 481 ~Y 485 The compound represented by the above formula (55) with -CR= and R being a hydrogen atom, Y 491 ~Y 497 The compound represented by the above formula (56) with -CR= and R being a hydrogen atom, Y 501 ~Y 505The compound represented by the above formula (57) with -CR= and R being a hydrogen atom, Y 511 ~Y 515 The compound represented by the above formula (58) with -CR= and R being a hydrogen atom, Y 521 ~Y 528 The compound represented by the above formula (59) with -CR= and R being a hydrogen atom, or Y 531 ~Y 539 The compound represented by the above formula (59) is -CR= and R is a hydrogen atom.

[0078]

[31]

[0079] According to the compound described in

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

[0080]

[32]

[0081] The compound according to any one of

[21] to

[31] , wherein X 11 and X 12 It represents a sulfur atom.

[0082] Invention Effects

[0083] According to the present invention, a photoelectric conversion element with excellent photoelectric conversion efficiency can be provided.

[0084] Furthermore, according to the present invention, it is possible to provide an imaging element, a light sensor, and a compound related to the above-mentioned photoelectric conversion element. Attached Figure Description

[0085] Figure 1 This is a cross-sectional schematic diagram showing a structural example of a photoelectric conversion element.

[0086] Figure 2 This is a cross-sectional schematic diagram showing a structural example of a photoelectric conversion element. Detailed Implementation

[0087] Hereinafter, a preferred embodiment of the photoelectric conversion element of the present invention will be described.

[0088] In this specification, halogen atoms include, for example, fluorine atoms, chlorine atoms, bromine atoms and iodine atoms, preferably fluorine atoms or chlorine atoms, and more preferably fluorine atoms.

[0089] In this specification, unless otherwise specified, aromatic ring groups can be monocyclic or polycyclic (e.g., 2- to 6-ring). A monocyclic aromatic ring group is an aromatic ring group having only one ring structure. A polycyclic (e.g., 2- to 6-ring) aromatic ring group is an aromatic ring group having multiple (e.g., 2- to 6) aromatic ring structures fused together.

[0090] The number of cyclic atoms in the above-mentioned aromatic cyclic group is preferably an integer from 5 to 15.

[0091] The aromatic cyclic group mentioned above can be an aromatic hydrocarbon cyclic group or an aromatic heterocyclic group.

[0092] When the aforementioned aromatic cyclic group is an aromatic heterocyclic group, the number of heteroatoms present as cyclic atom is, for example, 1 to 10. Examples of such heteroatoms include nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, phosphorus atom, silicon atom and boron atom.

[0093] Examples of aromatic hydrocarbon cyclic groups include phenylcycloyl, naphthyl, anthracenecycloyl, and phenanthrenecycloyl.

[0094] Examples of aromatic heterocyclic groups include pyridine cycloyl groups, pyrimidine cycloyl groups, pyridazine cycloyl groups, pyrazine cycloyl groups, triazine cycloyl groups (1,2,3-triazine cycloyl groups, 1,2,4-triazine cycloyl groups, 1,3,5-triazine cycloyl groups, etc.), tetraazine cycloyl groups (1,2,4,5-tetraazine rings, etc.), quinoxaline cycloyl groups, pyrrole cycloyl groups, furan cycloyl groups, thiophene cycloyl groups, imidazole cycloyl groups, oxazol cycloyl groups, thiazole cycloyl groups, and benzo[a] Pyrrole cycloyl, benzofuran cycloyl, benzothiophene cycloyl, benzoimidazol cycloyl, benzooxazole cycloyl, benzothiazole cycloyl, naphthopyrrole cycloyl, naphthofuran cycloyl, naphthothiophene cycloyl, naphthoimidazol cycloyl, 3H-pyrrolidinyl, pyrroloimidazol cycloyl (5H-pyrrolo[1,2-a]imidazolyl, etc.), imidazo[2,1-b]oxazole cycloyl, etc. ), thieno[2,3-d]thiazole cyclic group (thieno[2,3-d]thiazole cyclic group, etc.), benzothiadiazole cyclic group, benzodithiophene cyclic group (benzo[1,2-b:4,5-b']dithiazole cyclic group, etc.), thieno[3,2-b]thiazole cyclic group (thiazo[5,4-d]thiazole cyclic group, etc.), naphthodithiazole cyclic group (naphtho[2,3-b:6... [7-b′]dithiophene cycloyl, naphtho[2,1-b:6,5-b′]dithiophene cycloyl, naphtho[1,2-b:5,6-b′]dithiophene cycloyl, 1,8-dithiadicyclopentane[b,g]naphthyl cycloyl, etc.), benzothiophene-benzothiophene cycloyl, dithiaphene[3,2-b:2′,3′-d]thiophene cycloyl and 3,4,7,8-tetrathiadicyclopentane[a,e]pentene cycloyl.

[0095] In this specification, when referred to simply as an aromatic ring, examples of aromatic rings constituting the aforementioned aromatic ring group may be given.

[0096] When the aromatic ring group has a monovalent valence, such an aromatic ring group can be exemplified by a group formed by removing one hydrogen atom from the aromatic ring of the aforementioned aromatic ring group. In this case, the aromatic ring group is called an aryl or heteroaryl.

[0097] When the aromatic ring group is divalent, examples of such aromatic ring groups include those formed by removing two hydrogen atoms from the aromatic ring of the aforementioned aromatic ring group. These aromatic ring groups are then called aryl or heteroaryl. Alternatively, they can be called arylene or heteroarylene.

[0098] In this specification, when multiple identical symbols representing the types or quantities of groups exist in a single formula (general formula) representing a chemical structure, unless otherwise specified, the contents of these multiple identical symbols are independent of each other, and the contents of the same symbols may be the same or different.

[0099] In this specification, when multiple identical groups (aromatic cyclic groups, etc.) exist in a single formula (general formula) representing a chemical structure, unless otherwise specified, the specific contents of these multiple identical groups are independent of each other, and the specific contents of the identical groups may be the same or different.

[0100] Furthermore, in this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0101] In this specification, a hydrogen atom can be a light hydrogen atom (a typical hydrogen atom) or a heavy hydrogen atom (a dihydrogen atom, etc.).

[0102] Photoelectric conversion element

[0103] The photoelectric conversion element of the present invention comprises a conductive film, a photoelectric conversion film and a transparent conductive film in sequence, wherein the photoelectric conversion film comprises a compound represented by formula (1) (hereinafter also referred to as "specific compound").

[0104] The mechanism by which the photoelectric conversion element of the present invention can solve the above-mentioned problems by adopting this structure is not clear, but the inventors speculate as follows.

[0105] That is, the specific compound has a parent nucleus with an aromatic nitrogen-containing five-membered ring at both ends, and the parent nucleus has prescribed substituents at both ends. The parent nucleus has good crystallinity, and the types and configurations of substituents that the parent nucleus can have are limited to a range that does not hinder the crystallinity of the specific compound. Therefore, in the photoelectric conversion film, the specific compounds exhibit good charge transport among themselves, maintaining good charge transport even at low voltages. As a result, it is believed that the electric field strength dependence of the photoelectric conversion efficiency is suppressed in the photoelectric conversion element of the present invention containing the specific compound in the photoelectric conversion film.

[0106] Furthermore, the photoelectric conversion element of the present invention has good photoelectric conversion efficiency (especially for light with wavelengths of 400 to 700 nm), and dark current is also suppressed.

[0107] Hereinafter, the case in which the electric field strength dependence of the photoelectric conversion efficiency in the photoelectric conversion element is further suppressed, the case in which the photoelectric conversion efficiency is better and / or the dark current is further suppressed is also referred to as "the effect of the present invention is better".

[0108] Figure 1 The figure shows a cross-sectional schematic diagram of one embodiment of the photoelectric conversion element of the present invention.

[0109] Figure 1 The photoelectric conversion element 10a shown has the following structure, in which a conductive film (hereinafter also referred to as the lower electrode) 11, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound described later, and a transparent conductive film (hereinafter also referred to as the upper electrode) 15 are stacked in sequence.

[0110] Figure 2 The diagram shows a structural example of another photoelectric conversion element. Figure 2 The photoelectric conversion element 10b shown has the following structure: an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are sequentially stacked on the lower electrode 11. Furthermore, Figure 1 and Figure 2 The stacking order of the electron blocking film 16A, photoelectric conversion film 12 and hole blocking film 16B can also be appropriately changed according to the application and characteristics.

[0111] In the photoelectric conversion element 10a (or 10b), light is preferably incident on the photoelectric conversion film 12 via the upper electrode 15.

[0112] Furthermore, when using photoelectric conversion element 10a (or 10b), a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1×10⁻⁶ is applied between these pairs of electrodes. -5 ~1×10 7 A voltage of V / cm. From a performance and power consumption point of view, an applied voltage of 1×10 V / cm is more preferable. -4 ~1×10 7 V / cm, further preferably 1×10 -3 ~5×10 6 V / cm.

[0113] In addition, regarding the method of voltage application, in Figure 1 and Figure 2 In this case, the voltage is preferably applied with the electron blocking film 16A side serving as the cathode and the photoelectric conversion film 12 side serving as the anode. The same method can also be used when the photoelectric conversion element 10a (or 10b) is used as a light sensor or assembled into an imaging element.

[0114] As will be described in detail later, photoelectric conversion element 10a (or 10b) is preferably suitable for use as an imaging element.

[0115] The following describes in detail the configuration of each layer constituting the photoelectric conversion element of the present invention.

[0116] [Photoconversion film]

[0117] Photoelectric conversion films are films containing specific compounds.

[0118] The following is a detailed description of a specific compound.

[0119] <The compound represented by formula (1) (a specific compound)>

[0120] The specific compound is the compound represented by the following formula (1).

[0121] [Chemical Formula 2]

[0122]

[0123] In equation (1), X 11 and X 12 Each can be used to represent a sulfur atom or an oxygen atom independently.

[0124] Among them, X 11 and X 12 The preferred atom is sulfur.

[0125] Ar 11 ~Ar 16Each can be independently represented as a monocyclic aromatic ring group, a 2-cyclic aromatic ring group, or a 3-cyclic aromatic ring group.

[0126] Furthermore, the aforementioned aromatic cyclic group may have one or more substituents selected from the group consisting of halogen atoms (preferably fluorine atoms), cyano groups, and trifluoromethyl groups.

[0127] In other words, the above-mentioned aromatic cyclic group does not have any substituents other than one group selected from the group consisting of halogen atoms (preferably fluorine atoms), cyano groups and trifluoromethyl groups.

[0128] As Ar 11 ~Ar 16 The total number of the above-mentioned aromatic cyclic group having one or more of the above-mentioned groups as substituents, for example, is 0 to 5 independently.

[0129] Ar 11 ~Ar 14 It is a divalent aromatic cyclic group.

[0130] Ar 15 ~Ar 16 It is a monovalent aromatic cyclic group.

[0131] Ar 11 ~Ar 16 The aromatic cyclic group represented is preferably a nitrogen-containing aromatic cyclic group having one or more (e.g., 1 to 3) nitrogen atoms as cyclic elements.

[0132] Ar 11 with Ar 12 Preferably, the same aromatic ring group, Ar 13 with Ar 14 Preferably, the same aromatic ring group, Ar 15 with Ar 16 It is also preferred that they are the same aromatic ring groups. The same aromatic ring groups means that the aromatic ring groups used for comparison are the same groups, and the positional relationship of the structures constituting these aromatic ring groups (the heteroatoms and substituents that the aromatic ring groups may have) is also the same based on the parent nucleus of a specific compound (the part of the structure enclosed in parentheses marked with n17 in formula (1)).

[0133] From the viewpoint that the present invention offers superior performance, Ar 11 ~Ar 14 Preferably, each group is an independent group represented by any one of formulas (2) to (7).

[0134] [Chemical Formula 3]

[0135]

[0136] In equations (2) to (7), * represents the bonding position.

[0137] Regarding the two bonding positions in each of equations (2) to (7), the bonding position (*) on the left can be bonded to the nucleus side, and the bonding position (*) on the right can also be bonded to the nucleus side.

[0138] In equations (2) to (7), Y N The group represented is -CR= or a nitrogen atom. Y N In this context, "N" is an integer.

[0139] That is, in equations (2) to (7), Y 21 ~Y 24 Y 31 ~Y 36 Y 41 ~Y 42 Y 51 ~Y 54 Y 61 ~Y 62 and Y 71 They can be represented independently as -CR= or nitrogen atom (-N=).

[0140] In -CR=, R represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a cyano group, or a trifluoromethyl group.

[0141] In equations (2) to (7), X N The indicated groups represent sulfur atoms (-S-), oxygen atoms (-O-), or selenium atoms (-Se-). X N In this context, "N" is an integer.

[0142] That is, in equations (2) to (7), X 41 X 51 X 61 ~X 62 and X 71 Sulfur atom (-S-), oxygen atom (-O-) or selenium atom (-Se-) are represented independently, preferably sulfur atom or oxygen atom.

[0143] From the viewpoint that the present invention offers superior performance, Ar 15 ~Ar 16 Preferably, each group is represented independently by any one of the formulas (8) to (15) and (47) to (53).

[0144] [Chemical Formula 4]

[0145]

[0146] [Chemical Formula 5]

[0147]

[0148] In equations (8) to (15) and equations (47) to (53), * indicates the bonding position.

[0149] In equations (8) to (15) and equations (47) to (53), Y N The group represented is -CR= or a nitrogen atom. Y N In this context, "N" is an integer.

[0150] That is, in equations (8) to (15) and equations (47) to (53), Y 81 ~Y 85 Y 91 ~Y 97 Y 101 ~Y 103 Y 111 ~Y 115 Y 121 ~Y 123 Y 131 ~Y 137 Y 141 ~Y 145 Y 151 ~Y 157 Y 471 ~Y 475 Y 481 ~Y 485 Y 491 ~Y 497 Y 501 ~Y 505 Y 511 ~Y 515 Y 521 ~Y 529 and Y 531 ~Y 539 They can be represented independently as -CR= or nitrogen atom (-N=).

[0151] In -CR=, R represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a cyano group, or a trifluoromethyl group.

[0152] Among them, as Y 81 ~Y 85 Y 91 ~Y 97 Y 101 ~Y 103 Y 111 ~Y 115 Y 121 ~Y 123 Y 131 ~Y 137 Y 141 ~Y 145 Y151 ~Y 157 Y 471 ~Y 475 Y 481 ~Y 485 Y 491 ~Y 497 Y 501 ~Y 505 Y 511 ~Y 515 Y 521 ~Y 529 and Y 531 ~Y 539 Preferably, -CR=, more preferably -CR= where R is a hydrogen atom. That is, as Y 81 ~Y 85 Y 91 ~Y 97 Y 101 ~Y 103 Y 111 ~Y 115 Y 121 ~Y 123 Y 131 ~Y 137 Y 141 ~Y 145 Y 151 ~Y 157 Y 471 ~Y 475 Y 481 ~Y 485 Y 491 ~Y 497 Y 501 ~Y 505 Y 511 ~Y 515 Y 521 ~Y 529 and Y 531 ~Y 539 Preferably, -CH=.

[0153] In equations (8) to (15) and (47) to (53), X N The indicated groups represent sulfur atoms (-S-), oxygen atoms (-O-), or selenium atoms (-Se-). X N In this context, "N" is an integer.

[0154] That is, in equations (8) to (15) and (47) to (53), X 101 X 111 X 121 ~X 122 X 141 X 151 X 471~X 472 X 481 ~X 482 X 491 X 501 ~X 502 and X 511 ~X 512 Sulfur atom (-S-), oxygen atom (-O-) or selenium atom (-Se-) are represented independently, preferably sulfur atom or oxygen atom.

[0155] In equation (1), X 13 and X 14 Oxygen atoms (=O) or sulfur atoms (=S) can be represented independently, with oxygen atoms being preferred.

[0156] X 13 and X 14 Preferably, they are the same atoms.

[0157] In equation (1), n11 to n16 represent 0 or 1 independently.

[0158] n11 and n12 are preferably the same value, n13 and n14 are preferably the same value, and n15 and n16 are preferably the same value.

[0159] When n11 to n16 are 0, the groups enclosed in parentheses indicating n11 to n16 do not exist. For example, when n11 is 1 and n13 and n15 are 0, in equation (1), Ar 11 with Ar 15 Bonded by single bonds.

[0160] When n11 to n16 are all 0 and n17 is 1, Ar 15 and Ar 16 The aromatic ring group mentioned above is a 3-ring aromatic ring group.

[0161] Furthermore, when applying a specific compound to formula (1), if there exists a specific compound that can be interpreted as either an interpretation where n11 is 1 and n13 is 0, or an interpretation where n11 is 0 and n13 is 1, then the specific compound is preferably interpreted as a compound in formula (1) where n11 is 1 and n13 is 0.

[0162] Similarly, when applying a particular compound to formula (1), if there exists a particular compound that can be interpreted as either an interpretation of n12 being 1 and n14 being 0, or an interpretation of n12 being 0 and n14 being 1, then the particular compound is preferably interpreted as a compound in formula (1) where n12 is 1 and n14 is 0.

[0163] In equation (1), n17 represents 1 or 2.

[0164] When n17 is 2, the parent nucleus of a specific compound becomes a structure in which two aromatic ring groups of 4 or 5 rings are bonded together by a single bond.

[0165] When n17 is 2, X is also preferred to exist on the outer side of the parent nucleus. 11 and X 12 They are the same atoms.

[0166] When n17 is 2, X is preferably located inside the mother nucleus. 11 and X 12 They are the same atoms.

[0167] In equation (1), n18 represents 1 or 2.

[0168] Among them, the following examples can be cited as preferred combinations of n11 to n18 in equation (1).

[0169] Example A: n11~n12 represent 1, n13~n16 represent 0, n17 represents 1, and n18 represents a combination of 1 or 2.

[0170] Example B: n11~n14 represent 1, n15~n16 represent 0, n17 represents 1, and n18 represents a combination of 1 or 2.

[0171] Example C: n11 to n16 represent 0, n17 represents 1, and n18 represents a combination of 1 or 2.

[0172] Example D: n11~n12 represents 1, n13~n14 represents 0, n15~n16 represents 1, n17 represents 1, and n18 represents a combination of 1 or 2.

[0173] Example E: n11~n14 represent 0, n15~n16 represent 0 or 1 independently, n17 represents 2, and n18 represents the combination of 1.

[0174] From the viewpoint of achieving better results from the present invention, the specific compound is preferably a compound represented by any one of the formulas (16) to (46) and (54) to (60) shown below.

[0175] [Chemical Formula 6]

[0176]

[0177] [Chemical Formula 7]

[0178]

[0179] [Chemical Formula 8]

[0180]

[0181] [Chemical Formula 9]

[0182]

[0183] [Chemical Formula 10]

[0184]

[0185] [Chemical Formula 11]

[0186]

[0187] [Chemical Formula 12]

[0188]

[0189] [Chemical Formula 13]

[0190]

[0191] [Chemical Formula 14]

[0192]

[0193] In equations (16) to (46) and equations (54) to (60), Y N The group represented is -CR= or a nitrogen atom. Y N In this context, "N" is an integer.

[0194] That is, in equations (16) to (46), Y 21 ~Y 24 Y 41 ~Y 42 Y 51 ~Y 54 Y 61 ~Y 62 Y 71 Y 81 ~Y 85 Y 91 ~Y 97 Y 101 ~Y 103 Y 111 ~Y 115 Y 121 ~Y 123 Y 151 ~Y 157 Y 471 ~Y 475 Y 481 ~Y 485 Y 491 ~Y 497 Y 501 ~Y 505 Y 511 ~Y515 Y 521 ~Y 528 and Y 531 ~Y 539 They can be represented independently as -CR= or nitrogen atom (-N=).

[0195] In -CR=, R represents a hydrogen atom, a halogen atom (preferably a fluorine atom), a cyano group, or a trifluoromethyl group.

[0196] Among them, as Y 81 ~Y 85 Y 91 ~Y 97 Y 101 ~Y 103 Y 111 ~Y 115 Y 121 ~Y 123 Y 131 ~Y 137 Y 141 ~Y 145 Y 151 ~Y 157 Y 471 ~Y 475 Y 481 ~Y 485 Y 491 ~Y 497 Y 501 ~Y 505 Y 511 ~Y 515 Y 521 ~Y 529 and Y 531 ~Y 539 Preferably, -CR=, more preferably -CR= where R is a hydrogen atom. That is, as Y 81 ~Y 85 Y 91 ~Y 97 Y 101 ~Y 103 Y 111 ~Y 115 Y 121 ~Y 123 Y 131 ~Y 137 Y 141 ~Y 145 Y 151 ~Y 157 Y 471 ~Y 475 Y 481 ~Y 485 Y 491 ~Y 497 Y 501~Y 505 Y 511 ~Y 515 Y 521 ~Y 529 and Y 531 ~Y 539 Preferably, -CH=.

[0197] In equations (16) to (46) and equations (54) to (60), X 11 and X 12 They represent sulfur atoms (-S-) or oxygen atoms (-O-) independently, respectively.

[0198] In equations (16) to (46), X 13 and X 14 They can be used to represent sulfur atoms (=S) or oxygen atoms (=O) independently.

[0199] In equations (16) to (46), except for X 11 ~X 14 Other than X N The indicated groups represent sulfur atoms (-S-), oxygen atoms (-O-), or selenium atoms (-Se-). X N In this context, "N" is an integer.

[0200] In equations (16) to (46) and equations (54) to (60), X 41 X 51 X 61 ~X 62 X 71 X 101 X 111 X 121 ~X 122 X 151 X 471 X 481 ~X 482 X 491 X 501 ~X 502 and X 511 ~X 512 Sulfur atom (-S-), oxygen atom (-O-) or selenium atom (-Se-) are represented independently, preferably sulfur atom or oxygen atom.

[0201] Regarding a particular compound (especially when used as an n-type material as described later), it is preferable to satisfy the requirement of being Ar 11 and Ar 12 The ring structure has an aromatic cyclic group containing a -N= group or at least one of n15 and n16 being 1, and Ar 15 and Ar 16 Middle, Y 81 ~Y85 The group represented by formula (8) is -CF=, -C(CN)= or -N=.

[0202] Certain compounds (especially when used as p-type materials as described later) are preferably Y-type. 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (16) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 111 ~Y 115 The compound represented by the above formula (17) with -CR= and R being a hydrogen atom, Y 21 ~Y 24 and Y 111 ~Y 115 The compound represented by the above formula (21) with -CR = and R being a hydrogen atom, Y 21 ~Y 24 and Y 151 ~Y 157 The compound represented by the above formula (22) with -CR= and R being a hydrogen atom, Y 61 ~Y 62 and Y 81 ~Y 85 The compound represented by the above formula (24) with -CR= and R being a hydrogen atom, Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (27) with -CR= and R being a hydrogen atom, Y 151 ~Y 157 The compound represented by the above formula (28) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (29) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 91 ~Y 97 For -CR= and R is a hydrogen atom, the above formula (44) and Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (45) with -CR= and R being a hydrogen atom, Y 21 ~Y 24 Y 41 ~Y 42 and Y 81 ~Y85 The compound represented by the above formula (46) with -CR= and R being a hydrogen atom, Y 471 ~Y 475 The compound represented by the above formula (54) with -CR= and R being a hydrogen atom, Y 481 ~Y 485 The compound represented by the above formula (55) with -CR= and R being a hydrogen atom, Y 491 ~Y 497 The compound represented by the above formula (56) with -CR= and R being a hydrogen atom, Y 501 ~Y 505 The compound represented by the above formula (57) with -CR= and R being a hydrogen atom, Y 511 ~Y 515 The compound represented by the above formula (58) with -CR= and R being a hydrogen atom, Y 521 ~Y 528 The compound represented by the above formula (59) with -CR= and R being a hydrogen atom, or Y 531 ~Y 539 The compound represented by the above formula (59) is -CR= and R is a hydrogen atom.

[0203] Furthermore, the notation of the above compounds indicates that Y in each formula N (N is a number) indicates a group represented by -CR= (R represents a hydrogen atom). More specifically, for example, "Y 41 ~Y 42 and Y 81 ~Y 85 "The compound represented by the above formula (16) with -CR = and R being a hydrogen atom" refers to Y in formula (16). 41 ~Y 42 and Y 81 ~Y 85 Compounds with -CR= (R represents a hydrogen atom).

[0204] The specific compound (especially when used as an n-type material as described later) is preferably a compound represented by any one of the above formulas (16), (31), (32), (35), (37), (39) and (42).

[0205] The following are specific examples of particular compounds.

[0206] [Chemical Formula 15]

[0207]

[0208] [Chemical Formula 16]

[0209]

[0210] [Chemical Formula 17]

[0211]

[0212] [Chemical Formula 18]

[0213]

[0214] [Chemical Formula 19]

[0215]

[0216] [Chemical Formula 20]

[0217]

[0218] [Chemical Formula 21]

[0219]

[0220] [Chemical Formula 22]

[0221]

[0222] [Chemical Formula 23]

[0223]

[0224] [Chemical Formula 24]

[0225]

[0226] [Chemical Formula 25]

[0227]

[0228] [Chemical Formula 26]

[0229]

[0230] [Chemical Formula 27]

[0231]

[0232] [Chemical Formula 28]

[0233]

[0234] [Chemical Formula 29]

[0235]

[0236] [Chemical Formula 30]

[0237]

[0238] [Chemical Formula 31]

[0239]

[0240] [Chemical Formula 32]

[0241]

[0242] [Chemical Formula 33]

[0243]

[0244] [Chemical Formula 34]

[0245]

[0246] [Chemical Formula 35]

[0247]

[0248] There are no particular limitations on the molecular weight of the specific compound, but it is preferably 550 or more, more preferably 600 or more. The molecular weight of the specific compound is preferably 1200 or less, more preferably 1000 or less.

[0249] If the molecular weight is below 1200, the evaporation temperature will not increase, and the compound is less likely to decompose. If the molecular weight is above 550, the glass transition point of the evaporated film will not decrease, and the heat resistance of the photoelectric conversion element will be improved.

[0250] Certain compounds are particularly useful as materials for photoelectric conversion films used in imaging elements, optical sensors, or photovoltaic cells. Furthermore, these compounds can also be used as coloring materials, liquid crystal materials, organic semiconductor materials, charge transport materials, medical materials, and fluorescent diagnostic drug materials.

[0251] There are no particular limitations on the maximum absorption wavelength of a particular compound, but it is preferably in the range of 300 to 550 nm, and more preferably in the range of 400 to 550 nm.

[0252] Furthermore, the aforementioned maximum absorption wavelength is the value measured in solution (solvent: chloroform) at a concentration where the absorption spectrum of a specific compound is adjusted to achieve an absorbance of 0.5 to 1. However, when a specific compound is insoluble in chloroform, the maximum absorption wavelength will be measured using the value of the specific compound as a film obtained by vapor deposition.

[0253] There are no particular limitations on the maximum absorption wavelength of the photoelectric conversion film, but it is preferably in the range of 300 to 700 nm, and more preferably in the range of 400 to 700 nm.

[0254] Furthermore, certain compounds can be used as both p-type materials (materials with excellent hole transport properties) and n-type materials (materials with excellent electron transport properties).

[0255] When a particular compound is used as an n-type material, the particular compound preferably satisfies one or more of the following requirements.

[0256] Requirement 1: The specific compound has three or more (e.g., 4 to 16) fluorine atoms in its molecule (preferably Ar in formula (1)). 11 ~Ar 16 (The fluorine atom present is due to the substituent of the aromatic ring group).

[0257] Requirement 2: Ar 11 ~Ar 14 One or more (preferably 2 to 4) of the atoms are nitrogen-containing aromatic cyclic groups containing nitrogen atoms as cyclic elements, and the molecule has a total of one or more (e.g., 2 to 16) fluorine atoms or cyano groups (preferably Ar in formula (1)). 11 ~Ar 16 (The fluorine atom present is due to the substituent of the aromatic ring group).

[0258] When a specific compound is used as a p-type material, the specific compound is preferably a compound that does not satisfy any of the above requirements.

[0259] When a specific compound is used as a p-type material, the ionization potential of that specific compound is preferably 5.0 to 6.0 eV.

[0260] Furthermore, when a specific compound is used as an n-type material, the electron affinity of that specific compound is preferably 3.0 to 4.5 eV.

[0261] In this specification, the value of the opposite of the LUMO value (multiplied by -1) is used as the value of electron affinity, which is obtained by calculating B3LYP / 6-31G(d) using Gaussian'09 (software manufactured by Gaussian Corporation).

[0262] The specific compounds contained in the photoelectric conversion film can be specific compounds that are essentially used only as p-type materials, specific compounds that are essentially used only as n-type materials, or specific compounds that are used as both p-type and n-type materials.

[0263] The specific compounds contained in the photoelectric conversion film are essentially only those used as p-type materials. This means that, relative to all the specific compounds contained in the photoelectric conversion film, the content of the specific compounds used as p-type materials (= film thickness of the specific compounds used as p-type materials in monolayer form / total film thickness of all specific compounds in monolayer form × 100) is more than 90% by volume and less than 100% by volume (preferably 95 to 100% by volume, more preferably 99 to 100% by volume).

[0264] The specific compounds contained in the photoelectric conversion film are essentially only those used as n-type materials. This means that, relative to all the specific compounds contained in the photoelectric conversion film, the content of the specific compounds used as n-type materials (= film thickness of the specific compounds used as n-type materials in monolayer form / total film thickness of all specific compounds in monolayer form × 100) is more than 90% by volume and less than 100% by volume (preferably 95 to 100% by volume, more preferably 99 to 100% by volume).

[0265] When the specific compound contained in the photoelectric conversion film is both a specific compound used as a p-type material and a specific compound used as an n-type material, the ratio of the content of the specific compound used as a p-type material to the content of the specific compound used as an n-type material in the photoelectric conversion film (= film thickness of the specific compound used as a p-type material in monolayer conversion / film thickness of the specific compound used as an n-type material in monolayer conversion) is preferably 10 / 90 to 90 / 10, more preferably 40 / 60 to 60 / 40, and even more preferably 47 / 53 to 53 / 47.

[0266] Photoelectric conversion films can contain only one specific compound, or two, or even three or more.

[0267] The term "photoelectric conversion film containing only one specific compound" means that the photoelectric conversion film contains only one specific compound.

[0268] The fact that the photoelectric conversion film contains only one specific compound means that, relative to all the specific compounds contained in the photoelectric conversion film, the content of the most specific compound (=film thickness of the most specific compound in single layer / total film thickness of all specific compounds in single layer × 100) is more than 90% by volume and less than 100% by volume (preferably 95 to 100% by volume, more preferably 99 to 100% by volume).

[0269] When only one specific compound is contained, the aforementioned specific compound can be a specific compound used as a p-type material or a specific compound used as an n-type material.

[0270] The term "photoelectric conversion film contains two specific compounds" means that the photoelectric conversion film actually contains only two specific compounds.

[0271] The fact that the photoelectric conversion film contains only two specific compounds means that, relative to all the specific compounds contained in the photoelectric conversion film, the total content of the two most abundant specific compounds (= total film thickness of the two most abundant specific compounds in single-layer conversion / total film thickness of all specific compounds in single-layer conversion × 100) is more than 90% by volume and less than 100% by volume (preferably 95 to 100% by volume, more preferably 99 to 100% by volume).

[0272] When the two most abundant specific compounds are designated as specific compound A and specific compound B, the ratio of the content of specific compound A to specific compound B in the photoelectric conversion film (=film thickness of specific compound A in monolayer form / film thickness of specific compound B in monolayer form) is preferably 10 / 90 to 90 / 10, more preferably 40 / 60 to 60 / 40, and even more preferably 47 / 53 to 53 / 47.

[0273] When only two specific compounds are contained, the two specific compounds can be either specific compounds that are both used as p-type materials or specific compounds that are both used as n-type materials. It is also preferred that one of them is a specific compound used as a p-type material and the other is a specific compound used as an n-type material.

[0274] From the viewpoint of the responsiveness of the photoelectric conversion element, the content of a specific compound in the photoelectric conversion film (=film thickness of the specific compound in monolayer form / film thickness of the photoelectric conversion film × 100) is preferably 15 to 85% by volume.

[0275] When the photoelectric conversion element contains only one specific compound, the content of the specific compound in the photoelectric conversion film is more preferably 20-60% by volume, and even more preferably 25-40% by volume.

[0276] When the photoelectric conversion element contains two specific compounds, the content of the specific compounds in the photoelectric conversion film is more preferably 40-80% by volume, and even more preferably 60-75% by volume.

[0277] <pigment>

[0278] The photoelectric conversion film also preferably contains pigments as other components besides the specific compounds mentioned above.

[0279] The pigments mentioned above are preferably organic pigments.

[0280] Examples of the aforementioned pigments include anthocyanins, styrene pigments, hemicyanins, partial anthocyanins (including zero-methylene partial anthocyanins (simple partial anthocyanins)), rotannins, allopolar pigments, oxacyanins, hemioxacyanins, squaric acid cyanins, ketoneonium pigments, azamethine pigments, coumarin pigments, aryl pigments, anthraquinone pigments, triphenylmethane pigments, azo pigments, methylene azo pigments, metallocene pigments, fluorenone pigments, fulgide pigments, perylene pigments, and phenazines. Pigments, phenothiazine pigments, quinone pigments, diphenylmethane pigments, polyene pigments, acridine pigments, acridine ketone pigments, quinoxaline pigments, diphenylamine pigments, quinoline pigments, phenothiazine pigments, perylene pigments, dioxane pigments, porphyrin pigments, chlorophyll pigments, phthalocyanine pigments, subphthalocyanine pigments, metal complex pigments, compounds described in paragraphs

[0083] to

[0089] of Japanese Patent Application Publication No. 2014-82483, and paragraphs

[0029] to

[0033] of Japanese Patent Application Publication No. 2009-167348. The compounds described in the following documents: Japanese Patent Application Publication No. 2012-077064, Japanese Patent Application Publication No. 2012-077064, Japanese Patent Application Publication No. 2018-105269, Japanese Patent Application Publication No. 2018-186389, Japanese Patent Application Publication No. 2018-186397, Japanese Patent Application Publication No. 2019-009249 ... The compounds described in paragraphs

[0078] to

[0083] of WO2019-049946, the compounds described in paragraphs

[0054] to

[0056] of WO2019-054327, the compounds described in paragraphs

[0059] to

[0063] of WO2019-098161, and the compounds described in paragraphs

[0085] to

[0114] of WO2020-013246.

[0281] The pigment content in the photoelectric conversion film (=pigment thickness in monolayer conversion / photoelectric conversion film thickness × 100) is preferably 15 to 85% by volume, more preferably 20 to 60% by volume, and even more preferably 25 to 40% by volume.

[0282] The pigment content (=(film thickness of pigment in monolayer form / (film thickness of specific compound in monolayer form + film thickness of pigment in monolayer form) × 100)) is preferably 15 to 75% by volume, more preferably 20 to 65% by volume, and even more preferably 25 to 60% by volume, relative to the total content of specific compounds and pigments in the photoelectric conversion film.

[0283] In addition, one type of pigment can be used alone, or two or more types can be used.

[0284] <n-type semiconductor materials>

[0285] The photoelectric conversion film preferably contains an n-type semiconductor material as an additional component besides the aforementioned specific compounds and pigments.

[0286] When the photoelectric conversion film contains a specific compound used as a p-type material, it is preferable to contain an n-type semiconductor material. When the specific compound contained in the photoelectric conversion film is only a specific compound used as a p-type material, the photoelectric conversion film is more preferably containing an n-type semiconductor material. When the photoelectric conversion film contains only one specific compound and the aforementioned one specific compound is a specific compound used as a p-type material, the photoelectric conversion film is even more preferably containing an n-type semiconductor material.

[0287] n-type semiconductor materials are acceptor organic semiconductor materials (compounds), which refer to organic compounds that readily accept electrons.

[0288] More specifically, the n-type semiconductor material is preferably an organic compound that has a greater electron affinity than the specific compound when used in contact with it.

[0289] Furthermore, the n-type semiconductor material is preferably an organic compound with a greater electron affinity than the pigment when used in contact with the aforementioned pigment.

[0290] The preferred electron affinity of n-type semiconductor materials is 3.0–5.0 eV.

[0291] Regarding n-type semiconductor materials, examples include fullerenes selected from the group consisting of fullerenes and their derivatives; fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetraphenylene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); heterocyclic compounds having at least one nitrogen, oxygen, and sulfur atom in a 5- to 7-membered ring (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, borazine, isoquinoline, pteridine, acridine, phenazine, phenanthrene, tetrazolium, pyrazole, imidazole, and thiazole); polyarylene compounds; fluorene compounds; and cyclic compounds. Pentadiene compounds; silyl compounds; 1,4,5,8-naphthyltetracarboxylic anhydride; 1,4,5,8-naphthyltetracarboxylic anhydride imide derivatives, oxadiazole derivatives; anthraquinone dimethyl derivatives; dibenzoquinone derivatives; bathocuproine, phenanthrene-rhein, and their derivatives; triazole compounds; stilbene aryl derivatives; metal complexes having nitrogen-containing heterocyclic compounds as ligands; silole compounds; and compounds described in paragraphs

[0056] to

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

[0292] Among them, the n-type semiconductor material preferably includes fullerenes selected from the group consisting of fullerenes and their derivatives.

[0293] Regarding fullerenes, examples 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.

[0294] Regarding fullerene derivatives, examples include compounds in which substituents have been added to the fullerenes described above. The substituents are preferably alkyl, aryl, or heterocyclic groups. The fullerene derivatives are preferably compounds described in Japanese Patent Application Publication No. 2007-123707.

[0295] When the photoelectric conversion film contains n-type semiconductor material, the content of n-type semiconductor material in the photoelectric conversion film (=n-type semiconductor material thickness in monolayer form / photoelectric conversion film thickness × 100) is preferably 15-75% by volume, more preferably 20-60% by volume, and even more preferably 25-50% by volume.

[0296] In addition, n-type semiconductor materials can be used alone or in combination with two or more types.

[0297] Furthermore, when the n-type semiconductor material contains fullerenes, the content of fullerenes (=(film thickness of fullerenes in monolayer form / total film thickness of each n-type semiconductor material in monolayer form)×100) is preferably 50 to 100% by volume, more preferably 80 to 100% by volume, relative to the total content of the n-type semiconductor material.

[0298] In addition, fullerenes can be used alone or in combination with more than one type.

[0299] The molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.

[0300] The photoelectric conversion film is preferably composed substantially only of specific compounds, pigments, and n-type semiconductor materials. "Substantially composed of specific compounds, pigments, and n-type semiconductor materials" means that the total content of the specific compounds, pigments, and n-type semiconductor materials relative to the total mass of the photoelectric conversion film is 95–100% by mass.

[0301] <p-type semiconductor materials>

[0302] The photoelectric conversion film also preferably contains p-type semiconductor material as other components besides the aforementioned specific compounds and pigments.

[0303] When the photoelectric conversion film contains a specific compound used as an n-type material, it is preferable to contain a p-type semiconductor material. When the specific compound contained in the photoelectric conversion film is only a specific compound used as an n-type material, the photoelectric conversion film is more preferably containing a p-type semiconductor material. When the photoelectric conversion film contains only one specific compound and the aforementioned one specific compound is a specific compound used as an n-type material, the photoelectric conversion film is even more preferably containing a p-type semiconductor material.

[0304] p-type semiconductor materials are donor organic semiconductor materials (compounds), which are organic compounds that readily donate electrons.

[0305] More specifically, the p-type semiconductor material is preferably an organic compound with superior hole transport ratio compared to a specific compound in the photoelectric conversion film, and more preferably an organic compound with superior hole transport ratio compared to either the specific compound or the pigment.

[0306] In this specification, the hole transport properties (hole carrier mobility) of the compounds can be evaluated, for example, using the Time-of-Flight (TOF) method or field-effect transistor devices.

[0307] The hole carrier mobility of p-type semiconductor materials is preferably 10. -4 cm 2 / V·s or more, preferably 10 -3 cm 2 / V·s or higher, further preferably 10 -2 cm 2 / V·s or higher. There is no particular upper limit to the hole carrier mobility mentioned above, but from the viewpoint of suppressing minute current flow in the absence of light irradiation, a value of, for example, 10 cm⁻¹ is preferred. 2 / V·s and below.

[0308] Furthermore, it is preferable that the ionization potential of the p-type semiconductor material is smaller than that of the specific compound in the photoelectric conversion film, and more preferably that the ionization potential is smaller than that of either the specific compound or the pigment.

[0309] Regarding p-type semiconductor materials, examples 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 Japanese Patent Application Publication No. 2011-228614, compounds described in paragraphs

[0052] to

[0063] of Japanese Patent Application Publication No. 2011-176259, and paragraph

[0119] of Japanese Patent Application Publication No. 2011-225544). Compounds described in

[0158] , compounds described in

[0044] to

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

[0086] to

[0090] of Japanese Patent Application Publication No. 2012-094660, etc.), pyrazoline compounds, styreneamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (e.g., thiophene-1, thiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithiophene-1, thiophene-1, [1]benzothiophene-1, [3,2-b]thiophene (BTBT) derivatives, thiophene-1, [3,2-f:4,5-f′] bis[1]benzothiophene (TBBT) derivatives, compounds described in paragraphs

[0031] to

[0036] of Japanese Patent Application Publication No. 2018-014474, compounds described in paragraphs

[0043] to

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

[0025] to

[0037] ,

[0099] to

[0109] of WO2017-159684, and Japanese Patent Application Publication No. 2017-076766 The compounds described in paragraphs

[0029] to

[0034] of the announcement, the compounds described in paragraphs

[0015] to

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

[0045] to

[0053] of Japanese Patent Application Publication No. 2019-054228, the compounds described in paragraphs

[0045] to

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

[0063] to

[0024] of WO2019-081416. Compounds described in

[089] , compounds described in paragraphs

[0033] to

[0036] of Japanese Patent Application Publication No. 2019-080052, compounds described in paragraphs

[0044] to

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

[0041] to

[0046] of WO2019-093188, etc.), anthocyanin compounds, oxacyanine compounds, polyamine compounds, indole compounds, pyrrole compounds, pyrazole compounds, poly Arylidene compounds, fused aromatic carbocyclic compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetraphenylene derivatives, pentaphenylene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having nitrogen-containing heterocyclic compounds as ligands.

[0310] Furthermore, the p-type semiconductor material is preferably a compound represented by formula (p1), a compound represented by formula (p2), a compound represented by formula (p3), a compound represented by formula (p4), or a compound represented by formula (p5).

[0311] [Chemical Formula 36]

[0312]

[0313] In formulas (p1) to (p6), the two R's independently represent a hydrogen atom or a substituent (alkyl, alkoxy, halogen atom, alkylthio, (hetero)arylthio, alkylamino, (hetero)arylamino, or (hetero)aryl, etc. These groups may further have substituents where possible. For example, a (hetero)aryl can be an arylaryl that can further have substituents (i.e., a biaryl. At least one of the aryl groups constituting this group may be a heteroaryl)).

[0314] Furthermore, R is preferably the group represented by R in formula (IX) of WO2019-081416.

[0315] X and Y represent -CR independently. 2 2-, sulfur atom (-S-), oxygen atom (-O-), -NR 2 -or-SiR 2 2-.

[0316] R 2 Represents a hydrogen atom, an alkyl group (preferably methyl or trifluoromethyl), an aryl group (preferably substituted), or a heteroaryl group (preferably substituted). The presence of two or more R groups... 2 They can be the same or different.

[0317] Ar represents an aromatic cyclic group (preferably a benzene cyclic group).

[0318] The p-type semiconductor material is preferably the compound represented by formula (p1).

[0319] When the photoelectric conversion film contains p-type semiconductor material, the content of p-type semiconductor material in the photoelectric conversion film (=p-type semiconductor material thickness in monolayer form / photoelectric conversion film thickness × 100) is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 25 to 50% by volume.

[0320] In addition, n-type semiconductor materials can be used alone or in combination with two or more types.

[0321] The photoelectric conversion film is preferably composed substantially only of specific compounds, pigments, and p-type semiconductor materials. "Substantially composed of specific compounds, pigments, and p-type semiconductor materials" means that the total content of the specific compounds, pigments, and p-type semiconductor materials relative to the total mass of the photoelectric conversion film is 95–100% by mass.

[0322] The photoelectric conversion film is preferably composed substantially only of specific compounds, pigments, n-type semiconductor materials, and p-type semiconductor materials. "Substantially composed of specific compounds, pigments, n-type semiconductor materials, and p-type semiconductor materials" means that the total content of these components relative to the total mass of the photoelectric conversion film is 95–100% by mass.

[0323] When the photoelectric conversion film contains pigments, the photoelectric conversion film is preferably a hybrid layer formed in a state of mixing a specific compound and a pigment.

[0324] Furthermore, when the photoelectric conversion film contains n-type semiconductor materials and / or p-type semiconductor materials, the photoelectric conversion film is preferably a hybrid layer formed in a state of mixing a specific compound with n-type semiconductor materials and / or p-type semiconductor materials.

[0325] When the photoelectric conversion film contains pigments, n-type semiconductor materials and / or p-type semiconductor materials, the photoelectric conversion film is preferably a hybrid layer formed in a state of mixing a specific compound, pigments, n-type semiconductor materials and / or p-type semiconductor materials.

[0326] A hybrid layer is a layer in which two or more materials are mixed in a single layer.

[0327] Photoelectric conversion films containing specific compounds are non-luminescent films, possessing characteristics different from organic light-emitting diodes (OLEDs). A non-luminescent film refers to a film with a luminous quantum efficiency of less than 1%, preferably less than 0.5%, and more preferably less than 0.1%.

[0328] <Film Formation Method>

[0329] Photoelectric conversion films are primarily formed using dry deposition methods. Examples of dry deposition methods include vapor deposition (especially vacuum vapor deposition), sputtering, ion plating, and physical vapor deposition (PVD) methods such as MBE (Molecular Beam Epitaxy), as well as chemical vapor deposition (CVD) methods such as plasma polymerization. Vacuum vapor deposition is preferred. When forming photoelectric conversion films using vacuum vapor deposition, manufacturing conditions such as vacuum level and deposition temperature can be set using conventional methods.

[0330] The thickness of the photoelectric conversion film is preferably 10-1000 nm, more preferably 50-800 nm, even more preferably 50-500 nm, and especially preferably 50-400 nm.

[0331] [Electrode (Conductive Film)]

[0332] The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of conductive materials. Examples of conductive materials include metals, alloys, metal oxides, conductive compounds, and mixtures thereof.

[0333] Light is incident from the upper electrode 15, therefore, it is preferable that the upper electrode 15 is transparent to the light to be detected. Regarding the materials constituting the upper electrode 15, examples include conductive metal oxides such as tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine-doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO); metal thin films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as graphene and carbon nanotubes. Among these, conductive metal oxides are preferred from the viewpoint of high conductivity and transparency.

[0334] Typically, if the conductive film is made thinner than a certain range, the resistance value will increase sharply. However, in a solid-state imaging element assembled with the photoelectric conversion element of this embodiment, the film resistance can be, for example, 100 to 10000 Ω / □, and the range of film thickness that can be made thinner is highly flexible. Furthermore, the thinner the upper electrode (transparent conductive film) 15, the less light is absorbed, and the transmittance generally increases. The increase in transmittance increases light absorption in the photoelectric conversion film and increases photoelectric conversion energy, which is therefore preferred. Considering the suppression of leakage current, the increase in film resistance value, and the increase in transmittance associated with thinning, the film thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.

[0335] Depending on the application, the lower electrode 11 may be transparent or, conversely, opaque, causing light reflection. Examples of materials constituting the lower electrode 11 include conductive metal oxides such as tin oxide (ATO, FTO), zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) doped with antimony or fluorine; conductive compounds such as metals like gold, silver, chromium, nickel, titanium, tungsten, and aluminum, their oxides, or nitrides (e.g., titanium nitride (TiN)); mixtures or laminates of these metals with conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as graphene and carbon nanotubes.

[0336] There are no particular restrictions on the method of forming the electrode, and it can be appropriately selected according to the electrode material. Specifically, examples include wet methods such as printing and coating; physical methods such as vacuum evaporation, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD.

[0337] When the electrode material is ITO, methods such as electron beam method, sputtering method, resistance heating evaporation method, chemical reaction method (sol-gel method, etc.) and coating of indium tin oxide dispersion can be cited.

[0338] [Charge blocking membrane: electron blocking membrane, hole blocking membrane]

[0339] The photoelectric conversion element of the present invention preferably has one or more intermediate layers other than the photoelectric conversion film between the conductive film and the transparent conductive film. Examples of such intermediate layers include charge-blocking films. By incorporating this film into the photoelectric conversion element, the characteristics of the resulting photoelectric conversion element (photoelectric conversion efficiency, responsiveness, etc.) are superior. Examples of charge-blocking films include electron-blocking films and hole-blocking films. Each film will be described in detail below.

[0340] <Electron blocking membrane>

[0341] Electron blocking films are donor organic semiconductor materials (compounds), such as p-type organic semiconductors as described above. A single p-type organic semiconductor can be used, or two or more can be used.

[0342] Furthermore, as a p-type organic semiconductor used in electron blocking films, compounds with lower ionization potential than n-type semiconductor materials can be cited. As long as this condition is met, the pigments described above can also be used.

[0343] Furthermore, polymer materials can also be used as electron blocking films.

[0344] Regarding polymeric materials, examples include polymers such as phenylene, fluorene, carbazole, indole, pyrene, pyrrole, methylpyridine, thiophene, acetylene and diacetylene, as well as their derivatives.

[0345] In addition, electron blocking films can be composed of multiple films.

[0346] Electron blocking films can be made of inorganic materials. Generally, the dielectric constant of inorganic materials is greater than that of organic materials. Therefore, when inorganic materials are used in electron blocking films, a higher voltage is applied to the photoelectric conversion film, resulting in higher photoelectric conversion efficiency. Examples of inorganic materials that can serve as electron blocking films include calcium oxide, chromium oxide, copper chromium oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, copper gallium oxide, copper strontium oxide, niobium oxide, molybdenum oxide, copper indium oxide, silver indium oxide, and iridium oxide.

[0347] <Cavity blocking membrane>

[0348] Hole blocking membranes are acceptor organic semiconductor materials (compounds), and can utilize the aforementioned n-type semiconductor materials, etc.

[0349] There are no particular limitations on the manufacturing method of the charge blocking film; examples include dry film deposition and wet film deposition. Regarding dry film deposition methods, examples include vapor deposition and sputtering. Vapor deposition can be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), with vacuum vapor deposition and other physical vapor deposition methods being preferred. Regarding wet film deposition methods, examples include inkjet printing, spraying, nozzle printing, spin coating, dip coating, casting, molding, roll coating, bar coating, and gravure coating; from the viewpoint of high-precision patterning, inkjet printing is preferred.

[0350] The thickness of the charge blocking film (electron blocking film and hole blocking film) is preferably 3-200 nm, more preferably 5-100 nm, and even more preferably 5-30 nm.

[0351] [Substrate]

[0352] Photoelectric conversion elements may also have a substrate. There are no particular restrictions on the type of substrate used; examples include semiconductor substrates, glass substrates, and plastic substrates.

[0353] In addition, there are no particular restrictions on the position of the substrate. Typically, a conductive film, a photoelectric conversion film, and a transparent conductive film are stacked sequentially on the substrate.

[0354] [Sealing layer]

[0355] The photoelectric conversion element may also have a sealing layer. Due to the presence of degrading factors such as water molecules, the performance of photoelectric conversion materials can sometimes deteriorate significantly. Therefore, by covering and sealing the entire photoelectric conversion film with a sealing layer, the above-mentioned deterioration can be prevented. The sealing layer is a dense ceramic such as a metal oxide, metal nitride, or metal nitride that prevents water molecules from penetrating, or diamond-like carbon (DLC).

[0356] In addition, regarding the sealing layer, the materials can be selected and manufactured in accordance with the description in paragraphs

[0210] to

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

[0357] [Imaging element, light sensor]

[0358] An example of a photoelectric conversion element is an imaging element. An imaging element is a component that converts the light information of an image into electrical signals. Typically, it refers to a matrix of multiple photoelectric conversion elements arranged on the same plane. Each photoelectric conversion element (pixel) converts the light signal into an electrical signal, and can sequentially output this electrical signal to the outside of the imaging element for each pixel. Therefore, each pixel consists of one or more photoelectric conversion elements and one or more transistors.

[0359] Imaging elements are mounted in imaging components of digital cameras and digital camcorders, electronic endoscopes, and camera modules of mobile phones.

[0360] The photoelectric conversion element of the present invention is also preferably used in an optical sensor having the photoelectric conversion element of the present invention. Regarding the optical sensor, the above-described photoelectric conversion element can be used alone, or it can be used as a line sensor configured as a straight line or a two-dimensional sensor configured as a planar plane.

[0361] [Compound]

[0362] This invention also relates to compounds.

[0363] The compounds of the present invention are the same as the specific compounds described above (the compounds represented by formula (1)) and have the same preferred conditions.

[0364] Example

[0365] The present invention will now be described in further detail based on embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0366] [Compound (Evaluate Compounds)]

[0367] <Synthesis of Compounds (1-7)>

[0368] The following schemes were used to synthesize specific compounds, namely compounds (1-7).

[0369] [Chemical Formula 37]

[0370]

[0371] (Synthesis of compound (1-7-3))

[0372] Compound (1-7-1) (1.0 mmol), compound (1-7-2) (4.0 mmol), triethylamine (20 mmol), and 20 mL of tetrahydrofuran were added to a glass reaction vessel to obtain a mixture. The reaction vessel was purged with nitrogen, and the mixture was reacted under reflux for 5 hours. After the mixture was naturally cooled to room temperature (25°C), 40 mL of methanol was added, and the precipitate was collected by filtration. The resulting solid (filtered material) was suspended in 20 mL of tetrahydrofuran and heated under reflux for 1 hour, then filtered again. The solid (filtered material) was dried under reduced pressure to obtain 0.79 mmol of compound (1-7-3).

[0373] The following shows the compound (1-7-3) based on 1 Results of H NMR (nuclear magnetic resonance) analysis.

[0374] Compound (1-7-3): 1 H NMR(DMSO-d6)δ(ppm)7.31(2H,t,J=7.4Hz), 7.39(2H,t,J=8.9Hz), 7.48(2H,s), 7.67(2H,d,J=8.4Hz), 7 .71(2H,d,J=8.4Hz), 7.78(2H,d,J=4.0Hz), 8.12(2H,d,J=4.0Hz), 8.22(2H,s) 8.32(2H,s), 10.5(2H,s).

[0375] (Synthesis of compound (1-7-4))

[0376] Compound (1-7-3) (0.75 mmol), Lawesson's reagent (3.75 mmol), and 20 mL of o-dichlorobenzene were added to a glass reaction vessel to obtain a mixture. The reaction vessel was purged with nitrogen, and the mixture was reacted at 150 °C for 5 hours. After the mixture was allowed to cool naturally to room temperature (25 °C), the precipitate was collected by filtration. The resulting solid (filtered material) was suspended in 20 mL of tetrahydrofuran and heated under reflux for 1 hour, then filtered again. The solid (filtered material) was dried under reduced pressure to obtain 0.60 mmol of compound (1-7-4).

[0377] The following shows the compound (1-7-4) based on 1 Results of H NMR analysis.

[0378] Compound (1-7-4): 1H NMR(DMSO-d6)δ(ppm)7.31(2H,t,J=8.0Hz), 7.37(2H,t,J=8.0Hz), 7.50(2H,s), 7.66(2H,d,J=8.3Hz), 7 .71(2H,d,J=8.3Hz), 7.79(2H,d,J=4.1Hz), 8.03(2H,d,J=4.1Hz), 8.18(2H,s) 8.37(2H,s), 11.9(2H,s).

[0379] (Synthesis of compounds (1-7))

[0380] Compound (1-7-4) (0.60 mmol), cesium carbonate (2.4 mmol), and 17 mL of N,N-dimethylacetamide were added to a glass reaction vessel to obtain a mixture. The reaction vessel was purged with nitrogen, and the mixture was reacted at 150 °C for 5 hours. After the mixture was naturally cooled to room temperature (25 °C), the precipitate was collected by filtration. The resulting solid (filtered material) was suspended in water and then filtered again. The solid (filtered material) was dried under reduced pressure and purified by sublimation to give 0.45 mmol of compound (1-7).

[0381] Compounds (1-7) are poorly soluble, and therefore the results were identified by LDI-MS (Soft Laser Desorption / Ionization Mass Spectrometry). The identification results are shown below.

[0382] Compounds (1-7): LDI-MS: 638.1 (M + ).

[0383] Other specific compounds were also synthesized using the above synthetic method.

[0384] The following shows the specific compounds used in the experiment and the compounds used for comparison.

[0385] Hereinafter, compounds (1-1) to (1-36) and compounds (2-1) to (2-17) are specific compounds.

[0386] Hereinafter, specific compounds and comparative compounds will be collectively referred to as evaluation compounds.

[0387] [Chemical Formula 38]

[0388]

[0389] [Chemical Formula 39]

[0390]

[0391] [Chemical Formula 40]

[0392]

[0393] [Chemical Formula 41]

[0394]

[0395] [Chemical Formula 42]

[0396]

[0397] [Chemical Formula 43]

[0398]

[0399] [Pigment (Evaluation Pigment)]

[0400] The pigments shown below were used in the evaluation to fabricate the photoelectric conversion element described later.

[0401] [Chemical Formula 44]

[0402]

[0403] [Chemical Formula 45]

[0404]

[0405] [Chemical Formula 46]

[0406]

[0407] [n-type semiconductor materials]

[0408] Fullerene C60 was used as the n-type semiconductor material in the evaluation for the fabrication of photoelectric conversion elements described later.

[0409] [p-type semiconductor materials]

[0410] The p-type semiconductor material shown below was used as the p-type semiconductor material in the evaluation and was used to fabricate the photoelectric conversion element described later.

[0411] [Chemical Formula 47]

[0412]

[0413] [test]

[0414] The following tests X, Y, and Z were conducted using the materials shown in the previous paragraph.

[0415] In Experiment X, photoelectric conversion films were fabricated using specific compounds, n-type semiconductor materials, and pigments for evaluation. In Experiment Y, photoelectric conversion films were fabricated using two specific compounds and pigments for evaluation. In Experiment Z, photoelectric conversion films were fabricated using specific compounds, p-type semiconductor materials, and pigments for evaluation.

[0416] [Experiment X]

[0417] <Examples and Comparative Examples: Fabrication of Photoelectric Conversion Components>

[0418] The obtained compound was used to make Figure 2 The photoelectric conversion element is in the form of a photoelectric conversion element. Here, the photoelectric conversion element includes a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15.

[0419] Specifically, a lower electrode 11 (thickness: 30 nm) is formed on a glass substrate by sputtering an amorphous ITO film. An electron blocking film 16A (thickness: 30 nm) is then formed on the lower electrode 11 by vacuum heating evaporation of the following compound (C-1). Furthermore, a photoelectric conversion film 12, serving as a mixed layer, is formed by co-depositing the components shown in the various embodiments or comparative examples listed in the table onto the electron blocking film 16A. The evaporation rate ratio of each component is adjusted so that the film thickness, converted to a single layer, is the ratio shown in the "Component Ratio" column of the table.

[0420] Then, a hole-blocking film 16B (thickness: 10 nm) was formed by vapor deposition of the following compound (C-2) on the photoelectric conversion film 12. An amorphous ITO film was then formed on the hole-blocking film 16B by sputtering to form the upper electrode 15 (a transparent conductive film) (thickness: 10 nm). After forming a SiO film as a sealing layer on the upper electrode 15 by vacuum evaporation, an aluminum oxide (Al2O3) layer was formed on it by ALCVD (Atomic Layer Chemical Vapor Deposition), thereby fabricating the photoelectric conversion element of each embodiment or comparative example.

[0421] [Chemical Formula 48]

[0422]

[0423] Furthermore, in the photoelectric conversion film of the embodiment of Experiment X, compounds (1-1) to (1-36) exhibited properties as p-type semiconductors.

[0424] <Evaluation of Dark Current>

[0425] The dark current of each photoelectric conversion element was measured using the following method.

[0426] With an electric field strength of 2.5 × 10 5 A voltage was applied to the lower and upper electrodes of each photoelectric conversion element in the manner of V / cm, and the current value in the dark (dark current) was measured. Then, similarly, a voltage of 7.5 × 10⁻⁶ was measured. 4 A voltage was applied in the manner of electric field strength of V / cm, the current value in the dark (dark current) was measured, the relative ratio of dark current was calculated using the following formula, and evaluated according to the following criteria.

[0427] The relative ratio of dark current = (2.5 × 10) 5 Dark current (V / cm) / (7.5×10) 4 Dark current (V / cm)

[0428] A: The relative ratio of dark current is below 2.0.

[0429] B: The relative ratio of dark current is above 2.0 and less than 2.5.

[0430] C: The relative ratio of dark current is greater than 2.5 and less than 3.0.

[0431] D: The relative ratio of dark current is 3.0 or higher and less than 3.5.

[0432] E: The relative ratio of dark current is 3.5 or higher.

[0433] <Evaluation of photoelectric conversion efficiency (quantum efficiency)>

[0434] The driving mechanism of each obtained photoelectric conversion element was confirmed by the following method.

[0435] To become 7.5×10 4 A voltage of V / cm was applied to each photoelectric conversion element. Then, light was irradiated from the upper electrode (transparent conductive film) side, and the photoelectric conversion efficiency (external quantum efficiency) in the visible light region (400–700 nm) was evaluated.

[0436] Using the integral values ​​of photoelectric conversion efficiency in the range of 400–700 nm, the relative comparison of the integral values ​​of photoelectric conversion efficiency was calculated using Equation (S), and evaluated according to the following criteria.

[0437] Formula (S):

[0438] Relative comparison =

[0439] (Integral value of photoelectric conversion efficiency of the photoelectric conversion element of the evaluated object in the range of 400-700nm) / (Integral value of photoelectric conversion efficiency of the photoelectric conversion element of Example 1-1 in the range of 400-700nm)

[0440] A: The ratio of the integral value of the photoelectric conversion efficiency is above 1.4.

[0441] B: The ratio of the integral value of the photoelectric conversion efficiency to the ratio of 1.2 to 1.4 is greater than or equal to 1.2.

[0442] C: The ratio of the integral value of the photoelectric conversion efficiency to a value between 1.0 and 1.2 is greater than or equal to 1.0.

[0443] D: The ratio of the integral value of the photoelectric conversion efficiency to the ratio of 0.8 to less than 1.0.

[0444] E: The relative ratio of the integral value of the photoelectric conversion efficiency is less than 0.8.

[0445] <Evaluation of the electric field strength dependence of photoelectric conversion efficiency>

[0446] The electric field strength dependence of the quantum efficiency of each obtained photoelectric conversion element was confirmed by the following method.

[0447] To become 7.5×10 4 A voltage of V / cm was applied to each photoelectric conversion element. Then, light was irradiated from the upper electrode (transparent conductive film) side, and the photoelectric conversion efficiency (external quantum efficiency) in the visible light region (400–700 nm) was evaluated.

[0448] Therefore, it becomes 2.5×10 5 A voltage was applied to each photoelectric conversion element at an electric field strength of V / cm. Then, light was irradiated from the upper electrode (transparent conductive film) side, and the photoelectric conversion efficiency (external quantum efficiency) in the visible light region (400–700 nm) was evaluated.

[0449] The photoelectric conversion efficiency ratio was calculated using the integral values ​​of the photoelectric conversion efficiency measured at 400–700 nm under various electric field strengths, and the electric field strength dependence of the photoelectric conversion efficiency was evaluated according to the following criteria.

[0450] Photoelectric conversion efficiency ratio

[0451] = (in order to become 7.5 × 10) 4 The integral value of the photoelectric conversion efficiency in the 400–700 nm range under the condition of applied voltage (where the electric field strength is V / cm) / (where V / cm is the electric field strength). 5 The integral value of the photoelectric conversion efficiency of the photoelectric conversion element under the condition of applied voltage (V / cm) in the range of 400–700 nm is obtained by using an electric field strength of V / cm.

[0452] A: The photoelectric conversion efficiency ratio is above 0.9.

[0453] B: Photoelectric conversion efficiency ratio is 0.8 or higher and less than 0.9.

[0454] C: Photoelectric conversion efficiency ratio is 0.7 or higher and less than 0.8.

[0455] D: Photoelectric conversion efficiency ratio is 0.6 or higher and less than 0.7.

[0456] E: Photoelectric conversion efficiency ratio is less than 0.6

[0457] <Results of Experiment X>

[0458] The characteristics of the photoelectric conversion elements of each embodiment or comparative example in this test (Test X), and the results of the tests conducted using the photoelectric conversion elements of each embodiment or comparative example are shown in Table 1 below.

[0459] Furthermore, in the table, the "Formula" column indicates which of the above formulas the evaluation compound corresponds to. For example, the evaluation compound 1-1 used in Example 1-1 corresponds to the compound represented by formula (16).

[0460] [Table 1]

[0461]

[0462] [Table 2]

[0463]

[0464] Based on the results shown in Table 1, it is confirmed that the photoelectric conversion element of the present invention, using a photoelectric conversion film containing a specific compound, exhibits excellent performance.

[0465] Among them, in Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (16) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 111 ~Y 115 The compound represented by the above formula (17) with -CR= and R being a hydrogen atom, Y 21 ~Y 24 and Y 111 ~Y 115 The compound represented by the above formula (21) with -CR = and R being a hydrogen atom, Y 21 ~Y 24 and Y 151 ~Y 157 The compound represented by the above formula (22) with -CR= and R being a hydrogen atom, Y 61 ~Y 62 and Y81 ~Y 85 The compound represented by the above formula (24) with -CR= and R being a hydrogen atom, Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (27) with -CR= and R being a hydrogen atom, Y 151 ~Y 157 The compound represented by the above formula (28) with -CR= and R being a hydrogen atom, Y 41 ~Y 42 and Y 91 ~Y 97 For -CR= and R is a hydrogen atom, the above formula (44) and Y 51 ~Y 54 and Y 81 ~Y 85 The compound represented by the above formula (45) with -CR= and R being a hydrogen atom, Y 21 ~Y 24 Y 41 ~Y 42 and Y 81 ~Y 85 The compound represented by the above formula (46) with -CR= and R being a hydrogen atom, Y 471 ~Y 475 The compound represented by the above formula (54) with -CR= and R being a hydrogen atom, Y 481 ~Y 485 The compound represented by the above formula (55) with -CR= and R being a hydrogen atom, Y 491 ~Y 497 The compound represented by the above formula (56) with -CR= and R being a hydrogen atom, Y 501 ~Y 505 The compound represented by the above formula (57) with -CR= and R being a hydrogen atom, Y 511 ~Y 515 The compound represented by the above formula (58) with -CR= and R being a hydrogen atom, Y 521 ~Y 528 The compound represented by the above formula (59) with -CR= and R being a hydrogen atom, or Y 531 ~Y 539 The effect is even better in the case of compounds represented by the above formula (59) where -CR= and R is a hydrogen atom (Examples 1-1 to 1-33, Examples 1-46 to 1-47, Examples 1-52 to 1-58).

[0466] [Experiment Y]

[0467] <Examples and Comparative Examples: Fabrication of Photoelectric Conversion Components>

[0468] The photoelectric conversion elements of each embodiment or comparative example were fabricated in the same manner as in Experiment X.

[0469] Furthermore, in the photoelectric conversion film of the embodiment of Experiment Y, compounds (1-7) exhibited properties as p-type semiconductors, while compounds (2-1) to (2-17) exhibited properties as n-type semiconductors.

[0470] <Evaluation of Dark Current>

[0471] The dark current of each photoelectric conversion element was measured using the following method.

[0472] With an electric field strength of 2.5 × 10 5 A voltage was applied to the lower and upper electrodes of each photoelectric conversion element using a voltage-to-cm method, and the current value in the dark (dark current) was measured. The results confirmed that the dark current was 50 nA / cm in all photoelectric conversion elements. 2 The following shows a sufficiently low dark current.

[0473] <Evaluation of photoelectric conversion efficiency (quantum efficiency)>

[0474] Similar to Experiment X, the photoelectric conversion efficiency (quantum efficiency) of each obtained photoelectric conversion element was evaluated.

[0475] However, in this experiment (Experiment Y), the following formula was used as formula (S).

[0476] Formula (S):

[0477] Relative comparison =

[0478] (Integral value of photoelectric conversion efficiency of the photoelectric conversion element of the evaluated object in the range of 400-700nm) / (Integral value of photoelectric conversion efficiency of the photoelectric conversion element of Example 2-1 in the range of 400-700nm)

[0479] <Evaluation of the electric field strength dependence of photoelectric conversion efficiency>

[0480] Similar to Experiment X, the electric field strength dependence of the photoelectric conversion efficiency of each obtained photoelectric conversion element was evaluated. However, the applied voltage was set to 2.0 × 10⁻⁶. 5 V / cm and 2.5×10 5 V / cm, the photoelectric conversion efficiency ratio was calculated using the following formula.

[0481] Photoelectric conversion efficiency ratio

[0482] = (in order to become 2.0 × 10 5The integral value of the photoelectric conversion efficiency in the 400–700 nm range under the condition of applied voltage (where the electric field strength is V / cm) / (where V / cm is the electric field strength). 5 The integral value of the photoelectric conversion efficiency of the photoelectric conversion element under the condition of applied voltage (V / cm) in the range of 400–700 nm is obtained by using an electric field strength of V / cm.

[0483] <Results of Experiment Y>

[0484] The characteristics of the photoelectric conversion elements of each embodiment or comparative example in this test (Test Y), and the results of the tests conducted using the photoelectric conversion elements of each embodiment or comparative example are shown in Table 2 below.

[0485] The “Formula” column in Table 2 indicates which formula a compound described in one of the evaluation compounds corresponds to.

[0486] [Table 3]

[0487]

[0488] Based on the results shown in Table 2, it is confirmed that even when using a photoelectric conversion film containing two specific compounds, the photoelectric conversion element of the present invention exhibits excellent performance.

[0489] Among them, the specific compound used as an n-type material (the compound listed in the "One of the Evaluation Compounds" column) satisfies the requirement of being an Ar material. 11 and Ar 12 The ring structure has an aromatic cyclic group containing a -N= group or at least one of n15 and n16 being 1, and Ar 15 and Ar 16 Middle, Y 81 ~Y 85 In the case of groups represented by formula (8) such as -CF=, -C(CN)- or -N=, the effects of the present invention have been confirmed to be even better (see the results of Examples 2-3, 2-7, 2-9, 2-10, 2-12 to 2-17, etc.).

[0490] [Experiment Z]

[0491] <Examples and Comparative Examples: Fabrication of Photoelectric Conversion Components>

[0492] The photoelectric conversion elements of each embodiment or comparative example were fabricated in the same manner as in Experiment X.

[0493] Furthermore, in the photoelectric conversion film of the embodiment of Experiment Z, compounds (2-1) to (2-17) exhibited properties as n-type materials.

[0494] <Evaluation of Dark Current>

[0495] Similar to experiment Y, the current of each obtained photoelectric conversion element was evaluated.

[0496] The results confirmed that the dark current was 50 nA / cm² in any photoelectric conversion element. 2 The following shows a sufficiently low dark current.

[0497] <Evaluation of photoelectric conversion efficiency (quantum efficiency)>

[0498] Similar to Experiment X, the photoelectric conversion efficiency (quantum efficiency) of each obtained photoelectric conversion element was evaluated.

[0499] However, in this experiment (Experiment Z), the following formula was used as formula (S).

[0500] Formula (S):

[0501] Relative comparison =

[0502] (Integral value of photoelectric conversion efficiency of the photoelectric conversion element of the evaluated object in the range of 400-700nm) / (Integral value of photoelectric conversion efficiency of the photoelectric conversion element of Example 3-1 in the range of 400-700nm)

[0503] <Evaluation of the electric field strength dependence of photoelectric conversion efficiency>

[0504] Similar to experiment Y, the electric field strength dependence of the photoelectric conversion efficiency of each obtained photoelectric conversion element was evaluated.

[0505] <Results of Experiment Z>

[0506] The characteristics of the photoelectric conversion elements of each embodiment or comparative example in this test (Test Z) and the results of the tests conducted using the photoelectric conversion elements of each embodiment or comparative example are shown in Table 3 below.

[0507] [Table 4]

[0508]

[0509] Based on the results shown in Table 3, even when using a photoelectric conversion film containing a specific compound and a p-type semiconductor material, the excellent performance of the photoelectric conversion element of the present invention is confirmed.

[0510] Among them, the specific compound used as an n-type material satisfies the requirement of being Ar 11 and Ar 12 The ring structure has an aromatic cyclic group containing a -N= group or at least one of n15 and n16 being 1, and Ar 15 and Ar 16Middle, Y 81 ~Y 85 In the case of groups represented by formula (8) such as -CF=, -C(CN)= or -N=, the effects of the present invention have been confirmed to be even better (see the results of Examples 3-8, 3-12, 3-14, 3-15, 3-17 to 3-22, etc.).

[0511] Symbol Explanation

[0512] 10a, 10b - Photoelectric conversion element, 11 - Conductive film (lower electrode), 12 - Photoelectric conversion film, 15 - Transparent conductive film (upper electrode), 16A - Electron blocking film, 16B - Hole blocking film.

Claims

1. A photoelectric conversion element having, in order, a conductive film, a photoelectric conversion film, and a transparent conductive film, wherein the photoelectric conversion film contains a compound represented by formula (1), the compound represented by formula (1) is selected from the following compounds (1-1) to (1-36) and (2-1) to (2-17), In formula (1), X 11 and X 12 each independently represents a sulfur atom or an oxygen atom, X 13 and X 14 represents an oxygen atom, 2. The photoelectric conversion element according to claim 1, wherein n11 to n12 represent 1, n13 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2. wherein, when n11 to n16 are all 0 and n17 is 1, Ar 15 and Ar 16 is a 3-ring aromatic ring group, 3. The photoelectric conversion element according to claim 1, wherein n11 to n14 represent 1, n15 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

4. The photoelectric conversion element according to claim 1, wherein n11 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2. Ar 11 ~ Ar 14 are each independently selected from the group consisting of 11 Ar 12 is the same as Ar 13 is the same as Ar 14 is the same as Ar Ar 15 ~ Ar 16 the same, selected from the group consisting of, Ar 11 ~ Ar 16 does not have a substituent, or further has a halogen atom, a cyano group or a trifluoromethyl group as a substituent on a carbon atom.

5. The photoelectric conversion element according to claim 1, wherein n11 to n12 represent 1, n13 to n14 represent 0, n15 to n16 represent 1, n17 represents 1, and n18 represents 1 or 2.

6. The photoelectric conversion element according to claim 1, wherein n11 to n14 represent 0, n15 to n16 each independently represent 0 or 1, n17 represents 2, and n18 represents 1.

7. The photoelectric conversion element according to claim 1, wherein the compound represented by formula (1) is selected from the following compounds (1-1) to (1-36) and (2-1) to (2-17), 8. The photoelectric conversion element according to claim 1 or 2, wherein the photoelectric conversion film further contains a n-type semiconductor material.

9. The photoelectric conversion element according to claim 8, wherein the n-type semiconductor material contains a fullerene-based compound selected from the group consisting of a fullerene and a derivative thereof.

10. The photoelectric conversion element according to claim 1 or 2, wherein the photoelectric conversion film further contains a p-type semiconductor material.

11. The photoelectric conversion element according to claim 1 or 2, wherein the photoelectric conversion film contains two kinds of the compound represented by formula (1).

12. The photoelectric conversion element according to claim 1 or 2, wherein the photoelectric conversion film further contains a pigment.

13. The photoelectric conversion element according to claim 1 or 2, wherein between the conductive film and the transparent conductive film, one or more intermediate layers are provided in addition to the photoelectric conversion film.

14. An imaging element having the photoelectric conversion element according to any one of claims 1 to 13.

15. A light sensor having the photoelectric conversion element according to any one of claims 1 to 13.

16. A compound represented by formula (1), n11 to n16 each independently represent 0 or 1, X 11 and X 12 represents a sulfur atom. n17 represents 1 or 2, n18 represents 1 or 2, 18. The compound according to claim 17, wherein n11 to n12 represent 1, n13 to n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

19. The compound according to claim 17, wherein ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ In formula (1), X 11 and X 12 each independently represents a sulfur atom or an oxygen atom, X 13 and X 14 represents an oxygen atom, ​ wherein, when n11 to n16 are all 0 and n17 is 1, Ar 15 and Ar 16 is a 3-ring aromatic ring group, ​ ​ Ar 11 ~ Ar 14 are each independently selected from the group consisting of 11 Ar 12 is the same as Ar 13 Ar 14 is the same as Ar Ar 15 ~ Ar 16 the same, selected from the group consisting of, Ar 11 ~ Ar 16 does not have a substituent, or further has a halogen atom, a cyano group or a trifluoromethyl group as a substituent on a carbon atom. ​ ​ ​ n11-n14 represent 1, n15-n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

20. The compound according to claim 17, wherein, n11-n16 represent 0, n17 represents 1, and n18 represents 1 or 2.

21. The compound according to claim 17, wherein, n11-n12 represent 1, n13-n14 represent 0, n15-n16 represent 1, n17 represents 1, and n18 represents 1 or 2.

22. The compound according to claim 17, wherein, n11-n14 represent 0, n15-n16 each independently represent 0 or 1, n17 represents 2, and n18 represents 1.

23. The compound according to claim 17, wherein, the compound represented by the formula (1) is selected from the following compounds (1-1) to (1-36) and (2-1) to (2-17), 24. The compound of claim 17 or 18, wherein, X 11 and X 12 represents a sulfur atom.

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