Organic electronic element and compound

Abstract

The present invention provides: an organic electronic element which has improved hole transporting ability; and a compound which is used in the organic electronic element and is capable of improving the hole transporting ability.　Provided is an organic electronic element comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer contains a compound which has a partial structure represented by formula (1). (In formula (1), ring A represents an aromatic hydrocarbon ring which is a C6-30 monocycle or condensed ring which may have a substituent. The aromatic hydrocarbon ring may be linked, directly or via a linking group, to a heterocyclic aromatic ring or to another aromatic hydrocarbon ring which may have a substituent. Ar1 is any of (B1)-(B5), and * represents a bond. X represents a sulfur atom or an oxygen atom. It should be noted that when Ar1 and Ar2 are the same groups of (B1) or (B4), Ar1 has at least one group selected from a cyano group and a trifluoromethyl group, or when Ar1 does not have a group selected from a cyano group and a trifluoromethyl group, Ar1 has two or more groups selected from a fluoro group, a chloro group, a bromo group and an iodo group.)

Description

Organic electronic devices and compounds

[0001] The present invention relates to a compound having an imide skeleton as a partial structure, and an organic electronic device containing the compound.

[0002] Currently, active efforts are being made to create new, highly functional devices using organic materials. Research and development is particularly active on organic electronic devices, such as photoelectric conversion devices and organic electroluminescence (EL) devices, with advances being made in material and device design aimed at improving device performance. For example, in photoelectric conversion devices used for video recording, a problem exists in that slow transport of carriers (electrons and holes) generated in the light-receiving layer to the electrode can cause image retention. In organic EL devices, slow transport of carriers from the electrode to the light-emitting layer can increase the driving voltage. Therefore, highly efficient carrier movement within the device is required to achieve high device performance.

[0003] Incidentally, imide compounds have been disclosed as compounds for use as electron transport materials in electrophotographic photoreceptors (see Patent Document 1). However, further improvements in performance are required in the field of organic electronic devices, and therefore further improvements are necessary.

[0004] JP 2019-182789 A

[0005] An object of the present invention is to provide an organic electronic device capable of improving the hole transporting ability, and a compound for use in the organic electronic device capable of improving the hole transporting ability.

[0006] As a result of extensive research aimed at solving the above problems, the present inventors have found that a specific compound having an imide skeleton as a partial structure can improve the hole transport ability in organic electronic devices such as photoelectric conversion devices and organic EL devices, and have thus completed the present invention.

[0007] That is, the present invention includes the following aspects: [1] An organic electronic device including a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer contains a compound having a partial structure represented by the following formula (1): In formula (1), ring A represents a monocyclic or fused aromatic hydrocarbon ring having 6 to 30 carbon atoms, which may have a substituent. The aromatic hydrocarbon ring may be linked, directly or via a linking group, to another aromatic hydrocarbon ring or a heteroaromatic ring, which may have a substituent. Ar １ is any one of the following (B1) to (B5), and * represents a bond. X represents a sulfur atom or an oxygen atom. ２ represents a group having 1 to 3 unsaturated 6-membered rings composed of elements selected from the group consisting of hydrogen, carbon, and nitrogen, which may have a substituent (the unsaturated 6-membered ring may be a single ring, a linked ring, a condensed ring, or a ring formed by linking and condensing), and any of (B1) to (B5) above. １ ~R ４ represents a hydrogen atom, a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, a monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent, or a monocyclic or condensed ring heteroaromatic group which may have a substituent. ４ may each independently have two or more. １ and Ar ２ is the same group in (B1) or (B4), Ar １ has at least one group selected from a cyano group and a trifluoromethyl group, or Ar １ does not have a group selected from a cyano group and a trifluoromethyl group, Ar １ has at least two groups selected from a fluoro group, a chloro group, a bromo group, and an iodo group. ２ and the R １ ~ The above R ４wherein the optionally substituted substituent is a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms. [3] The organic electronic device according to [1], comprising a first electrode, a second electrode, and an organic layer and a light-receiving layer disposed between the first electrode and the second electrode, wherein the organic layer contains a compound having the partial structure represented by formula (1). [4] The organic electronic device according to [3], wherein the light-receiving layer is a layer containing at least two kinds of organic components. [5] An organic electronic device comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a hole transport layer and a hole transport promoting layer containing a compound having the partial structure represented by formula (1), or a layer comprising a mixture of a hole transport material and a compound having the partial structure represented by formula (1). [6] The organic electronic device according to [5], wherein the hole transport layer and the hole transport promoting layer are disposed adjacent to each other between the first electrode and the second electrode. [7] The organic electronic device according to [1], wherein the ring A in formula (1) is a benzene ring, naphthalene ring, phenylbenzene ring, diphenylbenzene ring, pyridylbenzene ring, or dipyridylbenzene ring optionally substituted with a cyano group, a fluoro group, a trifluoromethyl group, or a methyl group. [8] The organic electronic device according to [1], wherein the Ar in formula (1) １ is substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms, or is any one of the above-mentioned (B2), (B3), and (B5), which may be substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms. [9] The organic electronic device according to [1], ２is a phenyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, or any one of (B1) to (B5), each of which may be substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms.

[10] An imide compound represented by the following formula (1): In formula (1), ring A represents a monocyclic or fused aromatic hydrocarbon ring having 6 to 30 carbon atoms, which may have a substituent. The aromatic hydrocarbon ring may be linked, directly or via a linking group, to another aromatic hydrocarbon ring or a heteroaromatic ring, which may have a substituent. Ar １ is any one of the following (B1) to (B5), and * represents a bond. X represents a sulfur atom or an oxygen atom. ２ represents a group having 1 to 3 unsaturated 6-membered rings composed of elements selected from the group consisting of hydrogen, carbon, and nitrogen, which may have a substituent (the unsaturated 6-membered ring may be a single ring, a linked ring, a condensed ring, or a ring formed by linking and condensing), and any of (B1) to (B5) above. １ ~R ４ represents a hydrogen atom, a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, a monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent, or a monocyclic or condensed ring heteroaromatic group which may have a substituent. ４ may each independently have two or more. １ and Ar ２ is the same group in (B1) or (B4), Ar １ has at least one group selected from a cyano group and a trifluoromethyl group, or Ar １ does not have a group selected from a cyano group and a trifluoromethyl group, Ar １has at least two groups selected from a fluoro group, a chloro group, a bromo group, and an iodo group. ２ and the R １ ~ The above R ４ The imide compound according to

[10] , wherein the optionally substituted substituent is a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms.

[12] The imide compound according to

[10] , wherein the ring A in the formula (1) is a benzene ring, a naphthalene ring, a phenylbenzene ring, a diphenylbenzene ring, a pyridylbenzene ring, or a dipyridylbenzene ring, which may be substituted with a cyano group, a fluoro group, a trifluoromethyl group, or a methyl group.

[13] The imide compound according to

[10] , wherein the Ar in the formula (1) １ is substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms, and is either (B1) or (B4) above, or is optionally substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms, and is either (B2), (B3), or (B5) above. ２ is a phenyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, or any of (B1) to (B5), each of which may be substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms.

[15] The imide compound according to

[12] , wherein in formula (1), ring A is an unsubstituted benzene ring or a naphthalene ring.

[0008] According to the present invention, it is possible to provide an organic electronic device capable of improving the hole transporting ability, and a compound used in the organic electronic device capable of improving the hole transporting ability.

[0009] 1 is a schematic cross-sectional view showing an example of a layer structure of a photoelectric conversion element according to the present invention, and FIG. 2 is a schematic cross-sectional view showing an example of a layer structure of an organic EL element according to the present invention.

[0010] (Organic Electronic Element) The organic electronic element of the present invention includes a photoelectric conversion element and an organic electroluminescent element (organic EL element). The photoelectric conversion element is an element that converts light energy into electrical energy or an electrical signal, and includes an imaging element, a photosensor, a solar cell, etc.

[0011] The organic electronic device of the present invention includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode. The organic layer contains a compound having a partial structure represented by the following formula (1) (hereinafter, also referred to as the compound represented by formula (1)):

[0012] The compound represented by formula (1) will be described in detail later. The organic layer preferably includes a hole transport layer and a hole transport promoting layer containing the compound represented by formula (1), or a layer comprising a mixture of a hole transport material and the compound represented by formula (1). Here, the hole transport layer has a role of transporting holes and contains a hole transport material. The hole transport promoting layer is disposed between the first electrode and the hole transport layer and has a role of facilitating the exchange of holes between the hole transport layer and the electrode and contains a hole transport promoting material. In the present invention, the compound represented by formula (1) is used as a hole transport promoting material.

[0013] A preferred embodiment of the organic electronic device of the present invention is a photoelectric conversion device. The photoelectric conversion device includes a first electrode, a second electrode, and an organic layer and a light-receiving layer disposed between the first electrode and the second electrode. Hereinafter, the device configuration of the organic electronic device will be described using the photoelectric conversion device as an example.

[0014] <Configuration of Photoelectric Conversion Element> The photoelectric conversion element according to the present invention includes a first electrode, a second electrode, and an organic layer disposed between the first and second electrodes, the organic layer including a hole transport region. The hole transport region refers to the region between the first electrode and the light-receiving layer, and includes, for example, a hole transport layer and a hole transport promotion layer. In the present invention, the compound represented by the above formula (1) can be used as the hole transport promotion material contained in the hole transport promotion layer. The hole transport region is preferably adjacent to the first electrode. The photoelectric conversion element may include other layers. Examples of other layers include layers commonly used in photoelectric conversion elements. Examples include, but are not limited to, a light-receiving layer, an electron transport layer, a hole blocking layer, an electron blocking layer, and a buffer layer.

[0015] The photoelectric conversion element according to the present invention may have, for example, a first electrode, a hole transport promoting layer, a hole transport layer, and a second electrode laminated in this order, or a first electrode, a layer formed by mixing a hole transport material forming the hole transport layer with the compound represented by formula (1), and a second electrode laminated in this order. The photoelectric conversion element may also have, for example, the first electrode, the hole transport promoting layer, and the hole transport layer laminated adjacently in this order, or another layer such as a buffer layer may be interposed between the first electrode and the hole transport promoting layer or between the hole transport promoting layer and the hole transport layer.

[0016] In one embodiment, the photoelectric conversion element of the present invention comprises a first electrode, a hole transport promotion layer, a hole transport layer, a light-receiving layer, and a second electrode stacked in this order. In another embodiment, the photoelectric conversion element of the present invention comprises a first electrode, a hole transport promotion layer, a hole transport layer, a light-receiving layer, an electron transport layer, and a second electrode stacked in this order. The layers may be stacked adjacent to each other, or other layers may be interposed between any of the layers.

[0017] The photoelectric conversion element may receive light from either the first electrode side or the second electrode side, and either the first electrode or the second electrode may be a transparent electrode. For example, the photoelectric conversion element may have a structure in which a transparent electrode (second electrode), an electron transport layer, a light-receiving layer, a hole transport layer, a hole transport promotion layer, and a metal electrode (first electrode) are stacked in this order, or a structure in which a transparent electrode (first electrode), a hole transport promotion layer, a hole transport layer, a light-receiving layer, an electron transport layer, and a metal electrode (second electrode) are stacked in this order. Furthermore, both the first electrode and the second electrode may be transparent electrodes.

[0018] Next, the case where the organic electronic element is an organic EL element will be described.

[0019] <Structure of Organic EL Element> The organic EL element according to the present invention includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, the organic layer including a hole transport region. The hole transport region refers to the region between the first electrode and the light-emitting layer, and includes, for example, a hole transport layer and a hole transport promoting layer. In the present invention, the compound represented by the above formula (1) can be used as the hole transport promoting material contained in the hole transport promoting layer. The hole transport region is preferably adjacent to the first electrode. The organic EL element may include other layers. Examples of other layers include layers commonly used in organic EL elements. Examples include, but are not limited to, a light-emitting layer, an electron transport layer, a hole-blocking layer, an electron-blocking layer, and a buffer layer.

[0020] The organic EL device according to the present invention may have, for example, a first electrode, a hole transport promoting layer, a hole transport layer, and a second electrode laminated in this order, or a first electrode, a layer formed by mixing a hole transport material forming the hole transport layer with the compound represented by formula (1), and a second electrode laminated in this order. The organic EL device may also have, for example, the first electrode, the hole transport promoting layer, and the hole transport layer laminated adjacently in this order, or another layer such as a buffer layer may be interposed between the first electrode and the hole transport promoting layer or between the hole transport promoting layer and the hole transport layer.

[0021] In one embodiment, the organic EL device of the present invention comprises a first electrode, a hole transport promoting layer, a hole transport layer, a light-emitting layer, and a second electrode stacked in this order. In another embodiment, the organic EL device of the present invention comprises a first electrode, a hole transport promoting layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a second electrode stacked in this order. The layers may be stacked adjacent to each other, or other layers may be interposed between any of the layers.

[0022] The organic EL element may extract light from either the first electrode side or the second electrode side, and either the first electrode or the second electrode may be a transparent electrode. For example, the organic EL element may have a structure in which a transparent electrode (second electrode), an electron transport layer, a light-emitting layer, a hole transport layer, a hole transport promoting layer, and a metal electrode (first electrode) are laminated in this order, or a structure in which a transparent electrode (first electrode), a hole transport promoting layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode (second electrode) are laminated in this order. Furthermore, both the first electrode and the second electrode may be transparent electrodes.

[0023] Next, the compound represented by formula (1) contained in the organic layer as a hole transport promoting material in the organic electronic device of the present invention will be described.

[0024] <Compound Represented by Formula (1)> The organic layer in the organic electronic device of the present invention contains a compound represented by the following formula (1).

[0025]

[0026] In formula (1), ring A represents a monocyclic or fused aromatic hydrocarbon ring having 6 to 30 carbon atoms, which may have a substituent. The aromatic hydrocarbon ring may be linked, directly or via a linking group, to another aromatic hydrocarbon ring or a heteroaromatic ring, which may have a substituent. １ is any one of the following (B1) to (B5), and * represents a bond. X represents a sulfur atom or an oxygen atom. ２represents a group having 1 to 3 unsaturated 6-membered rings composed of elements selected from the group consisting of hydrogen, carbon, and nitrogen, which may have a substituent (the unsaturated 6-membered ring may be a single ring, a linked ring, a condensed ring, or a ring formed by linking and condensing), and any of (B1) to (B5) above. １ ~R ４ represents a hydrogen atom, a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, a monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent, or a monocyclic or condensed ring heteroaromatic group which may have a substituent. ４ may each independently have two or more. １ and Ar ２ is the same group in (B1) or (B4), Ar １ has at least one group selected from a cyano group and a trifluoromethyl group, or Ar １ does not have a group selected from a cyano group and a trifluoromethyl group, Ar １ has at least two groups selected from a fluoro group, a chloro group, a bromo group, and an iodo group.

[0027] The ring A, the Ar ２ , and the above R １ ~ Above R ４ In the above, examples of the substituent that may be substituted include a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, and an alkyl group having 2 to 10 carbon atoms. ２Examples of the unsaturated six-membered rings include groups each independently having one to three of one or more types of unsaturated six-membered rings. The unsaturated six-membered ring is preferably composed of one or more elements selected from the group consisting of hydrogen, carbon, and nitrogen, in terms of ease of synthesis. When nitrogen is included as a constituent element of the unsaturated six-membered ring, the number of nitrogen atoms per ring is preferably one to two, and more preferably one. The unsaturated six-membered ring may be a monocycle, a linked ring, a fused ring, or a linked and fused ring, and a monocycle is preferred in terms of ease of synthesis. The group having one to three unsaturated six-membered rings is preferably one or more rings selected from the group consisting of benzene, pyridine, pyrazine, and pyrimidine, in terms of excellent device performance, and is particularly preferably one or more rings selected from the group consisting of benzene and pyridine. Examples of the group having 1 to 3 unsaturated 6-membered rings include a phenyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, a naphthyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a quinazolyl group, a triazyl group, a biphenyl group, a bipyridyl group, a pyridylphenyl group, a phenylpyridyl group, a naphthylphenyl group, a phenylnaphthyl group, a terphenyl group, a bipyridylphenyl group, a diphenylpyridyl group, and a phenanthryl group.

[0028] In formula (1), examples of the monocyclic or fused aromatic hydrocarbon ring having 6 to 30 carbon atoms in ring A include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a perylene ring, a triphenylene ring, a tetracene ring, a chrysene ring, and a fluorene ring. Examples of the linking group include -O-, -S-, -C(=O)-, and -C(-R) ２- is mentioned. R includes a methyl group, a trifluoromethyl group, a phenyl group, a pyridyl group, etc., and when R is a phenyl group, the phenyl groups may be bonded to each other to form a fluorene ring. Examples of other aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a perylene ring, a triphenylene ring, a tetracene ring, a chrysene ring, and a fluorene ring. Examples of heteroaromatic rings include a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a quinazoline ring, a thiophene ring, a furan ring, a benzothiophene ring, a benzofuran ring, a dibenzothiophene ring, a dibenzofuran ring, a pyrrole ring, an indole ring, and a carbazole ring. Examples of ring A in formula (1) include the following (A-1) to (A-12).

[0029]

[0030] In formula (1), ring A is preferably (A-1), (A-2), (A-3), (A-4), (A-5), or (A-6) among the above (A-1) to (A-12), and (A-1), (A-2), (A-5), or (A-6) are more preferred in terms of having sufficient acceptor properties and expected performance. Furthermore, (A-1) or (A-2) is more preferred in terms of easy availability of raw materials. In formula (1), when ring A is formula (A-1) above, the imide compound of the present invention is represented, for example, by formula (1-1) below. In formula (1), when ring A is formula (A-2) above, the imide compound of the present invention is represented, for example, by formula (1-2) or formula (1-3) below.

[0031]

[0032]

[0033]

[0034] In formulas (1-1), (1-2), and formula (1-3), R ２１ ~R ２４each independently represents a hydrogen atom or a substituent. As described above, examples of the substituent include a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, and an alkyl group having 2 to 10 carbon atoms.

[0035] In formula (1), ring A is preferably a benzene ring, naphthalene ring, phenylbenzene ring, diphenylbenzene ring, pyridylbenzene ring, or dipyridylbenzene ring optionally substituted with a cyano group, a fluoro group, a trifluoromethyl group, or a methyl group, in terms of contributing to improving the performance of an organic electronic device. Furthermore, in terms of ease of synthesis, ring A is preferably other than a naphthalene ring substituted with a cyano group, and is more preferably an unsubstituted benzene ring or naphthalene ring.

[0036] In formula (1), Ar １ is an electron-withdrawing group. The electron-withdrawing group refers to a substituent that can deepen the LUMO level as a hole transport promoter, and indicates, for example, a substituent that is more likely to attract electrons from the atom to which it is bonded compared to a hydrogen atom. The Hammett value is known as an index showing electron-withdrawing properties, and groups showing a positive value are also cited as preferred examples of electron-withdrawing groups. In addition, Ar １ In order to further enhance the electron-withdrawing ability of Ar, it is more preferable that any of the groups (B1) to (B5) above is substituted with an electron-withdrawing substituent. １ and Ar ２ is the same group in (B1) or (B4), Ar １ has at least one group selected from a cyano group and a trifluoromethyl group, or Ar １ does not have a group selected from a cyano group and a trifluoromethyl group, Ar １ must have at least two groups selected from a fluoro group, a chloro group, a bromo group, and an iodo group. １is the above (B1) or (B4) substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms, and is preferably any of the above (B2), (B3), or (B5) optionally substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms, and is more preferably any of the above (B1) to (B5) substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms.

[0037] In addition, in formula (1), Ar ２ As for (B1), in terms of contributing to improving the performance of an organic electronic device, it is preferably a phenyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, which may be substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms, or any of the above (B1) to (B5), and it is more preferably a phenyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, which may be substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms, or any of the above (B1) to (B5).

[0038] In formula (1), Ar １ As described above, Ar can adjust the LUMO level of the compound. １ is preferably a group represented by any one of (B1) to (B5) having an electron-withdrawing substituent.

[0039] Preferred specific examples of the compound represented by formula (1) are shown below, but the compound of the present invention is not limited to these.

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058] [Production Method] The compound represented by formula (1) can be synthesized by a known method or a combination thereof. For example, a tetracarboxylic dianhydride represented by formula (2) below is reacted with an amine compound represented by formula (3) below to obtain a compound represented by formula (4) below. The obtained compound represented by formula (4) below is then reacted with an amine compound represented by formula (5) below to synthesize the imide compound represented by formula (1). The imide compound represented by formula (1) can be synthesized in two steps as described above, or in one step.

[0059] (In the formula, Ar １ , Ar ２and ring A have the same definition as in the above formula (1).) The imide compound represented by the above formula (4) or (1) can be synthesized, for example, by referring to known methods (Organic Chemistry Frontiers, 2021, Vol. 8, pp. 522-530; Chemistry A European Journal, 2006, Vol. 12, pp. 6592-6606; Journal of Materials Chemistry A, 2015, Vol. 3, pp. 878-885, etc.). Examples of solvents used in the reaction include dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), methanol, ethanol, propanol, butanol, cresol, water, acetic acid, formic acid, and trifluoromethanesulfonic acid, and a mixed solvent of a plurality of these solvents may also be used. Furthermore, a general acid, base, or condensation promoter may also be added as a reaction additive.

[0060] <<Action and Effect of the Compound Represented by Formula (1)>> The compound represented by formula (1) has a pyromellitic diimide skeleton, a naphthalene tetracarboxylic diimide skeleton, or a similar specific skeleton structure, and therefore this strong acceptor skeleton is expected to have a strong interaction with the HOMO orbital of the hole transport material. In other words, when a layer (e.g., a hole transport promotion layer) in an organic electronic device (e.g., a photoelectric conversion device) contains a compound represented by formula (1), it is expected that the interaction with the HOMO orbital of an adjacent hole transport layer will be enhanced, and carrier exchange between the hole transport layer and the hole transport promotion layer will be promoted. In this way, the compound represented by formula (1) has an extremely deep LUMO level, and therefore it is expected that the exchange of holes between the hole transport layer and the electrode will be smooth. Furthermore, since the compound represented by formula (1) has a pyromellitic diimide skeleton, a naphthalene tetracarboxylic diimide skeleton, or a similar specific skeleton structure, thermal stability, high reduction resistance, etc. can also be expected.

[0061] As described above, the present inventors have found that the compound represented by formula (1) can be effectively used as a hole transport promoting material that facilitates the exchange of holes between a hole transport layer and an electrode. They have also confirmed that, in a photoelectric conversion element, the hole transport ability is promoted when the compound represented by formula (1) (hole transport promoting material) is combined with a hole transport material. That is, they have confirmed that, in a photoelectric conversion element, the energy barrier when carriers generated in the light-receiving layer are extracted to the electrode side can be reduced by the compound represented by formula (1), which is the hole transport promoting material of the present invention.

[0062] <Embodiments> Examples of the laminate structure of the organic electronic element (e.g., photoelectric conversion element) of the present invention include the following structures (i) and (ii): (i): first electrode / hole transport promoting layer / hole transport layer / light-receiving layer / second electrode (ii): first electrode / hole transport promoting layer / hole transport layer / light-receiving layer / electron transport layer / second electrode When the organic electronic element is, for example, an organic EL element, the "light-receiving layer" in the structure (i) or (ii) can be read as the "light-emitting layer".

[0063] The photoelectric conversion element and organic EL element according to the present invention will be described in more detail below, taking the above-mentioned configuration (ii) as an example, with reference to Fig. 1 and Fig. 2. Fig. 1 is a schematic cross-sectional view showing an example of the layered configuration of the photoelectric conversion element according to the present invention, and Fig. 2 is a schematic cross-sectional view showing an example of the organic EL element according to the present invention.

[0064] <<First Embodiment>> A photoelectric conversion element according to a first embodiment is an organic imaging element or photosensor having the layered structure shown in Fig. 1. The photoelectric conversion element 1 includes a first electrode 11 (first electrode), a hole transport promotion layer 12, a hole transport layer 13, a light-receiving layer 14, an electron transport layer 15, and a second electrode 16 (second electrode), in this order. However, some of these layers may be omitted, or other layers may be added.

[0065] In the photoelectric conversion element 1 shown in FIG. 1 , light is incident from above the transparent first electrode 11 and is received by the light-receiving layer 14. For convenience, FIG. 1 illustrates light as being incident from the side of the light-receiving layer 14. Furthermore, a voltage is applied to the photoelectric conversion element 1 so that, of the charges (holes and electrons) generated by photoelectric conversion in the light-receiving layer 14, the holes are moved to the first electrode 11 and the electrons are moved to the second electrode 16. That is, the first electrode 11 serves as a hole-collecting electrode, and the second electrode 16 serves as an electron-collecting electrode. Note that the substrate provided on the top surface of the first electrode 11 is omitted in FIG. 1 . The substrate here is not particularly limited, and examples include a glass plate, a quartz plate, and a plastic plate. Furthermore, in a configuration in which light is incident from the substrate side, the substrate is transparent to the wavelength of light. Each of the above layers will be described below.

[0066] [First Electrode 11] A first electrode 11 or a second electrode 16 is provided on a substrate. In the case of a photoelectric conversion element configured so that light passes through the first electrode 11 and enters the light-receiving layer 14, the first electrode is formed of a transparent material that transmits or substantially transmits the light. Here, "transmits light" means that the average transmittance is 80% or more, and "substantially transmits light" means that the average transmittance is 50% or more. In other words, in this specification, "transparent" means that the average transmittance is 50% or more.

[0067] The transparent material used for the first electrode 11 or the second electrode 16 is not particularly limited, but examples thereof include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, and metal sulfides such as zinc sulfide.

[0068] In the case of a photoelectric conversion element configured so that light enters the light-receiving layer 14 only from the second electrode 16 side, the transmittance characteristics of the first electrode 11 are not important. Therefore, examples of materials that can be used for the first electrode in this case include gold, iridium, molybdenum, palladium, and platinum.

[0069] [Hole Transport Promotion Layer 12] The hole transport promotion layer 12 is provided between the first electrode 11 and the hole transport layer 13 described below. The hole transport promotion layer 12 is provided to promote hole transport from the hole transport layer 13 to the first electrode 11. The hole transport promotion layer 12 contains the compound represented by formula (1) above. The hole transport promotion layer 12 may also contain a compound other than the compound represented by formula (1). Examples of compounds that can be contained in the hole transport promotion layer 12 include conventionally known hole transport materials, such as the compounds used in the hole transport layer 13 described below.

[0070] [Hole Transport Layer 13] The hole transport layer 13 is provided between the hole transport promotion layer 12 and the light-receiving layer 14. The hole transport layer 13 has a role of transporting holes generated in the light-receiving layer 14 from the light-receiving layer 14 to the first electrode 11, and a role of blocking electrons generated in the light-receiving layer 14 from moving toward the first electrode 11. Depending on the application, the hole transport layer 13 may also have a role of blocking electron injection from the first electrode 11.

[0071] The hole transport layer 13 may have a single layer structure made of one or more materials, or may have a laminate structure made of multiple layers of the same or different compositions. The hole transport material that can be contained in the hole transport layer 13 may be a known hole transport material. Examples of known hole transport materials include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetracene compounds, pentacene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, picene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds. Among these, fluorene compounds, carbazole compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, etc. are preferred, and fluorene compounds, carbazole compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are particularly preferred.

[0072] [Light-receiving layer 14] The light-receiving layer 14 is provided between the hole-transporting layer 13 and the electron-transporting layer 15 described below. Examples of materials for the light-receiving layer 14 include materials having a photoelectric conversion function.

[0073] The absorption layer 14 may have a single layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions. In particular, in order to increase the photoelectric conversion efficiency, the absorption layer is preferably made of a layer containing at least two materials (organic components).

[0074] Examples of materials used for the light-receiving layer 14, which has a single-layer structure made of one material, include (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, etc. Materials used for the light-receiving layer 14, which has a single-layer structure made of two materials, include the aforementioned combinations of (i) coumarin and its derivatives, quinacridone and its derivatives, and phthalocyanine and its derivatives with (ii) fullerene and its derivatives and other acceptor materials. The light-receiving layer 4 made of these materials can be formed by vapor deposition of a premixed powder or by co-evaporation in any ratio. Examples of materials used for the light-receiving layer 14, which has a single-layer structure made of three materials, include the aforementioned combinations of (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, (ii) fullerene and its derivatives, other acceptor materials, and (iii) hole-transport materials. The light-receiving layer 14 made of these materials can be formed by vapor deposition of a premixed powder or by co-evaporation in any ratio.

[0075] (i) Specific examples of coumarin derivatives include coumarin 6 and coumarin 30. Specific examples of quinacridone derivatives include N,N-dimethylquinacridone. Specific examples of phthalocyanine derivatives include boron subphthalocyanine chloride and boron subnaphthalocyanine chloride (SubNC). (ii) Specific examples of fullerenes and their derivatives include

[60] fullerene,

[70] fullerene, and [6,6]-phenyl-C61-methyl butyrate (

[60] PCBM). (iii) Preferred compounds and specific examples of hole transport materials include the same compounds as those used in the hole transport layer 13 described above.

[0076] Furthermore, the material having a photoelectric conversion function is not limited to being contained only in the light-receiving layer 14. For example, the material having a photoelectric conversion function may be contained in a layer adjacent to the light-receiving layer 14 (hole transport layer 13 or electron transport layer 15).

[0077] [Electron Transport Layer 15] The electron transport layer 15 is provided between the light-receiving layer 14 and the second electrode 16 described below. The electron transport layer 15 has a role of transporting electrons generated in the light-receiving layer 14 to the second electrode 16 and a role of blocking the movement of holes from the second electrode 16, to which the electrons have been transported, to the light-receiving layer 14. Depending on the application, the electron transport layer 15 may also have a role of blocking hole injection from the second electrode 16.

[0078] The electron transport material that can be contained in the electron transport layer 15 may be a known electron transport material. Examples of the electron transport material include fullerene, fullerene derivatives, triazine derivatives, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), and Bp hen(4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic acid diimide, and N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide.

[0079] The electron transport layer 15 may have a single layer structure made of one or more materials, or may have a laminate structure made of multiple layers of the same or different compositions.

[0080] [Second Electrode 16] A second electrode 16 is provided on the electron transport layer 15. Examples of materials for the second electrode 16 include indium-tin oxide (ITO), indium-zinc oxide (IZO), sodium, a sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, and aluminum / aluminum oxide (Al ２ O ３) mixture, indium, lithium / aluminum mixture, gold, platinum, rare earth metals, molybdenum oxide, etc. The first electrode 11 and the second electrode 16 may be the same or different.

[0081] [Method of Forming Each Layer] Each layer except for the first electrode 11 and the second electrode 16 described above can be formed by thinning the material of each layer (together with a material such as a binder resin and a solvent, if necessary) by a known method such as vacuum deposition, spin coating, casting, LB (Langmuir-Blodgett) method, etc. There are no particular restrictions on the film thickness of each layer formed in this manner and it can be selected appropriately depending on the situation, but it is usually in the range of 5 nm to 5 μm.

[0082] The first electrode 11 and the second electrode 16 can be formed by thinning an electrode material by a method such as vapor deposition or sputtering. A pattern may be formed through a mask of a desired shape during vapor deposition or sputtering, or a pattern of a desired shape may be formed by photolithography after forming a thin film by vapor deposition or sputtering.

[0083] The film thickness of the first electrode 11 and the second electrode 16 is preferably 1 μm or less, and more preferably 10 nm or more and 200 nm or less.

[0084] The materials constituting the first electrode 11 and the second electrode 16 may be interchanged as necessary (also called an inverted structure). In such a structure, a photoelectric conversion element is formed in which light passes through the second electrode 16 and enters the light-receiving layer 14.

[0085] An imaging element including the photoelectric conversion element of this embodiment can be applied to, for example, an imaging element of a digital camera or a digital video camera, and an imaging element built into a mobile phone, etc. An optical sensor can be applied to, for example, a television remote control, an air conditioner switch, an automatic door opener, etc.

[0086] <<Second Embodiment>> A photoelectric conversion element according to a second embodiment of the present invention is a solar cell having the layered structure shown in Fig. 1. In the solar cell 1, a hole transport promotion layer 12 and a hole transport layer 13 are provided between a first electrode 11 and a light-receiving layer 14, and an electron transport layer 15 is provided between a second electrode 16 and the light-receiving layer 14. However, some of these layers may be omitted, or other layers may be added.

[0087] [First Electrode 11] The first electrode 11 is made of, for example, a transparent material, and the transparent material can be the transparent material in the first embodiment. The first electrode 11 may be formed on any substrate (for example, a transparent substrate such as glass, plastic, or polymer film).

[0088] [Hole Transport Promotion Layer 12] The material of the hole transport promotion layer 12 is the same as the material of the hole transport promotion layer 12 in the first embodiment (the compound represented by formula (1)). The material of the hole transport promotion layer 12 may contain a conventionally known hole transport material in addition to the material in the first embodiment.

[0089] [Hole Transport Layer 13] The material of the hole transport layer 13 is the same as the material of the hole transport layer 13 in the first embodiment. The material of the hole transport layer 13 may contain a conventionally known hole transport material in addition to the hole transport material in the first embodiment.

[0090] [Light-Receiving Layer 14] The light-receiving layer 14 may be made of an electron-donating material and an electron-accepting material. This may be a planar bond type in which the electron-donating material and the electron-accepting material are bonded together at their respective planes, or a bulk heterobond type in which the electron-donating material and the electron-accepting material are mixed and formed into a film. The electron-donating material is not particularly limited, but an organic semiconductor is preferred. Examples of electron-donating materials include polymeric compounds and copolymers thereof, such as polythiophene derivatives, polyfluorene derivatives, and polyphenylene vinylene derivatives, as well as low-molecular-weight compounds, such as phthalocyanine derivatives and their metal complexes, porphyrin derivatives and their metal complexes, acene derivatives such as pentacene, and diamine derivatives. The electron-donating material may be an inorganic semiconductor in addition to an organic semiconductor, provided that the effects of the present invention are not impaired. The electron-accepting material is not particularly limited, but an organic semiconductor is preferred. Examples of electron-accepting materials include fullerene derivatives, perylene derivatives, and naphthalene derivatives.

[0091] [Electron Transport Layer 15] The electron transport material in the first embodiment can be used as the material for the electron transport layer 15. Alternatively, the electron transport material may be an alkali metal halide such as sodium fluoride or cesium fluoride, an alkaline earth metal halide such as calcium fluoride, a carbonate such as cesium carbonate, or an inorganic n-type semiconductor such as titanium oxide or zinc oxide.

[0092] [Second Electrode 16] The second electrode 16 may be made of, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or an alloy thereof, but is not limited to these.

[0093] The materials constituting the first electrode 11 and the second electrode 16 may be interchanged as necessary (also called an inverted structure). In such a structure, a photoelectric conversion element is formed in which light passes through the second electrode 16 and enters the light-receiving layer 14.

[0094] [Method of Forming Each Layer] The method of forming each layer is not particularly limited. For example, the first electrode 11, the hole transport promotion layer 12, the hole transport layer 13, the light-receiving layer 14, the electron transport layer 15, and the second electrode 16 may be sequentially laminated on a substrate using a vapor deposition method, a spin coating method, a casting method, a pattern transfer method, or the like. Alternatively, the hole transport promotion layer 12, the hole transport layer 13, the light-receiving layer 14, and the electron transport layer 15 may be laminated, and then the first electrode 11 and the second electrode 16 may be formed on this laminate by transfer, vapor deposition, sputtering, or the like.

[0095] <<Third Embodiment>> An organic electronic element according to a third embodiment of the present invention is an organic EL element having the layered structure shown in Fig. 2. That is, the organic EL element 2 has a first electrode 21, a hole transport promotion layer 22, a hole transport layer 23, a light-emitting layer 24, an electron transport layer 25, and a second electrode 26 provided in this order. However, some of these layers may be omitted, or other layers may be added.

[0096] [First Electrode 21] The first electrode 21 has a role of injecting holes from the hole transport layer to the light emitting layer. As the first electrode 21, a transparent electrode such as indium tin oxide (ITO), indium zinc oxide (IZO), gold, silver, platinum, copper, or the like, a metal or alloy such as aluminum, molybdenum, chromium, nickel, a polythiophene derivative having high charge transportability, a polyaniline derivative, or the like can be used, but is not limited to these.

[0097] The organic electronic element may emit light from either the first electrode 21 or the second electrode 26, or from both sides. The electrode from which light is extracted is formed of a transparent material such as ITO or IZO. For convenience, FIG. 2 shows light emitted from the side of the light-emitting layer 24.

[0098] [Hole Transport Promotion Layer 22] The hole transport promotion layer 22 is provided between the first electrode 21 and the hole transport layer 23 described below. The hole transport promotion layer 22 is provided to promote hole transport from the first electrode 21 to the hole transport layer 23. The hole transport promotion layer 22 contains the compound represented by the above formula (1) as a hole transport promotion material. The hole transport promotion layer 22 may also contain compounds other than the compound represented by the above formula (1). Examples of compounds that can be contained in the hole transport promotion layer 22 include conventionally known hole transport materials.

[0099] [Hole Transport Layer 23] The hole transport layer 23 is provided between the hole transport promotion layer 22 and the light-emitting layer 24. The hole transport layer 23 has a role of transporting holes injected from the first electrode 21 to the light-emitting layer 24. The hole transport layer 23 may have a single-layer structure made of one or more materials, or may have a laminate structure made of multiple layers of the same composition or different compositions. The hole transport material that can be contained in the hole transport layer 23 may be the same as the material of the hole transport layer 13 in the first embodiment.

[0100] [Light-emitting layer 24] The light-emitting layer 24 has a role of generating light emission (phosphorescence or fluorescence) through recombination of holes injected from the first electrode 21 and electrons injected from the second electrode 26, and contains a light-emitting material and, if necessary, a light-emitting host material. The light-emitting material and the light-emitting host material can be appropriately selected from known materials. Examples of the light-emitting material and the light-emitting host material include carbon-fused ring dyes such as triazine derivatives (including TADF materials substituted with carbazole or the like), pyrimidine derivatives, carbazole derivatives, anthracene derivatives, tetracene derivatives, pyrene derivatives, rubrene derivatives, and decacyclene derivatives; perylene derivatives such as perylene diimide; xanthene dyes such as rhodamine B; cyanine dyes; coumarin dyes such as coumarin 6 and C545T; quinacridone dyes such as Qd4 and DEQ; squarylium dyes; styryl dyes; pyrazolone derivatives; phenoxazone dyes such as NileRed; carbazole; triarylamine; and tris(2-phenylpyridine). Examples of suitable metal complexes include, but are not limited to, iridium complexes such as iridium(III) (Ir(ppy)), tris[2-phenyl-4-(2-ethylcyclohexyloxy)pyridine]iridium(III) (Ir(ehppy)), aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, europium complexes, and metal complexes composed of a central metal such as Al, Zn, Be, or a rare earth metal such as Tb, Eu, or Dy, and a ligand such as an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, or quinoline structure.

[0101] [Electron Transport Layer 25] The electron transport layer 25 is provided between the second electrode and the light-emitting layer, and has the function of transporting electrons injected from the second electrode to the light-emitting layer. Examples of the electron transport material include, but are not limited to, triazine derivatives, tris(8-quinolinolato)aluminum (Alq), bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum (BAlq), 1,4,4'-bis(2,2'-diphenylvinyl)-1,1'-bipheny (DPVBi), (2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole) (PBD), triazole derivatives (TAZ), bathocuproine (BCP), and silole derivatives.

[0102] [Second Electrode 26] The second electrode 26 has a role of injecting electrons from the electron transport layer 25 to the light-emitting layer 24. The second electrode 26 may be made of aluminum, a magnesium-silver alloy, an aluminum-lithium alloy, lithium, sodium, potassium, cesium, cesium-doped ITO, or the like, but is not limited to these.

[0103] [Method of Forming Each Layer] To form each layer of the organic EL element 2, for example, first, a thin film made of the material of the first electrode 21 is formed on a suitable light-transmitting substrate (not shown) by a method such as vapor deposition or sputtering. A hole transport promotion layer 22 and a hole transport layer 23 are then formed on the first electrode 21 in this order. The hole transport promotion layer 22 and the hole transport layer 23 can be formed by a method such as vacuum deposition, spin coating, casting, or the LB method. Next, a light-emitting layer 24 is provided on the hole transport layer 23. The light-emitting layer 24 can also be formed by forming a thin film of a desired organic light-emitting material by a method such as vacuum deposition, sputtering, spin coating, or casting. Next, an electron transport layer 25 is formed on the light-emitting layer 24. The electron transport layer 25 can be formed by the same method as the hole transport layer and the light-emitting layer. Finally, a second electrode 26 is laminated on the electron transport layer 25. The second electrode 26 can be formed by a method such as vapor deposition or sputtering of a desired metal material. The method for forming each layer of the organic EL element is not limited to the above-mentioned methods, and any known method can be appropriately used, such as vacuum deposition, molecular beam deposition (MBE), dipping using a solution in which a material is dissolved in a solvent, spin coating, casting, bar coating, roll coating, or other coating methods.

[0104] The organic electronic device (e.g., photoelectric conversion device, organic EL device) of the present invention and the method for forming each layer of the device are not limited to the device and method described in the above-described embodiment. For example, the materials of the first electrode, light-receiving layer (or light-emitting layer), electron transport layer, and second electrode can be appropriately replaced with other known materials. In addition, the hole transport promotion layer and the hole transport layer can be replaced with a layer formed by mixing the compound represented by formula (1) with a hole transport material.

[0105] The present invention will be described in more detail below with reference to examples, but the present invention should not be construed as being limited to these examples.

[0106] (Synthesis Example 1: Synthesis of Compound (C1)) Under a nitrogen stream, 1.1 g (5.0 mmol) of benzene-1,2,4,5-tetracarboxylic anhydride, 1.3 g (10.5 mmol) of 2-aminothiazole-5-carbonitrile, and 30 mL of m-cresol were added to a 100 mL three-neck flask and stirred at 150°C for 12 hours. After cooling to room temperature, the precipitated solid was filtered and washed with ethanol. The resulting solid was then recrystallized from dimethylformamide to obtain the target compound (C1) (1.4 g, yield 65%). The resulting compound (C1) was identified using FD-MS and １ H-NMR mass spectrometry (FD-MS): 432 １ H-NMR (DMSO-d6) δ (ppm): 8.71 (s, 2H), 8.63 (s, 2H)

[0107] (Synthesis Example 2: Synthesis of Compound (C55)) Under a nitrogen stream, 1.3 g (5.0 mmol) of naphthalene-1,4,5,8-tetracarboxylic dianhydride, 1.3 g (10.5 mmol) of 2-aminothiazole-5-carbonitrile, 0.6 g (4.3 mmol) of isoquinoline, and 30 mL of m-cresol were added to a 100 mL three-neck flask and stirred at 120°C for 12 hours. After cooling to room temperature, the precipitated solid was filtered and washed with ethanol. The obtained solid was then recrystallized from dimethylformamide / toluene to obtain the target compound (C55) (0.8 g, yield 33%). The obtained compound (C55) was identified as follows: １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.84 (s, 2H), 8.77 (br-s, 4H)

[0108] (Synthesis Example 3: Synthesis of Compound (C56)) The same procedure as in Synthesis Example 2 was carried out, except that 1.3 g (10.5 mmol) of 2-amino-4-cyanothiazole was used instead of 1.3 g (10.5 mmol) of 2-aminothiazole-5-carbonitrile, to obtain the target compound (C56) (1.3 g, yield 54%). The obtained compound (C56) was identified by FD-MS and １ H-NMR mass spectrometry (FD-MS): 482１ H-NMR (DMSO-d6) δ (ppm): 9.14 (s, 2H), 8.78 (br-s, 4H)

[0109] (Synthesis Example 4: Synthesis of Compound (C2)) The same procedure as in Synthesis Example 1 was carried out, except that 1.3 g (10.5 mmol) of 2-amino-4-cyanothiazole was used instead of 1.3 g (10.5 mmol) of 2-aminothiazole-5-carbonitrile, to obtain the target compound (C2) (1.3 g, yield 60%). １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.88 (s, 2H), 8.59 (s, 2H)

[0110] (Synthesis Example 5: Synthesis of Compound (C5)) The same procedure as in Synthesis Example 1 was carried out, except that 1.8 g (10.5 mmol) of 4-(trifluoromethyl)thiazol-2-amine was used instead of 1.3 g (10.5 mmol) of 2-aminothiazole-5-carbonitrile, to obtain the target compound (C5) (1.4 g, yield 55%). １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.06 (s, 2H), 7.89 (s, 2H)

[0111] (Synthesis Example 6: Synthesis of Compound (C15)) The same procedure as in Synthesis Example 1 was carried out, except that 2.3 g (10.5 mmol) of 2-amino-4-(4-fluorophenyl)thiazole-5-carbonitrile was used instead of 1.3 g (10.5 mmol) of 2-aminothiazole-5-carbonitrile, to obtain the target compound (C15) (1.2 g, yield 38%). The obtained compound (C15) was identified by FD-MS. Mass spectrometry (FD-MS): 620

[0112] (Synthesis Example 7: Synthesis of compound (C39)) The same procedure as in Synthesis Example 1 was carried out, except that 1.8 g (10.5 mmol) of 6-amino-2-cyanobenzothiazole was used instead of 1.3 g (10.5 mmol) of 2-aminothiazole-5-carbonitrile, to obtain the target compound (C39) (0.32 g, yield 12%). The obtained compound (C39) was identified by FD-MS. Mass spectrometry (FD-MS): 532

[0113] (Synthesis Example 8: Synthesis of Compound (C68)) The same procedure as in Synthesis Example 2 was carried out, except that 2.1 g (10.5 mmol) of 2-amino-4-phenylthiazole-5-carbonitrile was used instead of 1.3 g (10.5 mmol) of 2-aminothiazole-5-carbonitrile, to obtain the target compound (C68) (0.51 g, yield 16%). １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.88 (d, 2H), 8.81 (br-s, 4H), 8.32 (d, 2H), 8.06 (d, 2H)

[0114] (Synthesis Example 9: Synthesis of compound (C91)) The same procedure as in Synthesis Example 2 was carried out, except that 1.8 g (10.5 mmol) of 2-aminobenzothiazole-6-carbonitrile was used instead of 1.3 g (10.5 mmol) of 2-aminothiazole-5-carbonitrile, to obtain the target compound (C91) (0.64 g, yield 22%). １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.80 (br-s, 4H), 8.09-8.06 (m, 4H), 7.65-7.58 (m, 6H)

[0115] (Synthesis Example 10: Synthesis of Compound (C120)) Under a nitrogen stream, 10.3 g (38.4 mmol) of naphthalene-1,4,5,8-tetracarboxylic dianhydride, 3.8 g (32.0 mmol) of 4-aminobenzonitrile, and 200 mL of dimethylformamide were added to a 1000 mL three-neck flask and stirred at 120°C for 6 hours. After cooling to room temperature, 500 mL of purified water was added, and the precipitated solid was filtered and washed with ethanol. 200 mL of saturated aqueous sodium bicarbonate solution was added to the obtained solid, and the mixture was stirred at room temperature for 18 hours. After filtering the reaction solution, 2 M hydrochloric acid was added to the filtrate to adjust the pH to 1-2. After stirring at room temperature for 1 hour, the precipitated solid was filtered. Subsequently, 100 mL of acetic anhydride was added to the obtained solid, and the mixture was stirred at 120°C for 5 hours. After cooling to room temperature, the resulting solid was filtered to obtain 4-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydro-7H-isochromeno[6,5,4-def]isoquinolin-7-yl)benzonitrile (yield: 2.6 g, 22%). The compound obtained was identified as follows: １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.76-8.69 (m, 4H), 8.06 (d, 2H), 7.21 (d, 2H). Subsequently, under a nitrogen stream, 1.8 g (5.0 mmol) of 4-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydro-7H-isochromeno[6,5,4-def]isoquinolin-7-yl)benzonitrile, 0.75 g (6.0 mmol) of 2-amino-4-cyanothiazole, 0.3 g (2.5 mmol) of isoquinoline, and 25 mL of m-cresol were added to a 100 mL three-neck flask and stirred at 150°C for 18 hours. After cooling to room temperature, 50 mL of ethanol was added, and the precipitated solid was filtered and washed with ethanol. The resulting solid was then recrystallized from dimethylformamide / toluene to obtain the target compound (C120) (1.2 g, yield 52%). The resulting compound (C120) was identified as follows: １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 9.14 (s, 1H), 8.78-8.73 (m, 4H), 8.08 (d, 2H), 7.73 (d, 2H)

[0116] (Synthesis Example 11: Synthesis of compound (C131)) The same procedure as in Synthesis Example 10 was carried out, except that 1.2 g (6.0 mmol) of 2-amino-4-phenylthiazole-5-carbonitrile was used instead of 0.75 g (6.0 mmol) of 2-amino-4-cyanothiazole, to obtain the target compound (C131) (1.1 g, yield 40%). １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.80-8.74 (m, 4H), 8.10-8.06 (m, 4H), 7.73 (d, 2H), 7.65-7.60 (m, 3H)

[0117] (Synthesis Example 12: Synthesis of compound (C140)) Under a nitrogen stream, 2.7 g (10.0 mmol) of naphthalene-1,4,5,8-tetracarboxylic dianhydride and 400 mL of purified water were added to a 1000 mL three-neck flask, followed by 50 mL of 1 M aqueous potassium hydroxide solution. The mixture was then stirred at room temperature for 18 hours. Next, 1 M aqueous phosphoric acid solution was added to adjust the pH to 6.0-6.5, and 1.2 g (13.0 mmol) of aniline was added. The mixture was then stirred at 100°C for 8 hours. The reaction solution was then filtered at 80°C, and the solution was allowed to cool to room temperature. 2 M hydrochloric acid was added to adjust the pH to 1-2, and the precipitated solid was filtered and washed with ethanol. Next, 180 mL of toluene and 9.5 g (50.0 mmol) of p-toluenesulfonic acid monohydrate were added to the resulting solid, and the mixture was stirred at 100°C for 8 hours. After the reaction was completed, toluene was concentrated under reduced pressure, 200 mL of water was added to the residue, and the precipitated solid was filtered to obtain 7-phenyl-1H-isochromeno[6,5,4-def]isoquinoline-1,3,6,8(7H)-tetraone (2.0 g, yield 58%). The compound obtained was identified as follows: １ H-NMR was used. １H-NMR (DMSO-d6) δ (ppm): 8.77-8.67 (m, 4H), 7.59-7.53 (m, 2H), 7.52-7.42 (m, 1H), 7.47-7.42 (m, 2H). Subsequently, under a nitrogen stream, 1.7 g (5.0 mmol) of 7-phenyl-1H-isochromeno[6,5,4-def]isoquinoline-1,3,6,8(7H)-tetraone, 1.3 g (6.0 mmol) of 6-(trifluoromethyl)benzo[d]thiazol-2-amine, 0.3 g (2.5 mmol) of isoquinoline, and 25 mL of m-cresol were added to a 100 mL three-neck flask and stirred at 150 ° C. for 12 hours. After cooling to room temperature, 50 mL of ethanol was added, and the precipitated solid was filtered and washed with ethanol. The resulting solid was then recrystallized from dimethylformamide / toluene to obtain the target compound (C140) (0.68 g, yield 25%). The resulting compound (C140) was identified by FD-MS. Mass spectrometry (FD-MS): 543

[0118] (Synthesis Example 13: Synthesis of compound (D59)) Under a nitrogen stream, 1.3 g (5.0 mmol) of naphthalene-1,4,5,8-tetracarboxylic dianhydride, 1.6 g (10.5 mmol) of 4-(trifluoromethyl)oxazol-2-amine, 0.6 g (4.3 mmol) of isoquinoline, and 30 mL of m-cresol were added to a 100 mL three-neck flask and stirred at 140°C for 12 hours. After cooling to room temperature, 30 mL of toluene was added, and insoluble matter was filtered. Subsequently, a mixed solvent of ethanol / water (volume ratio = 1 / 1) was added to the filtrate, and the precipitated solid was filtered and washed with ethanol. Next, the obtained solid was recrystallized from dimethylformamide / toluene to obtain the target compound (D59) (0.32 g, yield 12%). The obtained compound (D59) was identified as follows: １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 9.33 (s, 2H), 8.79 (s, 4H)

[0119] (Synthesis Example 14: Synthesis of compound (D135)) The same procedure as in Synthesis Example 10 was carried out, except that 1.3 g (10.0 mmol) of 2-aminobenzoxazole was used instead of 0.75 g (6.0 mmol) of 2-amino-4-cyanothiazole, to obtain the target compound (D135) (0.22 g, yield 9%). The obtained compound (D135) was identified by the following: １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.82-8.75 (m, 4H), 8.09 (d, 2H), 7.99-7.91 (m, 2H), 7.74 (d, 2H), 7.64-7.54 (m, 2H)

[0120] (Comparative Synthesis Example 1: Synthesis of Compound (E1)) Compound 1-23 (corresponding to the above-mentioned compound (E1)) described on pages 194-195 of JP 2019-182789 A was synthesized by the method described in the patent document. The obtained compound (E1) was identified by １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.74 (s, 4H), 7.79 (s, 2H), 4.13 (q, 4H), 3.90 (s, 4H), 1.21 (t, 6H)

[0121] Comparative Synthesis Example 2: Synthesis of Compound (E2) The same procedure as in Synthesis Example 2 was carried out, except that aniline (0.98 g, 10.5 mmol) was used instead of 1.5 g (10.5 mmol) of 2-amino-1-methyl-1H-imidazole-4,5-dicarbonitrile, to obtain the target compound (E2) (yield: 0.84 g, 40%). １ H-NMR was used. １ H-NMR (DMSO-d6) δ (ppm): 8.72 (s, 4H), 7.59-7.45 (m, 10H)

[0122] <Heat Resistance Evaluation> [Heat Resistance Example 1: Sublimation Purification of Compound (C91)] The compound (C91) obtained in Synthesis Example 9 was purified by sublimation in a 1.0 × 10 －３ The solid was purified by sublimation at 370° C. under a reduced pressure of 100 Pa. The obtained solid showed no change in purity or discoloration as determined by HPLC, and was confirmed to have high heat resistance.

[0123] [Heat Resistance Comparative Example 1: Sublimation Purification of Compound (E1)] The compound (E1) obtained in Synthesis Comparative Example 1 was purified by sublimation in a 1.0 × 10 －３ The solid was purified by sublimation at 290° C. under a reduced pressure of 100 Pa. HPLC analysis revealed that the resulting solid had a significant decrease in purity and discoloration, confirming that it had poor heat resistance.

[0124] [Compounds used in evaluation]

[0125] <Preparation 1 and Evaluation 1 of Hole-Only Device (HOD)> [Element Example 1] A hole-only device having a structure consisting of a first electrode / hole injection layer / hole transport layer / hole transport promotion layer / second electrode was prepared, and the hole transport properties of the device were evaluated. (First Electrode) A glass substrate with an ITO transparent electrode, on whose surface an ITO film (thickness 110 nm) was patterned in a stripe shape, was prepared as a substrate having a first electrode. This substrate was washed with isopropyl alcohol and then subjected to surface treatment by ozone ultraviolet cleaning.

[0126] (Preparation for Vacuum Vapor Deposition) Each layer was vacuum-deposited by a vacuum deposition method on the surface on which the ITO film was formed, of the two surfaces of the substrate that had been subjected to the surface treatment described above. First, the glass substrate was placed in a vacuum deposition chamber, and 1.0 × 10 －４ The pressure was reduced to Pa. Then, each layer was formed in the following order according to the film formation conditions.

[0127] (Fabrication of hole injection layer) MoO ３ A 1 nm thick film was formed to prepare a hole injection layer. (Preparation of Hole Transport Layer) A 100 nm thick film of (HTL-1) was formed as a hole transport material to prepare a hole transport layer. (HTL-1) was synthesized by the method described in JP 2018-193371 A. (Preparation of Hole Transport Promotion Layer) A 10 nm thick film of the sublimation-purified compound (C56) was formed to prepare a hole transport promotion layer.

[0128] (Fabrication of Second Electrode) A 80 nm thick Au film was formed to fabricate a second electrode.

[0129] (Evaluation of hole transport capability of hole-only device) A positive electric field and a negative electric field of 10 mA / cm were applied to the first electrode and the second electrode of the hole-only device of Example 1, respectively. ２ The voltage value at a current density of 1000 kJ / s was measured. The results are shown in Table 1.

[0130] [Element Example 2] A hole-only device was fabricated in the same manner as in Element Example 1, except that compound (C5) was used instead of compound (C56) used in the preparation of the hole transport promotion layer in Example 1. The hole transport ability of the resulting hole-only device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0131] [Element Example 3] A hole-only device was fabricated in the same manner as in Element Example 1, except that compound (C120) was used instead of compound (C56) used in the preparation of the hole transport promotion layer in Example 1. The hole transport ability of the resulting hole-only device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0132] [Element Example 4] A hole-only device was fabricated in the same manner as in Element Example 1, except that compound (D135) was used instead of compound (C56) used in the preparation of the hole transport promotion layer in Example 1. The hole transport ability of the resulting hole-only device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0133] [Comparative Element Example 1] A hole-only device was fabricated in the same manner as in Element Example 1, except that the hole-transport promoting layer was not provided. The hole-transport capability of the resulting hole-only device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0134] A hole-only device was fabricated in the same manner as in Element Example 1, except that compound (NPT) was used instead of compound (C56) used in the preparation of the hole transport promotion layer in Example 1. The hole transport ability of the resulting hole-only device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0135]

[0136] The elements of element example 1 (HOD voltage: 2.35 V), element example 2 (HOD voltage: 1.98 V), element example 3 (HOD voltage: 2.14 V), and element example 4 (HOD voltage: 2.38 V), which used compound (C56) as the hole transport promoting material, showed lower HOD voltages than the element of element example 1 (HOD voltage: 4.60 V), which did not use a hole transport promoting material, and element example 2 (HOD voltage: 3.82 V), which used the known material NPT.

[0137] <Preparation and Evaluation of Photoelectric Conversion Element> [Element Example 5] A photoelectric conversion element 1 having a layered structure consisting of a substrate / second electrode 16 / electron transport layer 15 / light-receiving layer 14 / hole transport layer 13 / hole transport promotion layer 12 / first electrode 11 was prepared, and the dark current and external quantum efficiency of the photoelectric conversion element were evaluated.

[0138] (Preparation of Substrate and Second Electrode 16) A glass substrate with an ITO transparent electrode, on which a 2 mm wide indium-tin oxide (ITO) film (film thickness 110 nm) was patterned in stripes, was prepared as a substrate having a second electrode on its surface. Next, this substrate was washed with isopropyl alcohol, and then subjected to surface treatment by ozone ultraviolet cleaning. (Preparation of Vacuum Vapor Deposition) Each layer was vacuum-deposited by vacuum deposition on the surface-treated substrate after cleaning, and each layer was laminated. First, the glass substrate was placed in a vacuum deposition chamber, and 7.0 × 10 －５The pressure was reduced to 100 Pa. Then, each layer was fabricated in the following order according to the film formation conditions. (Fabrication of Electron Transport Layer 15) The compound 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, which had been purified by sublimation, was deposited to a thickness of 10 nm at a rate of 0.03 nm / sec to fabricate the electron transport layer 15. (Fabrication of Light Receiving Layer 14) N,N-dimethylquinacridone and fullerene C60 were mixed in a mass ratio of 4:1 to fabricate the light receiving layer 14, forming a film of 250 nm. The film formation rate was 0.13 nm / sec. (Fabrication of Hole Transport Layer 13) The hole transport material (HTL-1) was deposited to a thickness of 10 nm at a rate of 0.10 nm / sec to fabricate the hole transport layer 13. (Preparation of Hole Transport Promotion Layer 12) Compound (C56) was deposited at a rate of 0.20 nm / sec to a thickness of 10 nm to prepare the hole transport promotion layer 12. (Preparation of First Electrode 11) Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and the first electrode 11 was deposited. For the first electrode, an Au film was deposited to a thickness of 80 nm. The Au deposition rate was 0.1 nm / sec.

[0139] From the above, the area is 4 mm ２ A photoelectric conversion element 1 shown in FIG. 1 was fabricated. A voltage of 2.5 V (absolute value) was applied to the photoelectric conversion element fabricated as described above so that electrons were transported to the second electrode 16 side and holes were transported to the first electrode 11 side. The current in a dark place (dark current) and external quantum efficiency were evaluated. Dark current (A / cm ２ The external quantum efficiency (%) was measured using a Keithley Source Measure Unit 2636B. A solar cell spectral response measurement device (Soma Optical Co., Ltd.) was used to measure the external quantum efficiency (%). The wavelength of the irradiated light was 560 nm, and the intensity was 50 μW / cm. ２ The measurements were carried out at 100°C. The results are shown in Table 2. The dark current and external quantum efficiency are relative values, with the result of Comparative Example 3 of the device described below being set as the reference value (100). The lower the dark current value, the better the performance, and the higher the external quantum efficiency value, the better the performance.

[0140] A photoelectric conversion element of Element Example 6 was prepared in the same manner as in Element Example 5, except that compound (C1) was used instead of compound (C56) in the preparation of the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Element Example 5. The results are shown in Table 2.

[0141] [Element Example 7] A photoelectric conversion element of Element Example 7 was prepared in the same manner as in Element Example 5, except that compound (C5) was used instead of compound (C56) in the preparation of the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Element Example 5. The results are shown in Table 2.

[0142] [Element Example 8] A photoelectric conversion element of Element Example 8 was prepared in the same manner as in Element Example 5, except that compound (C68) was used instead of compound (C56) in preparing the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Element Example 5. The results are shown in Table 2.

[0143] [Element Example 9] A photoelectric conversion element of Element Example 9 was prepared in the same manner as in Element Example 5, except that compound (C91) was used instead of compound (C56) in preparing the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Element Example 5. The results are shown in Table 2.

[0144] [Element Example 10] A photoelectric conversion element of Element Example 10 was prepared in the same manner as in Element Example 5, except that compound (C120) was used instead of compound (C56) in the preparation of the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Element Example 5. The results are shown in Table 2.

[0145] [Element Example 11] A photoelectric conversion element of Element Example 11 was prepared in the same manner as in Element Example 5, except that compound (C140) was used instead of compound (C56) in preparing the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Element Example 5. The results are shown in Table 2.

[0146] [Element Example 12] A photoelectric conversion element of Element Example 12 was prepared in the same manner as in Element Example 5, except that compound (D59) was used instead of compound (C56) in the preparation of the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Element Example 5. The results are shown in Table 2.

[0147] A photoelectric conversion element of Element Example 13 was prepared in the same manner as in Element Example 5, except that compound (D135) was used instead of compound (C56) in the preparation of the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Element Example 5. The results are shown in Table 2.

[0148] A photoelectric conversion element of Comparative Example 3 was prepared in the same manner as in Example 5, except that compound (NPT) was used instead of compound (C56) in the preparation of the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Example 5. The results are shown in Table 2.

[0149] A photoelectric conversion element of Comparative Example 4 was prepared in the same manner as in Example 5, except that compound (E2) was used instead of compound (C56) in the preparation of the hole transport promotion layer 12, and the dark current and external quantum efficiency were measured in the same manner as in Example 5. The results are shown in Table 2.

[0150] A photoelectric conversion element of Comparative Example 5 was prepared in the same manner as in Example 5, except that the hole transport promotion layer 12 was not provided, and the dark current and external quantum efficiency were measured in the same manner as in Example 5. The results are shown in Table 2.

[0151]

[0152] As shown in Table 2, in the element examples using the photoelectric conversion element material for an imaging element of the present invention, dark current was suppressed and high external quantum efficiency was obtained compared to the element examples of the element comparison examples.

[0153] By including the compound represented by formula (1), the organic electronic device of the present invention can improve hole transport ability, and when used in a photoelectric conversion device, can perform photoelectric conversion more efficiently. Furthermore, by including the compound represented by formula (1), the organic electronic device of the present invention can suppress dark current, and is expected to reduce noise when used in a photoelectric conversion device such as an imaging device. Furthermore, by including the compound represented by formula (1), the organic electronic device of the present invention can have high external quantum efficiency and can convert light into current without loss, and is expected to achieve high sensitivity when used in, for example, a photoelectric conversion device.

[0154] 1. Photoelectric conversion element 11. First electrode 12. Hole transport promoting layer 13. Hole transport layer 14. Light-receiving layer 15. Electron transport layer 16. Second electrode 2. Organic EL element 21. First electrode 22. Hole transport promoting layer 23. Hole transport layer 24. Light-emitting layer 25. Electron transport layer 26. Second electrode

Claims

1. An organic electronic device comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer contains a compound having a partial structure represented by the following formula (1): In formula (1), ring A represents a monocyclic or condensed aromatic hydrocarbon ring having 6 to 30 carbon atoms which may have a substituent. The aromatic hydrocarbon ring may be linked, directly or via a linking group, to another aromatic hydrocarbon ring or a heteroaromatic ring which may have a substituent. １ is any one of the following (B1) to (B5), and * represents a bond. X represents a sulfur atom or an oxygen atom. ２ R represents a group having 1 to 3 unsaturated 6-membered rings composed of elements selected from the group consisting of hydrogen, carbon, and nitrogen, which may have a substituent (the unsaturated 6-membered ring may be a single ring, a linked ring, a condensed ring, or a ring formed by linking and condensing), and any of the above (B1) to (B5). １ ~R ４ represents a hydrogen atom, a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, a monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent, or a monocyclic or condensed ring heteroaromatic group which may have a substituent. ４ may each independently have two or more. １ and Ar ２ is the same group in (B1) or (B4), Ar １ has at least one group selected from a cyano group and a trifluoromethyl group, or Ar １ does not have a group selected from a cyano group and a trifluoromethyl group, Ar １ has at least two groups selected from a fluoro group, a chloro group, a bromo group, and an iodo group.

2. The ring A and the Ar ２ and the R １ ~ The above R ４ The organic electronic device according to claim 1, wherein the optionally substituted substituent is a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms.

3. The organic electronic device according to claim 1, comprising a first electrode, a second electrode, and an organic layer and a light receiving layer disposed between the first electrode and the second electrode, wherein the organic layer contains a compound having a partial structure represented by formula (1).

4. The organic electronic device according to claim 3, wherein the light-receiving layer is a layer containing at least two kinds of organic components.

5. An organic electronic device comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a hole transport layer and a hole transport promotion layer containing a compound having the partial structure represented by formula (1), or comprises a layer comprising a mixture of a hole transport material and a compound having the partial structure represented by formula (1). The organic electronic device according to claim 1.

6. The organic electronic device according to claim 5, wherein the hole transport layer and the hole transport promotion layer are disposed adjacent to each other between the first electrode and the second electrode.

7. The organic electronic device according to claim 1, wherein in formula (1), ring A is a benzene ring, a naphthalene ring, a phenylbenzene ring, a diphenylbenzene ring, a pyridylbenzene ring or a dipyridylbenzene ring optionally substituted with a cyano group, a fluoro group, a trifluoromethyl group or a methyl group.

8. In the formula (1), the Ar １ is substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms; or is any of (B2), (B3), and (B5) which may be substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms.

9. In the formula (1), the Ar ２ is a phenyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, or any one of (B1) to (B5), which may be substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms.

10. An imide compound represented by the following formula (1): In formula (1), ring A represents a monocyclic or condensed aromatic hydrocarbon ring having 6 to 30 carbon atoms which may have a substituent. The aromatic hydrocarbon ring may be linked, directly or via a linking group, to another aromatic hydrocarbon ring or a heteroaromatic ring which may have a substituent. １ is any one of the following (B1) to (B5), and * represents a bond. X represents a sulfur atom or an oxygen atom. ２ R represents a group having 1 to 3 unsaturated 6-membered rings composed of elements selected from the group consisting of hydrogen, carbon, and nitrogen, which may have a substituent (the unsaturated 6-membered ring may be a single ring, a linked ring, a condensed ring, or a ring formed by linking and condensing), and any of the above (B1) to (B5). １ ~R ４ represents a hydrogen atom, a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, a monocyclic or condensed ring aromatic hydrocarbon group which may have a substituent, or a monocyclic or condensed ring heteroaromatic group which may have a substituent. ４ may each independently have two or more. １ and Ar ２ is the same group in (B1) or (B4), Ar １ has at least one group selected from a cyano group and a trifluoromethyl group, or Ar １ does not have a group selected from a cyano group and a trifluoromethyl group, Ar １ has at least two groups selected from a fluoro group, a chloro group, a bromo group, and an iodo group.

11. The ring A and the Ar ２ and the R １ ~ The above R ４ The imide compound according to claim 10, wherein the optionally substituted substituent is a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a cyanoalkyl group having 2 to 10 carbon atoms, a fluoroalkyl group having 2 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms.

12. The imide compound according to claim 10, wherein in formula (1), ring A is a benzene ring, a naphthalene ring, a phenylbenzene ring, a diphenylbenzene ring, a pyridylbenzene ring or a dipyridylbenzene ring, each of which may be substituted with a cyano group, a fluoro group, a trifluoromethyl group or a methyl group.

13. In the formula (1), the Ar １ is substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms, or is any of (B2), (B3), and (B5) which may be substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms.

14. In the formula (1), the Ar ２ is a phenyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, or any one of (B1) to (B5), which may be substituted with at least one group selected from the group consisting of a cyano group, a fluoro group, a trifluoromethyl group, and a cyanoalkyl group having 2 to 10 carbon atoms.

15. The imide compound according to claim 12, wherein in formula (1), ring A is an unsubstituted benzene ring or naphthalene ring.

Images