Organic electronic element and compound

Abstract

Provided are an organic electronic element capable of improving the hole transport ability, and a compound capable of improving the hole transport ability used in the organic electronic element. An organic electronic element including 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 layer and a hole transport promoting layer including a compound having a partial structure represented by formula (1), or a layer formed by mixing a hole transport material and a compound having a partial structure represented by formula (1), the organic electronic element including a light-receiving layer. # imgabs0 # (In formula (1), # imgabs1 # represents a bond, and formula (1) forms a cyclic imide structure; ar1 represents a monocyclic or fused aromatic hydrocarbon group which may have a substituent, or a monocyclic or fused heteroaromatic group which may have a substituent. The aromatic hydrocarbon group can be a group formed by connecting a plurality of aromatic hydrocarbon groups directly or through a connecting group, and the heteroaromatic group can be a group formed by connecting a plurality of heteroaromatic groups directly or through a connecting group. In addition, Ar1 may be a group in which the aromatic hydrocarbon group and the heteroaromatic group are linked. The substituent which may be substituted in the aromatic hydrocarbon group or the heteroaromatic group is a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, a fluoroalkyl group having 2-10 carbon atoms, a fluoroalkoxy group having 1-10 carbon atoms, or an alkyl group having 2-10 carbon atoms).

Description

Technical Field

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

[0002] At present, active attempts are being made to create new high-functional devices using organic substances. In particular, research and development of organic electronic devices such as photoelectric conversion elements and organic EL elements are actively underway, and material and device designs aiming at higher performance of the devices are being promoted. For example, in a photoelectric conversion element for use in dynamic image shooting, there is a problem that if the speed at which carriers (electrons and holes) generated in the light-receiving layer are transported to the electrodes is slow, it causes afterimages. Therefore, for higher performance of the device, efficient movement of carriers within the element is required.

[0003] However, an electronic material using an electron transport material containing a pyrazole derivative has been disclosed (see Patent Document 1). Among them, as the pyrazole derivative, a pyrazole derivative having an imide skeleton as a partial structure is shown.

[0004] However, in the field of organic electronic devices, further improvement in performance is required, and thus further improvement is needed.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2017-200912 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] An object of the present invention is to provide an organic electronic device for a photoelectric conversion element that can improve the transport ability of holes generated in a light-receiving layer, and a compound that can improve the transport ability of holes used in the organic electronic device.

[0010] Means for Solving the Problems

[0011] The present inventors repeatedly conducted in-depth studies to solve the above technical problems, and as a result, found that a compound having an imide skeleton as a partial structure can improve the hole transport ability in an organic electronic device for a photoelectric conversion element, thereby completing the present invention.

[0012] That is, the present invention includes the following aspects.

[0013] [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,

[0014] The organic layer includes a hole transport layer and a hole transport promoting layer containing a compound having a partial structure represented by the following formula (1), or includes a layer formed by mixing a hole transport material and a compound having the partial structure represented by the formula (1).

[0015] The organic electronic element includes a light-receiving layer.

[0016] [Chemical formula 1]

[0017]

[0018] (In formula (1), represents a bonding bond, and formula (1) forms a cyclic imide structure;

[0019] Ar 1 represents a monocyclic or polycyclic aromatic hydrocarbon group which may have a substituent, or a monocyclic or polycyclic heteroaromatic group which may have a substituent. The aromatic hydrocarbon group may be a group formed by directly connecting or connecting via a linking group multiple aromatic hydrocarbon groups, and the heteroaromatic group may be a group formed by directly connecting or connecting via a linking group multiple heteroaromatic groups. In addition, Ar 1 may be a group formed by connecting the aromatic hydrocarbon group and the heteroaromatic group.

[0020] As the substituent that may substitute in the aromatic hydrocarbon group or the heteroaromatic group, it is a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, 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.)

[0021] [2] The organic electronic element according to [1], wherein the hole transport layer and the hole transport promoting layer are adjacently disposed between the first electrode and the second electrode.

[0022] [3] The organic electronic element according to [1] or [2], wherein the compound having the partial structure represented by the formula (1) is a compound represented by the following formula (2).

[0023] [Chemical formula 2]

[0024]

[0025] (In formula (2),

[0026] Ar 1 represents the same group as Ar in the formula (1). It should be noted that one Ar 1 and another Ar 1 and 1 are the same group.

[0027] Ring A represents a monocyclic or fused-ring aromatic hydrocarbon ring. The aromatic hydrocarbon ring may be a group formed by directly connecting or connecting via a linking group multiple aromatic hydrocarbon rings.)

[0028] [4] The organic electronic device according to [3], wherein in the formula (2), ring A is represented by any one of the following (A-1) to (A-9).

[0029] [Chemical formula 3]

[0030]

[0031] [5] The organic electronic device according to [4], wherein in the formula (2), ring A is the formula (A-1) or formula (A-2).

[0032] [6] The organic electronic device according to any one of [1] to [5], wherein in the formula (1), the Ar 1 is an electron-withdrawing substituent.

[0033] [7] The organic electronic device according to any one of [1] to [6], wherein in the formula (1), Ar 1 is a phenyl, pyridyl, pyrazinyl or pyrimidinyl group substituted by at least one group selected from a cyano group, a fluoro group and a trifluoromethyl group.

[0034] [8] An imide compound represented by the following formula (3).

[0035] [Chemical formula 4]

[0036]

[0037] (In the formula (3),

[0038] Ar 2 represents a pyridyl, pyrazinyl or pyrimidinyl group substituted by at least one group selected from a cyano group, a fluoro group and a trifluoromethyl group. It should be noted that one Ar 2 and another Ar 2 are the same group.

[0039] Ring A represents any one of the following (A-1) to (A-9).)

[0040] [Chemical formula 5]

[0041]

[0042] [9] The imide compound according to [8], wherein in the formula (3), ring A is the formula (A-1) or formula (A-2).

[0043] Advantages of the Invention

[0044] According to the present invention, an organic electronic device capable of improving the hole transport ability and a compound capable of improving the hole transport ability used in the organic electronic device can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 It is a schematic cross-sectional view showing an example of the laminated structure of the photoelectric conversion device according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0046] (Organic Electronic Device)

[0047] The organic electronic device of the present invention is directed to a photoelectric conversion device including a light-receiving layer. A photoelectric conversion device is a device that converts light energy into electrical energy or an electrical signal, and includes an imaging device, a light sensor, a solar cell, and the like.

[0048] 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.

[0049] The organic layer includes a hole transport layer and a hole transport promoting layer containing a compound having a partial structure represented by the following formula (1), or a layer formed by mixing a hole transport material and a compound having the partial structure represented by the formula (1).

[0050] The organic electronic device includes a light-receiving layer.

[0051] [Chemical Formula 6]

[0052]

[0053] A detailed description of the compound having the partial structure represented by the above formula (1) will be given later.

[0054] The hole transport layer has a function 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, has a function of facilitating the hole transport and the exchange of holes between the electrodes, and contains a hole transport promoting material.

[0055] In the present invention, the compound having the partial structure represented by the above formula (1) is used as a hole transport promoting material.

[0056] As a preferred embodiment of the organic electronic device of the present invention, a photoelectric conversion device can be cited. The photoelectric conversion device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode.

[0057] Hereinafter, taking the photoelectric conversion device as an example of the organic electronic device, the device structure of the photoelectric conversion device will be described.

[0058] <Structure of the Photoelectric Conversion Element>

[0059] The photoelectric conversion element 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 includes 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 promoting layer.

[0060] In the present invention, as the hole transport promoting material contained in the hole transport promoting layer, a compound having a partial structure represented by the above formula (1) can be used.

[0061] The hole transport region is preferably adjacent to the first electrode.

[0062] The photoelectric conversion element can include other layers. As the other layers, layers commonly used in photoelectric conversion elements can be cited. For example, a light-receiving layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a buffer layer, etc. can be cited, but it is not limited to these.

[0063] The photoelectric conversion element of the present invention, for example, sequentially stacks a first electrode, a hole transport promoting layer, a hole transport layer, and a second electrode, or sequentially stacks a first electrode, a layer formed by mixing a hole transport material forming a hole transport layer and a compound having a partial structure represented by the above formula (1), and a second electrode.

[0064] In addition, the photoelectric conversion element can, for example, sequentially and adjacently stack a first electrode, a hole transport promoting layer, and a hole transport layer, or other layers such as a buffer layer can be interposed between the first electrode and the hole transport promoting layer, or between the hole transport promoting layer and the hole transport layer.

[0065] In one mode, the photoelectric conversion element of the present invention sequentially stacks a first electrode, a hole transport promoting layer, a hole transport layer, a light-receiving layer, and a second electrode. In another mode, the photoelectric conversion element of the present invention sequentially stacks a first electrode, a hole transport promoting layer, a hole transport layer, a light-receiving layer, an electron transport layer, and a second electrode. The above-mentioned layers can be stacked adjacently, or other layers can be interposed between any of the above-mentioned layers.

[0066] The photoelectric conversion element can receive incident light from either the first electrode side or the second electrode side, and either the first electrode or the second electrode can be a transparent electrode. For example, it can have a structure in which layers are stacked in the order of a transparent electrode (second electrode), an electron transport layer, a light-receiving layer, a hole transport layer, a hole transport promoting layer, and a metal electrode (first electrode), or it can have a structure in which layers are stacked in the order of a transparent electrode (first electrode), a hole transport promoting layer, a hole transport layer, a light-receiving layer, an electron transport layer, and a metal electrode (second electrode). In addition, both the first electrode and the second electrode can be transparent electrodes.

[0067] Next, a compound having a partial structure represented by the following 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.

[0068] <Compound having a partial structure represented by the following formula (1)>

[0069] The organic layer in the organic electronic device of the present invention contains a compound having a partial structure represented by the following formula (1).

[0070] [Chemical formula 7]

[0071]

[0072] In formula (1),

[0073] In formula (1), represents a bonding bond, and formula (1) forms a cyclic imide structure;

[0074] Ar 1 represents a monocyclic or polycyclic aromatic hydrocarbon group which may have a substituent, or a monocyclic or polycyclic heteroaromatic group which may have a substituent. The aromatic hydrocarbon group may be a group formed by directly connecting or connecting via a linking group multiple aromatic hydrocarbon groups, and the heteroaromatic group may be a group formed by directly connecting or connecting via a linking group multiple heteroaromatic groups. In addition, Ar 1 may be a group formed by connecting the aromatic hydrocarbon group and the heteroaromatic group.

[0075] As the substituent that can be substituted in the aromatic hydrocarbon group or the heteroaromatic group, it is a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, 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.

[0076] The so-called group formed by connecting the aromatic hydrocarbon group and the heteroaromatic group means, for example, a group formed by directly connecting or connecting via a linking group a monocyclic, polycyclic or connected aromatic hydrocarbon group and a monocyclic, polycyclic or connected heteroaromatic group.

[0077] In the above formula (1), the aromatic hydrocarbon group which is a monocyclic or condensed ring is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms. Further, the heteroaromatic group which is a monocyclic or condensed ring is preferably a heteroaromatic group having 3 to 20 carbon atoms.

[0078] As Ar 1 , it is preferably phenyl, naphthyl, pyridyl, pyrimidinyl, pyrazinyl, quinolinyl, quinoxalinyl, quinazolinyl, or triazinyl which may be substituted.

[0079] As Ar 1 The substituent which may be substituted in Ar

[0080] As Ar 1Specific examples are not particularly limited. For example, the following can be cited: phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, fluoranthenyl, triphenylenyl, biphenyl, terphenyl, methylphenyl, methylanthryl, methylphenanthryl, fluorophenyl, fluoronaphthyl, fluoroanthryl, fluorophenanthryl, cyanophenyl, cyanonaphthyl, cyanoanthryl, cyanophenanthryl, pyridylphenyl, pyridylnaphthyl, pyridylanthryl, pyridylphenanthryl, dimethylphenyl, dicyanophenyl, bis(trifluoromethyl)phenyl, bis(trifluoromethyl)naphthyl, bis(trifluoromethyl)anthryl, bis(trifluoromethyl)phenanthryl, phenyl substituted with cyano and fluoro groups, phenyl substituted with cyano and trifluoromethyl groups, phenyl substituted with fluoro and cyano groups, phenyl substituted with fluoro and trifluoromethyl groups, trifluorophenyl, pentafluorophenyl, bipyridylphenyl, bipyridyl, terpyridyl, quinolinyl, isoquinolinyl, pyrazinyl, pyrimidinyl, quinoxalinyl, quinazolinyl, methylpyridyl, methylquinolinyl, methylisoquinolinyl, methylpyrazinyl, methylpyrimidinyl, dimethylpyridyl, dimethylquinolinyl, dimethylisoquinolinyl, dimethylpyrazinyl, dimethylpyrimidinyl, pyridyl substituted with methyl and cyano groups, fluoropyridyl, fluoroquinolinyl, fluoroisoquinolinyl, fluoropyrazinyl, fluoropyrimidinyl, fluoroquinoxalinyl, fluoroquinazolinyl, difluoropyridyl, difluoroquinolinyl, difluoroisoquinolinyl, difluoropyrazinyl, difluoropyrimidinyl, difluoroquinoxalinyl, difluoroquinazolinyl, trifluoropyridyl, trifluoroquinolinyl, trifluoroisoquinolinyl, trifluoropyrazinyl, trifluoropyrimidinyl, trifluoroquinoxalinyl, trifluoroquinazolinyl, tetrafluoropyridyl, tetrafluoroquinolinyl, tetrafluoroisoquinolinyl, trifluoromethylpyridyl, trifluoromethylquinolinyl, trifluoromethylisoquinolinyl, trifluoromethylpyrazinyl, trifluoromethylpyrimidinyl, trifluoromethylquinoxalinyl, trifluoromethylquinazolinyl, bis(trifluoromethyl)pyridyl, bis(trifluoromethyl)quinolinyl, bis(trifluoromethyl)isoquinolinyl, bis(trifluoromethyl)pyrazinyl, bis(trifluoromethyl)pyrimidinyl, bis(trifluoromethyl)quinoxalinyl, bis(trifluoromethyl)quinazolinyl, tris(trifluoromethyl)pyridyl, tris(trifluoromethyl)quinolinyl, tris(trifluoromethyl)isoquinolinyl, tris(trifluoromethyl)pyrazinyl, tris(trifluoromethyl)pyrimidinyl, tris(trifluoromethyl)quinoxalinyl, tris(trifluoromethyl)quinazolinyl, cyanopyridyl, cyanoquinolinyl, cyanoisoquinolinyl, cyanopyrazinyl, cyanopyrimidinyl, cyanoquinoxalinyl, cyanoquinazolinyl, dicyanopyridyl, dicyanoquinolinyl, dicyanoisoquinolinyl, dicyanopyrazinyl, dicyanopyrimidinyl, dicyanoquinoxalinyl, dicyanoquinazolinyl, tricyanopyridyl, tricyanoquinolinyl, tricyanoisoquinolinyl, tricyanopyrazinyl, tricyanopyrimidinyl, tricyanoquinoxalinyl, tricyanoquinazolinyl, pyridyl substituted with cyano and fluoro groups, pyridyl substituted with cyano and trifluoromethyl groups, pyridyl substituted with fluoro and cyano groups, pyridyl substituted with fluoro and trifluoromethyl groups, quinoxalinyl substituted with cyano and trifluoromethyl groups, quinazolinyl substituted with cyano and trifluoromethyl groups, triazinyl, diphenyltriazinyl, dicyanotriazinyl, dipyridyltriazinyl, bis(trifluoromethyl)triazinyl, bisadamantyltriazinyl,Biscadamantylpyrimidinyl, biscadamantylpyridinyl, dicyclohexyltriazinyl, dicyclohexylpyrimidinyl, dicyclohexylpyridinyl, etc., and may also be a group formed by combining two or more of these groups.

[0081] From the aspect of being able to deepen the LUMO energy level of the hole transport promoting material and approach the HOMO energy level of the hole transport material, the compound having a partial structure shown in the above formula (1) preferably has an electron-withdrawing substituent. In the above formula (1), Ar 1 is preferably an electron-withdrawing substituent.

[0082] Here, the electron-withdrawing substituent refers to a substituent that can further deepen the LUMO energy level of the hole transport promoting material compared to the case without a substituent.

[0083] The electron-withdrawing substituent is not particularly limited and can be appropriately selected. Among the groups used as the above Ar 1 for example, the following can be cited:

[0084] Cyano group, fluoro group, chloro group, bromo group, iodo group, trifluoromethyl group, fluoroalkyl group having 2 to 10 carbon atoms, or fluoroalkoxy group having 1 to 10 carbon atoms,

[0085] Aromatic hydrocarbon group substituted with any one or more of cyano group, fluoro group, chloro group, bromo group, iodo group, and trifluoromethyl group,

[0086] Heteroaromatic group substituted with any one or more of cyano group, fluoro group, chloro group, bromo group, iodo group, and trifluoromethyl group, or

[0087] A group formed by combining two or more selected from the above groups, etc.

[0088] In addition, as an index indicating electron-withdrawing property, the Hammett value is known, and substituents showing a positive value can also be preferably cited as electron-withdrawing substituents.

[0089] In Ar of the above formula (1) 1 in the aromatic hydrocarbon group or heteroaromatic group, the number of substituents for substitution can be plural, and in the case of being plural, the types of substituents can be the same or different.

[0090] In the above formula (1), Ar 1 is preferably phenyl, pyridyl, pyrazinyl, or pyrimidinyl that can be substituted with at least one group selected from cyano group, fluoro group, and trifluoromethyl group.

[0091] The compound having a partial structure shown in the above formula (1) is preferably a compound shown in the following formula (2).

[0092] [Chemical formula 8]

[0093]

[0094] In formula (2), Ar 1 represents the same group as Ar in the aforementioned formula (1). It should be noted that one Ar 1 and another Ar 1 are the same group. 1

[0095] In formula (2), ring A represents a monocyclic or fused-ring aromatic hydrocarbon ring. The aromatic hydrocarbon ring may be a group formed by directly connecting or connecting via a linking group multiple aromatic hydrocarbon rings.

[0096] In formula (2), as ring A, for example, any one of the following (A-1) to (A-9) is preferably shown.

[0097] [Chemical formula 9]

[0098]

[0099] In formula (2), as ring A, particularly more preferably, it is the aforementioned formula (A-1) or formula (A-2).

[0100] In formula (2), when ring A is the aforementioned formula (A-1), the imide compound of the present invention is represented, for example, by the following formula (2-1); when ring A is the aforementioned formula (A-2), the imide compound of the present invention is represented, for example, by the following formula (2-2) or the following formula (2-3).

[0101] [Chemical formula 10]

[0102]

[0103] [Chemical formula 11]

[0104]

[0105] [Chemical formula 12]

[0106]

[0107] Preferred specific examples of the compound having the partial structure shown in formula (1) (more specifically, the compound shown in formula (2)) are as follows, but the compounds of the present invention are not limited thereto.

[0108] [Chemical formula 13]

[0109]

[0110] [Chemical formula 14]

[0111] ​

[0112] [Chemical Formula 15]

[0113]

[0114] [Chemical Formula 16]

[0115]

[0116] [Chemical Formula 17]

[0117]

[0118] [Chemical Formula 18]

[0119]

[0120] [Chemical Formula 19]

[0121]

[0122] [Chemical Formula 20]

[0123]

[0124] [Chemical Formula 21]

[0125]

[0126] [Chemical Formula 22]

[0127]

[0128] [Chemical Formula 23]

[0129]

[0130] [Chemical Formula 24]

[0131]

[0132] [Chemical Formula 25]

[0133]

[0134] [Chemical Formula 26]

[0135]

[0136] [Chemical Formula 27]

[0137]

[0138] The compound represented by the above formula (2) can be synthesized by known methods or combinations thereof. For example, the compound represented by formula (2) can be synthesized by (Journal of Materials Chemistry A, 2015, 3, 878 - 885).

[0139] [Chemical formula 28]

[0140]

[0141] (In the formula,

[0142] Ar 1 represents the same group as Ar in the above formula (1). It should be noted that one Ar 1 and another Ar 1 are the same group.) 1 is the same group.)

[0143] Ring A represents a monocyclic or polycyclic aromatic hydrocarbon ring. The aromatic hydrocarbon ring can be a group formed by directly connecting or connecting via a linking group multiple aromatic hydrocarbon rings.)

[0144] <<Function and effect of the compound represented by formula (2)>>

[0145] The compound represented by formula (2) has an imide skeleton as a partial structure. Through this strong acceptor skeleton, a strong interaction with the HOMO orbital of the hole - transporting material can be expected. That is, by making the layer (such as a hole - transport promoting layer) in an organic electronic device (such as a photoelectric conversion device) contain the compound represented by formula (2), an enhanced interaction with the HOMO orbital of the adjacent hole - transport layer can be expected, promoting the carrier transfer between the hole - transport layer and the hole - transport promoting layer. As described above, since the compound represented by formula (2) has a very deep LUMO energy level, smooth hole exchange between the hole - transport layer and the electrode can be expected.)

[0146] In addition, since the compound represented by formula (2) has a symmetric imide structure, thermal stability, high reduction resistance, etc. can also be expected.)

[0147] As described above, the inventors of the present invention found that the compound represented by formula (2) can be effectively used as a hole - transport promoting material to make the hole exchange between the hole - transport layer and the electrode smooth. Moreover, it was confirmed that in a photoelectric conversion device, when the compound represented by formula (2) (hole - transport promoting material) is combined with a hole - transport material, its hole - transport ability is promoted. That is, it was confirmed that in a photoelectric conversion device, through the compound represented by formula (2) as the hole - transport promoting material of the present application, the energy barrier when extracting carriers generated in the light - receiving layer to the electrode side can be reduced.)

[0148] <Embodiment>

[0149] As the laminated structure of the organic electronic element (e.g., a photoelectric conversion element) of the present invention, for example, the structures of the following (i) or the following (ii) can be cited.

[0150] (i): First electrode / hole transport promoting layer / hole transport layer / light receiving layer / second electrode

[0151] (ii): First electrode / hole transport promoting layer / hole transport layer / light receiving layer / electron transport layer / second electrode

[0152] Hereinafter, taking the structure of the above (ii) as an example, reference is made to Figure 1 to further describe in detail the photoelectric conversion element of the present invention. Figure 1 is a schematic cross-sectional view showing an example of the laminated structure of the photoelectric conversion element of the present invention.

[0153] <<First Embodiment>>

[0154] The photoelectric conversion element based on the first embodiment is an organic imaging element or a photosensor having Figure 1 the laminated structure shown.

[0155] The photoelectric conversion element 1 sequentially includes a first electrode 11 (first electrode), a hole transport promoting layer 12, a hole transport layer 13, a light receiving layer 14, an electron transport layer 15, and a second electrode 16 (second electrode). However, some of these layers may be omitted, and conversely, other layers may be added.

[0156] In Figure 1 In the photoelectric conversion element 1 shown, light enters from above the transparent first electrode 11 and is received by the light receiving layer 14. It should be noted that in Figure 1 , for convenience, it is shown that light enters from the side of the light receiving layer 14. In addition, in the photoelectric conversion element 1, a voltage is applied so that holes among the charges (holes and electrons) generated by photoelectric conversion in the light receiving layer 14 move to the first electrode 11 and electrons move to the second electrode 16. That is, the first electrode 11 serves as a hole collection electrode, and the second electrode 16 serves as an electron collection electrode. It should be noted that in Figure 1 , the substrate provided on the upper surface of the first electrode 11 is omitted. The substrate here is not particularly limited, and for example, a glass plate, a quartz plate, a plastic plate, etc. can be cited. In addition, in the case of a structure in which light enters from the substrate side, the substrate is transparent with respect to the wavelength of light. Hereinafter, each of the above layers will be described.

[0157] [First electrode 11]

[0158] The first electrode 11 or the second electrode 16 is provided on the substrate.

[0159] In the case of a photoelectric conversion element having a structure in which light passes through the first electrode 11 and is incident on the light-receiving layer 14, the first electrode is formed of a transparent material that allows the light to pass through or substantially pass through. Here, "allowing light to pass through" means that the average transmittance is 80% or more, and "substantially passing through" means that the average transmittance is 50% or more. That is, in this specification, "transparent" means that the average transmittance is 50% or more.

[0160] The transparent material used for the first electrode 11 or the second electrode 16 is not particularly limited, and examples thereof include indium-tin oxide (ITO; Indium Tin Oxide), indium-zinc oxide (IZO; Indium Zinc Oxide), 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.

[0161] It should be noted that in the case of a photoelectric conversion element having a structure in which light is incident on the light-receiving layer 14 only from the second electrode 16 side, the transmission characteristics of the first electrode 11 are not important. Therefore, as an example of the material used for the first electrode in this case, gold, iridium, molybdenum, palladium, platinum, etc. can be cited.

[0162] [Hole transport promoting layer 12]

[0163] A hole transport promoting layer 12 is provided between the first electrode 11 and the hole transport layer 13 described later. The hole transport promoting layer 12 is provided to promote the hole transport from the hole transport layer 13 to the first electrode 11. The hole transport promoting layer 12 contains a compound having a partial structure represented by the formula (1). In addition, a compound other than the compound having a partial structure represented by the formula (1) can also be contained together. As the compound that can be contained in the hole transport promoting layer 12, for example, a conventionally known hole transport material can be cited, and a compound used in the hole transport layer 13 described later can be cited.

[0164] [Hole transport layer 13]

[0165] A hole transport layer 13 is provided between the hole transport promoting layer 12 and the light-receiving layer 14.

[0166] The hole transport layer 13 has the function of transporting the holes generated in the light-receiving layer 14 from the light-receiving layer 14 to the first electrode 11, and the function of blocking the movement of electrons generated in the light-receiving layer 14 to the first electrode 11 side. In addition, depending on the use, it sometimes has the function of blocking the electron injection from the first electrode 11.

[0167] The hole transport layer 13 may be a single-layer structure containing one or more than two materials, or may be a laminated structure of multiple layers with the same or different compositions. The hole transport materials that can be contained in the hole transport layer 13 may be well-known hole transport materials. As well-known hole transport materials, 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, naphthalenedithiophene compounds, naphthothiophenothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenedithiophene compounds, benzothiophenobenzothiophene compounds, indolocarbazole compounds, etc. can be cited.

[0168] Among them, fluorene compounds, carbazole compounds, naphthalenedithiophene compounds, naphthothiophenothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenedithiophene compounds, benzothiophenobenzothiophene compounds, indolocarbazole compounds, etc. are preferred, and fluorene compounds, carbazole compounds, chrysenedithiophene compounds, benzothiophenobenzothiophene compounds, indolocarbazole compounds are particularly preferred.

[0169] [Light-receiving layer 14]

[0170] A light-receiving layer 14 is provided between the hole transport layer 13 and the electron transport layer 15 described later.

[0171] As the material of the light-receiving layer 14, materials having a photoelectric conversion function can be cited.

[0172] The light-receiving layer 14 may be a single-layer structure containing one or more than two materials, or may be a laminated structure of multiple layers with the same or different compositions.

[0173] Among them, in order to improve the photoelectric conversion efficiency, the light-receiving layer preferably contains a layer containing at least two materials (organic components).

[0174] As the material used in the light-receiving layer 14 having a single-layer structure containing one material, for example, (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, etc. can be cited.

[0175] As the material used in the light-receiving layer 14 having a single-layer structure containing two materials, for example, combinations of the above (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives and (ii) fullerene and its derivatives, other acceptor materials can be cited. The light-receiving layer 4 containing these materials can be formed by vapor deposition in a state where the powders are pre-mixed, or can be formed by co-vapor deposition in any ratio.

[0176] As the material used in the light-receiving layer 14 which is a single-layer structure containing three materials, for example, combinations of the above (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, (ii) fullerene and its derivatives, other acceptor materials, and (iii) hole-transporting materials can be cited. The light-receiving layer 14 containing these materials can be formed by vapor deposition in a state where the powders are pre-mixed, or can be formed by co-evaporation at an arbitrary ratio.

[0177] (i) As specific examples of coumarin derivatives, coumarin 6 and coumarin 30 can be cited. As specific examples of quinacridone derivatives, N,N-dimethylquinacridone can be cited. As specific examples of phthalocyanine derivatives, boron subphthalocyanine chloride and boron subnaphthalocyanine chloride (Sub NC) can be cited.

[0178] (ii) As specific examples of fullerene and its derivatives,

[60] fullerene,

[70] fullerene, and [6,6]-phenyl-C61-butyric acid methyl ester (

[60] PCBM) can be cited.

[0179] (iii) As preferred compounds and specific examples of hole-transporting materials, the same compounds and specific examples as those used in the above hole-transporting layer 13 can be cited.

[0180] In addition, the material having a photoelectric conversion function is not limited to being contained only in the light-receiving layer. For example, the material having a photoelectric conversion function can also be contained in a layer (hole-transporting layer 13 or electron-transporting layer 15) adjacent to the light-receiving layer 14.

[0181] [Electron-transporting layer 15]

[0182] An electron-transporting layer 15 is provided between the light-receiving layer 14 and the second electrode 16 described later.

[0183] The electron-transporting layer 15 has the function of transporting the electrons generated in the light-receiving layer 14 to the second electrode 16, and the function of blocking the movement of holes from the second electrode 16 which is the electron transport destination to the light-receiving layer 14. In addition, depending on the use, it sometimes has the function of blocking the hole injection from the second electrode 16.

[0184] In addition, the electron transport material that can be contained in the electron transport layer 15 can be a known electron transport material. Examples of the electron transport material include: fullerenes, fullerene derivatives, triazine derivatives, manganese bis(8-hydroxyquinoline), aluminum tris(8-hydroxyquinoline), aluminum tris(2-methyl-8-hydroxyquinoline), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-hydroxyquinoline)-4-(phenylphenol)aluminum), 4,6-bis(3,5-bis(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic diimide, and N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic diimide, etc.

[0185] The electron transport layer 15 can be a single-layer structure containing one or more than two materials, or a multilayer stacked structure containing the same composition or different compositions.

[0186] [Second Electrode 16]

[0187] A second electrode 16 is provided on the electron transport layer 15.

[0188] Examples of the material for the second electrode 16 include: indium-tin oxide (ITO), indium-zinc oxide (IZO), sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al2O3) mixture, indium, lithium / aluminum mixture, gold, platinum, rare earth metals, molybdenum oxide, etc. It should be noted that the first electrode 11 and the second electrode 16 can be the same or different.

[0189] [Formation Method of Each Layer]

[0190] Except for the first electrode 11 and the second electrode 16 described above, each layer can be formed by thinning the material of each layer (together with materials such as a binder resin and a solvent as needed) by a known method such as vacuum evaporation, spin coating, casting, LB (Langmuir-Blodgett method), etc.

[0191] The film thickness of each layer formed in this way is not particularly limited and can be appropriately selected according to the situation. Usually, it is in the range of 5 nm or more and 5 μm or less.

[0192] The first electrode 11 and the second electrode 16 can be formed by thinning the electrode material by methods such as evaporation and sputtering. A pattern can be formed by a mask with a desired shape during evaporation and sputtering, or a pattern with a desired shape can be formed by photolithography after forming a thin film by evaporation, sputtering, etc.

[0193] The film thicknesses of the first electrode 11 and the second electrode 16 are preferably 1 μm or less, more preferably 10 nm or more and 200 nm or less.

[0194] The first electrode 11 and the second electrode 16 can replace their respective constituent materials as needed (also referred to as the reverse type structure). In the case of such a structure, it becomes a photoelectric conversion element having a structure in which light passes through the second electrode 16 and is incident on the light receiving layer 14.

[0195] An imaging element including the photoelectric conversion element of the present embodiment can be applied, for example, to an imaging element of a digital camera or a digital video camera, and an imaging element incorporated in a mobile phone or the like. A light sensor can be applied, for example, to a remote controller of a television, a switch of an air conditioner, opening and closing of an automatic door, and the like.

[0196] <<Second Embodiment>>

[0197] The photoelectric conversion element according to the second embodiment of the present invention includes Figure 1 a solar cell having the laminated structure shown. In the solar cell 1, a hole transport promoting layer 12 and a hole transport layer 13 are provided between the first electrode 11 and the light receiving layer 14, and an electron transport layer 15 is provided between the second electrode 16 and the light receiving layer 14. However, some of these layers may be omitted, and conversely, other layers may be added.

[0198] [First Electrode 11]

[0199] The first electrode 11 is made of a transparent material, for example, and the transparent material that can be used is the transparent material in the first embodiment. The first electrode 11 can also be formed on an arbitrary substrate (for example, a transparent substrate such as glass, plastic, or polymer film).

[0200] [Hole Transport Promoting Layer 12]

[0201] The material of the hole transport promoting layer 12 is the same as the material of the hole transport promoting layer 12 in the first embodiment (a compound having a partial structure represented by formula (1)). The material of the hole transport promoting layer 12 may contain a conventionally known hole transport material in addition to the material in the first embodiment.

[0202] [Hole Transport Layer 13]

[0203] 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.

[0204] [Light Receiving Layer 14]

[0205] The material of the light-receiving layer 14 only needs to be a material that uses an electron-donating material and an electron-accepting material. It can be a planar combination type in which the electron-donating material and the electron-accepting material are combined with each other in a plane, or a bulk heterojunction type in which the electron-donating material and the electron-accepting material are mixed to form a film.

[0206] The electron-donating material is not particularly limited, and an organic semiconductor is preferred. As the electron-donating material, for example, the following can be cited: polymer compounds such as polythiophene derivatives, polyfluorene derivatives, poly(phenylene vinylene) derivatives, and their copolymers, or phthalocyanine derivatives and their metal complexes, porphyrin derivatives and their metal complexes, acene derivatives such as pentacene, and low-molecular compounds such as diamine derivatives. Regarding the electron-donating material, within the range that does not impair the effects of the present invention, an inorganic semiconductor can also be used together with the organic semiconductor.

[0207] The electron-accepting material is not particularly limited, and an organic semiconductor is preferred. As the electron-accepting material, for example, fullerene derivatives, perylene derivatives, and naphthalene derivatives can be cited.

[0208] [Electron transport layer 15]

[0209] The material of the electron transport layer 15 can use the electron transport material in the first embodiment. In addition, as the electron transport material, alkali metal halides such as sodium fluoride and cesium fluoride, alkaline earth metal halides such as calcium fluoride, carbonates such as cesium carbonate, and inorganic n-type semiconductors such as titanium oxide and zinc oxide can also be used.

[0210] [Second electrode 16]

[0211] Examples of the second electrode 16 include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or their alloys.

[0212] The first electrode 11 and the second electrode 16 can replace their respective constituent materials as needed (also referred to as an inverted structure). In the case of such a structure, it becomes a photoelectric conversion element having a structure in which light passes through the second electrode 16 and is incident on the light-receiving layer 14.

[0213] [Forming method of each layer]

[0214] The forming method of each layer is not particularly limited. For example, on a substrate, the first electrode 11, the hole transport promoting layer 12, the hole transport layer 13, the light-receiving layer 14, the electron transport layer 15, and the second electrode 16 can be sequentially laminated using a vapor deposition method, a spin coating method, a casting method, a pattern transfer method, etc. Alternatively, after laminating the hole transport promoting layer 12, the hole transport layer 13, the light-receiving layer 14, and the electron transport layer 15, the first electrode 11 and the second electrode 16 can be formed on the laminate by transfer, vapor deposition, sputtering, etc., respectively.

[0215] The organic electronic device (photoelectric conversion device) of the present invention and the method for forming each layer of the device are not limited to the device and method shown in the above embodiments. For example, the materials of the first electrode, light-receiving layer, electron transport layer, and second electrode can be appropriately replaced with other known materials. In addition, the hole transport promoting layer and the hole transport layer can also be replaced with a layer formed by mixing a compound having a partial structure shown in formula (1) with a hole transport material.

[0216] (Compound that can be used in an organic electronic device)

[0217] The present invention provides a novel compound that can improve the transport ability of holes used in an organic electronic device.

[0218] The novel imide compound of the present invention that can be used in an organic electronic device is represented by the following formula (3).

[0219] [Chemical formula 29]

[0220]

[0221] (In formula (3),

[0222] Ar 2 represents a pyridyl, pyrazinyl, or pyrimidinyl group substituted with at least one group selected from a cyano group, a fluoro group, and a trifluoromethyl group. It should be noted that one Ar 2 and another Ar 2 are the same group.

[0223] Ring A represents any one of the following (A-1) to (A-9).)

[0224] [Chemical formula 30]

[0225]

[0226] In the above formula (3), among the pyridyl, pyrazinyl, and pyrimidinyl groups of Ar 2 , from the viewpoint of physical properties, the pyridyl group is preferred.

[0227] In the above formula (3), ring A is preferably the above formula (A-1) or formula (A-2).

[0228] When ring A in the above formula (3) is the above formula (A-1) or formula (A-2), the imide compound is synonymous with the case where ring A is shown in the above formula (2).

[0229] Examples

[0230] The present invention will be further described in detail below by way of examples, but the present invention is not limited to these examples.

[0231] [Compound for evaluation]

[0232] [Chemical formula 31]

[0233]

[0234] [Synthesis Example 1: Synthesis of Compound (B-3)]

[0235] [Chemical formula 32]

[0236]

[0237] Under a nitrogen stream, 1.1 g (5.0 mmol) of benzene-1,2,4,5-tetracarboxylic dianhydride, 1.2 g (10.5 mmol) of 4-aminobenzonitrile, 0.6 g (4.3 mmol) of isoquinoline, and 20 mL of m-cresol were added to a 100 mL three-necked flask, and the mixture was stirred at 180 °C for 4 hours. After cooling to room temperature, the precipitated solid was filtered and washed with ethanol. Then, the obtained solid was recrystallized with dimethylformamide to obtain the target (B-3) (1.7 g, yield 81%).

[0238] The obtained compound (B-3) was identified by 1 1H-NMR.

[0239] 1 1H-NMR (DMSO-d6) δ (ppm): 8.49 (s, 2H), 8.11 (d, 4H), 7.78 (d, 4H)

[0240] [Synthesis Example 2: Synthesis of Compound (B-31)]

[0241] [Chemical formula 33]

[0242]

[0243] Using 2.0 g (10.5 mmol) of 5-amino-2-cyanobenzotrifluoride instead of 1.2 g (10.5 mmol) of 4-aminobenzonitrile, the same operations as in Synthesis Example 1 were carried out to obtain the target (B-31) (2.3 g, yield 83%).

[0244] The obtained compound (B-31) was identified by FD-MS and 1 1H-NMR.

[0245] Mass spectrometry (FD-MS): 554

[0246] 11H-NMR (DMSO-d6) δ (ppm): 8.55 (s, 2H), 8.44 (d, 2H), 8.24 (d, 2H), 8.11 (d, 2H)

[0247] [Synthesis Example 3: Synthesis of Compound (B-2)]

[0248] [Chemical Formula 34]

[0249]

[0250] Using 1.2 g (10.5 mmol) of 3-aminobenzonitrile instead of 1.2 g (10.5 mmol) of 4-aminobenzonitrile, the same operations as in Synthesis Example 1 were carried out, and the target (B-2) (1.5 g, yield 71%) was obtained.

[0251] The obtained compound (B-2) was identified by FD-MS.

[0252] Mass spectrometry (FD-MS): 418

[0253] [Synthesis Example 4: Synthesis of Compound (B-103)]

[0254] [Chemical Formula 35]

[0255]

[0256] Under a nitrogen stream, 1.3 g (5.0 mmol) of naphthalene-1,4,5,8-tetracarboxylic dianhydride, 1.9 g (10.5 mmol) of 5-amino-2-cyanobenzotrifluoride, 0.6 g (4.3 mmol) of isoquinoline, and 20 mL of m-cresol were added to a 100 mL three-necked flask, and the mixture was stirred at 180 °C for 5 hours. After cooling to room temperature, the precipitated solid was filtered and washed with ethanol. Subsequently, the obtained solid was recrystallized from dimethylformamide to obtain the target (B-103) (1.7 g, yield 56%).

[0257] The obtained compound (B-103) was identified by 1 1H-NMR.

[0258] 1 1H-NMR (DMSO-d6) δ (ppm): 8.77 (s, 4H), 8.46 (d, 2H), 8.31 (s, 2H), 8.11 (d, 2H)

[0259] [Synthesis Example 5: Synthesis of Compound (B-63)]

[0260] [Chemical Formula 36]

[0261]

[0262] Using 1.7 g (10.5 mmol) of 4-amino-2-(trifluoromethyl)pyridine instead of 1.2 g (10.5 mmol) of 4-aminobenzonitrile, the same operations as in Synthesis Example 1 were carried out, and the target (B-63) (1.4 g, yield 55%) was obtained.

[0263] The obtained compound (B-63) was identified by 1 1H-NMR.

[0264] 1 1H-NMR (DMSO-d6) δ (ppm): 9.02 (d, 2H), 8.57 (s, 2H), 8.16 (d, 2H), 8.00 (d, 2H)

[0265] [Synthesis Example 6: Synthesis of Compound (B-135)]

[0266] [Chemical Formula 37]

[0267]

[0268] Using 1.7 g (10.5 mmol) of 4-amino-2-(trifluoromethyl)pyridine instead of 1.9 g (10.5 mmol) of 5-amino-2-cyanobenzotrifluoride, the same operations as in Synthesis Example 4 were carried out, and the target (B-135) (1.8 g, yield 64%) was obtained.

[0269] The obtained compound (B-135) was identified by 1 1H-NMR.

[0270] 1 1H-NMR (DMSO-d6) δ (ppm): 9.06 (d, 2H), 8.78 (s, 4H), 8.21 (s, 2H), 7.96 (d, 2H)

[0271] [Synthesis Example 7: Synthesis of Compound (B-8)]

[0272] [Chemical Formula 38]

[0273]

[0274] Under a nitrogen stream, 1.1 g (5.0 mmol) of benzene-1,2,4,5-tetracarboxylic dianhydride, 1.5 g (10.5 mmol) of 4-aminophthalonitrile, 0.6 g (4.3 mmol) of isoquinoline, and 20 mL of m-cresol were added to a 100 mL three-necked flask and stirred at 140 °C for 10 hours. After cooling to room temperature, the precipitated solid was filtered and washed with ethanol. Subsequently, the obtained solid was recrystallized from dimethylformamide / toluene to obtain the target (B-8) (1.2 g, yield 52%).

[0275] The obtained compound (B-8) was identified by 1 1H-NMR.

[0276] 1 1H-NMR (DMSO-d6) δ (ppm): 8.57 (s, 2H), 8.38 (d, 2H), 8.30 (d, 2H), 8.11 (d, 2H)

[0277] [Synthesis Example 8: Synthesis of Compound (B-67)]

[0278] [Chemical Formula 39]

[0279]

[0280] Using 1.3 g (10.5 mmol) of 2-amino-5-cyanopyridine instead of 1.5 g (10.5 mmol) of 4-aminophthalonitrile, the same procedure as in Synthesis Example 7 was carried out to obtain the target (B-67) (0.59 g, yield 28%).

[0281] The obtained compound (B-67) was identified by FD-MS.

[0282] Mass spectrometry (FD-MS): 420

[0283] [Synthesis Example 9: Synthesis of Compound (B-68)]

[0284] [Chemical Formula 40]

[0285]

[0286] Using 1.3 g (10.5 mmol) of 5-aminopyrazine-2-carbonitrile instead of 1.5 g (10.5 mmol) of 4-aminophthalonitrile, the same procedure as in Synthesis Example 7 was carried out to obtain the target (B-68) (0.63 g, yield 30%).

[0287] The obtained compound (B-68) was identified by 1 1H-NMR.

[0288] 1 1H-NMR (DMSO-d6) δ (ppm): 9.40 (s, 2H), 9.07 (s, 2H), 8.62 (s, 2H)

[0289] [Synthesis Example 10: Synthesis of Compound (B-177)]

[0290] [Chemical Formula 41]

[0291]

[0292] Using 1.3 g (10.5 mmol) of 5-aminopicolinonitrile instead of 1.5 g (10.5 mmol) of 4-aminophthalonitrile, the same procedure as in Synthesis Example 7 was carried out to obtain the target (B-177) (1.3 g, yield 64%).

[0293] The obtained compound (B-177) was identified by 1 1H-NMR.

[0294] 1 1H-NMR (DMSO-d6) δ (ppm): 8.96 (d, 2H), 8.57 (s, 2H), 8.32 (d, 2H), 8.26 (dd, 2H)

[0295] [Synthesis Example 11: Synthesis of Compound (B-178)]

[0296] [Chemical Formula 42]

[0297]

[0298] Using 1.3 g (10.5 mmol) of 5-aminonicotinonitrile instead of 1.5 g (10.5 mmol) of 4-aminophthalonitrile, the same procedure as in Synthesis Example 7 was carried out to obtain the target (B-178) (1.2 g, yield 58%).

[0299] The obtained compound (B-178) was identified by 1 1H-NMR.

[0300] 1 1H-NMR (DMSO-d6) δ (ppm): 9.16 (d, 2H), 9.06 (d, 2H), 8.59 (s, 2H), 8.52 (t, 2H)

[0301] [Synthesis Example 12: Synthesis of Compound (B-187)]

[0302] [Chemical Formula 43]

[0303]

[0304] Using 2.0 g (10.5 mmol) of 5-amino-3-(trifluoromethyl)picolinonitrile instead of 1.5 g (10.5 mmol) of 4-aminophthalonitrile, the same operation as in Synthesis Example 7 was carried out except for this, and the target (B-187) (1.1 g, yield 40%) was obtained.

[0305] The obtained compound (B-187) was identified by FD-MS.

[0306] Mass spectrometry (FD-MS): 556

[0307] [Synthesis Example 13: Synthesis of compound (B-201)]

[0308] [Chemical formula 44]

[0309]

[0310] 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 5-aminopicolinonitrile, 0.6 g (4.3 mmol) of isoquinoline, and 20 mL of m-cresol were added to a 100 mL three-necked flask, and the mixture was stirred at 140 °C for 10 hours. After cooling to room temperature, the precipitated solid was filtered and washed with ethanol. Subsequently, the obtained solid was recrystallized from dimethylformamide / toluene, whereby the target (B-201) (1.4 g, yield 59%) was obtained.

[0311] The obtained compound (B-201) was identified by 1 1H-NMR.

[0312] 1 1H-NMR (DMSO-d6) δ (ppm): 8.92 (d, 2H), 8.78 (s, 4H), 8.34 (d, 2H), 8.27 (dd, 2H)

[0313] [Synthesis Example 14: Synthesis of compound (B-204)]

[0314] [Chemical formula 45]

[0315]

[0316] Using 1.3 g (10.5 mmol) of 4-aminopicolinonitrile instead of 1.3 g (10.5 mmol) of 5-aminopicolinonitrile, the same operation as in Synthesis Example 13 was carried out except for this, and the target (B-204) (0.94 g, yield 40%) was obtained.

[0317] The identification of the obtained compound (B-204) was carried out by 1 1H-NMR.

[0318] 1 1H-NMR (DMSO-d6) δ (ppm): 9.04 (d, 2H), 8.79 (s, 4H), 8.28 (d, 2H), 8.00 (dd, 2H)

[0319] [Synthesis Example 15: Synthesis of Compound (B-209)]

[0320] [Chemical Formula 46]

[0321]

[0322] Using 1.3 g (10.5 mmol) of 5-aminopyrimidine-2-carbonitrile instead of 1.3 g (10.5 mmol) of 5-aminopicolinonitrile, the same operation as in Synthesis Example 13 was carried out, and the target (B-209) (1.2 g, yield 50%) was obtained.

[0323] The identification of the obtained compound (B-209) was carried out by FD-MS.

[0324] Mass spectrometry (FD-MS): 472

[0325] [Synthesis Example 16: Synthesis of Compound (B-258)]

[0326] [Chemical Formula 47]

[0327]

[0328] Using 1.3 g (10.5 mmol) of 2-amino-6-cyanopyrazine instead of 1.3 g (10.5 mmol) of 5-aminopicolinonitrile, the same operation as in Synthesis Example 13 was carried out, and the target (B-258) (0.35 g, yield 15%) was obtained.

[0329] The identification of the obtained compound (B-258) was carried out by 1 1H-NMR.

[0330] 1 1H-NMR (DMSO-d6) δ (ppm): 9.48 (s, 2H), 9.30 (s, 2H), 8.81 (br-s, 4H)

[0331] <Fabrication 1 and Evaluation 1 of Single-Hole Devices>

[0332] [Element Example 1]

[0333] Fabricate a single-hole device with a structure including a first electrode / a first hole injection layer / a hole transport layer / a hole transport promoting layer / a second electrode, and evaluate the hole transport characteristics of the device.

[0334] (First Electrode)

[0335] As a substrate having a first electrode on its surface, prepare a glass substrate with an ITO transparent electrode where the ITO film (film thickness 110 nm) is patterned into stripes. After cleaning the substrate with isopropyl alcohol, perform surface treatment by ozone-ultraviolet cleaning.

[0336] (Preparation for Vacuum Evaporation)

[0337] On the side of the substrate that has undergone the above surface treatment and where the ITO film is formed on both sides, perform vacuum evaporation of each layer using the vacuum evaporation method to stack and form each layer.

[0338] First, introduce the above glass substrate into the vacuum evaporation chamber and reduce the pressure to 1.0×10 -4 Pa. Then, fabricate according to the film-forming conditions of each layer in the following order.

[0339] (Fabrication of the First Hole Injection Layer)

[0340] Deposit 1 nm of MoO3 on the ITO film to fabricate the hole injection layer.

[0341] (Fabrication of the Hole Transport Layer)

[0342] Deposit 100 nm of (HTL-1), which is a hole transport material, to fabricate the hole transport layer. It should be noted that (HTL-1) is synthesized by the method described in JP-A-2018-193371.

[0343] (Fabrication of the Hole Transport Promoting Layer)

[0344] Deposit 10 nm of the sublimation-purified compound (B-3) to fabricate the hole transport promoting layer.

[0345] (Fabrication of the Second Electrode)

[0346] Deposit 80 nm of Au to fabricate the second electrode.

[0347] (Evaluation of the Hole Transport Ability of the Single-Hole Device)

[0348] Apply positive and negative electric fields to the first electrode and the second electrode of the single-hole device of Component Example 1, respectively, and measure the voltage value at a current density of 10 mA / cm 2 . Show the obtained results in Table 1.

[0349] [Component Example 2]

[0350] The single-hole device was fabricated in the same manner as in Element Example 1, except that compound (B-31) was used instead of compound (B-3) used in the fabrication of the hole transport promoting layer in Example 1. The hole transport ability of the obtained single-hole device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0351] [Element Example 3]

[0352] The single-hole device was fabricated in the same manner as in Element Example 1, except that compound (B-63) was used instead of compound (B-3) used in the fabrication of the hole transport promoting layer in Example 1. The hole transport ability of the obtained single-hole device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0353] [Element Example 4]

[0354] The single-hole device was fabricated in the same manner as in Element Example 1, except that compound (B-68) was used instead of compound (B-3) used in the fabrication of the hole transport promoting layer in Example 1. The hole transport ability of the obtained single-hole device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0355] [Element Example 5]

[0356] The single-hole device was fabricated in the same manner as in Element Example 1, except that compound (B-178) was used instead of compound (B-3) used in the fabrication of the hole transport promoting layer in Example 1. The hole transport ability of the obtained single-hole device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0357] [Element Example 6]

[0358] The single-hole device was fabricated in the same manner as in Element Example 1, except that compound (B-201) was used instead of compound (B-3) used in the fabrication of the hole transport promoting layer in Example 1. The hole transport ability of the obtained single-hole device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0359] [Element Comparative Example 1]

[0360] The single-hole device was fabricated in the same manner as in Element Example 1, except that it did not have a hole transport promoting layer. The hole transport ability of the obtained single-hole device was evaluated in the same manner as in Element Example 1. The results are shown in Table 1.

[0361] [Element Comparative Example 2]

[0362] Compound (NPT) was used instead of compound (B-3) used in the fabrication of the hole transport promoting layer in Example 1. Except for this, a single-hole device was fabricated by the same method as in Device Example 1. The hole transport ability of the single-hole device obtained by evaluation by the same method as in Device Example 1 was evaluated. The results are shown in Table 1.

[0363] [Table 1]

[0364]

[0365] For the device of Device Example 1 using compounds (B-3), (B-31), (B-63), (B-68), (B-178), and (B-201) as hole transport promoting materials (HOD voltages were 2.51 V, 2.77 V, 1.01 V, 1.98 V, 2.15 V, and 2.33 V respectively), compared with the device of Comparative Example 1 without using a hole transport promoting material (HOD voltage was 4.70 V), the HOD voltage decreased. Additionally, for the device of Device Example 1 using compounds (B-3), (B-31), (B-63), (B-68), (B-178), and (B-201) as hole transport promoting materials (HOD voltages were 2.51 V, 2.77 V, 1.01 V, 1.98 V, 2.15 V, and 2.33 V respectively), compared with the device of Comparative Example 2 using the known material NPT (HOD voltage was 3.90 V), the HOD voltage decreased.

[0366] <Fabrication and Evaluation of Photovoltaic Conversion Element>

[0367] [Device Example 7]

[0368] A photovoltaic conversion element 1 having a laminated structure including a substrate / second electrode 16 / electron transport layer 15 / light-receiving layer 14 / hole transport layer 13 / hole transport promoting layer 12 / first electrode 11 was fabricated, and the dark current and external quantum efficiency of the photovoltaic conversion element were evaluated.

[0369] (Preparation of Substrate and Second Electrode 16)

[0370] As a substrate having a second electrode on its surface, a glass substrate with an indium tin oxide (ITO) film (film thickness 110 nm) 2 mm wide patterned into stripes was prepared. Then, the substrate was cleaned with isopropyl alcohol and surface-treated by ozone ultraviolet cleaning.

[0371] (Preparation for Vacuum Evaporation)

[0372] On the substrate that has undergone surface treatment with cleaning, vacuum evaporation is performed for each layer using the vacuum evaporation method, and each layer is formed by stacking.

[0373] First, the above-mentioned glass substrate is introduced into the vacuum evaporation chamber, and the pressure is reduced to 7.0×10 -5 Pa. Then, it is fabricated according to the film-forming conditions of each layer in the following order.

[0374] (Fabrication of the electron transport layer 15)

[0375] The sublimation-purified compound 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine is formed into a film at a rate of 0.03 nm / second for 10 nm to fabricate the electron transport layer 15.

[0376] (Fabrication of the light-receiving layer 14)

[0377] N,N-dimethylquinacridone and fullerene C60 are formed into a film at a ratio of 4:1 (mass ratio) for 250 nm to fabricate the photoelectric conversion layer 14. The film-forming rate is 0.13 nm / second.

[0378] (Fabrication of the hole transport layer 13)

[0379] The hole transport material (HTL-1) is formed into a film at a rate of 0.10 nm / second for 10 nm to fabricate the hole transport layer 13.

[0380] (Fabrication of the hole transport promoting layer 12)

[0381] The compound (B-3) is formed into a film at a rate of 0.20 nm / second for 10 nm to fabricate the hole transport promoting layer 12.

[0382] (Fabrication of the first electrode 11)

[0383] Finally, a metal mask is arranged in a direction orthogonal to the ITO stripes on the substrate, and the first electrode 11 is formed into a film. The first electrode is formed by depositing 80 nm of Au. The film-forming rate of Au is 0.1 nm / second.

[0384] Thus, a device with an area of 4 mm 2 of Figure 1The photoelectric conversion element 1 shown above. A voltage with an absolute value of 2.5 V is applied to the photoelectric conversion element fabricated in the above-described manner so that electrons are transmitted to the second electrode 16 side and holes are transmitted to the first electrode 11 side, and the current in the dark (dark current) and the external quantum efficiency at this time are evaluated. The measurement of the dark current is evaluated using a Source-Measure Unit 2636B manufactured by Keithley. The measurement of the external quantum efficiency is performed using a solar cell spectral sensitivity measurement device (manufactured by Soma Optical Co., Ltd.). The wavelength of the irradiated light is measured at 560 nm and the intensity is 50 μW / cm 2 is measured. The results are shown in Table 2. It should be noted that the dark current and the external quantum efficiency are relative values based on the results in Comparative Example 3 of the element described hereinafter (100). The lower the value of the dark current, the better the performance, and the higher the value of the external quantum efficiency, the better the performance.

[0385] [Element Example 8]

[0386] In the production of the hole transport promoting layer 12, compound (B-31) is used instead of compound (B-3). Other than this, the photoelectric conversion element of Element Example 8 is fabricated by the same method as in Element Example 7, and the dark current and the external quantum efficiency are measured by the same method as in Element Example 7. The results are shown in Table 2.

[0387] [Element Example 9]

[0388] In the production of the hole transport promoting layer 12, compound (B-63) is used instead of compound (B-3). Other than this, the photoelectric conversion element of Element Example 9 is fabricated by the same method as in Element Example 7, and the dark current and the external quantum efficiency are measured by the same method as in Element Example 7. The results are shown in Table 2.

[0389] [Element Example 10]

[0390] In the production of the hole transport promoting layer 12, compound (B-135) is used instead of compound (B-3). Other than this, the photoelectric conversion element of Element Example 10 is fabricated by the same method as in Element Example 7, and the dark current and the external quantum efficiency are measured by the same method as in Element Example 7. The results are shown in Table 2.

[0391] [Element Example 11]

[0392] In the production of the hole transport promoting layer 12, compound (B-8) is used instead of compound (B-3). Other than this, the photoelectric conversion element of Element Example 11 is fabricated by the same method as in Element Example 7, and the dark current and the external quantum efficiency are measured by the same method as in Example 7. The results are shown in Table 2.

[0393] [Element Embodiment 12]

[0394] In the production of the hole transport promoting layer 12, compound (B-68) was used instead of compound (B-3). Otherwise, the photoelectric conversion element of Element Embodiment 12 was produced by the same method as in Element Embodiment 7, and the dark current and external quantum efficiency were measured by the same method as in Embodiment 7. The results are shown in Table 2.

[0395] [Element Embodiment 13]

[0396] In the production of the hole transport promoting layer 12, compound (B-177) was used instead of compound (B-3). Otherwise, the photoelectric conversion element of Element Embodiment 13 was produced by the same method as in Element Embodiment 7, and the dark current and external quantum efficiency were measured by the same method as in Element Embodiment 7. The results are shown in Table 2.

[0397] [Element Embodiment 14]

[0398] In the production of the hole transport promoting layer 12, compound (B-178) was used instead of compound (B-3). Otherwise, the photoelectric conversion element of Element Embodiment 14 was produced by the same method as in Element Embodiment 7, and the dark current and external quantum efficiency were measured by the same method as in Element Embodiment 7. The results are shown in Table 2.

[0399] [Element Embodiment 15]

[0400] In the production of the hole transport promoting layer 12, compound (B-187) was used instead of compound (B-3). Otherwise, the photoelectric conversion element of Element Embodiment 15 was produced by the same method as in Element Embodiment 7, and the dark current and external quantum efficiency were measured by the same method as in Element Embodiment 7. The results are shown in Table 2.

[0401] [Element Embodiment 16]

[0402] In the production of the hole transport promoting layer 12, compound (B-204) was used instead of compound (B-3). Otherwise, the photoelectric conversion element of Element Embodiment 16 was produced by the same method as in Element Embodiment 7, and the dark current and external quantum efficiency were measured by the same method as in Element Embodiment 7. The results are shown in Table 2.

[0403] [Element Embodiment 17]

[0404] In the production of the hole transport promoting layer 12, compound (B-209) was used instead of compound (B-3). Other than this, the photoelectric conversion element of Element Example 17 was produced by the same method as in Element Example 7, and the dark current and external quantum efficiency were measured by the same method as in Element Example 7. The results are shown in Table 2.

[0405] [Element Comparative Example 3]

[0406] In the production of the hole transport promoting layer 12, compound (NPT) was used instead of compound (B-3). Other than this, the photoelectric conversion element of Element Comparative Example 3 was produced by the same method as in Element Example 7, and the dark current and external quantum efficiency were measured by the same method as in Element Example 7. The results are shown in Table 2.

[0407] [Element Comparative Example 4]

[0408] The hole transport promoting layer 12 was not provided. Other than this, the photoelectric conversion element of Element Comparative Example 4 was produced by the same method as in Element Example 7, and the dark current and external quantum efficiency were measured by the same method as in Element Example 7. The results are shown in Table 2.

[0409] [Table 2]

[0410]

[0411] As shown in Table 2, in the elements of the element examples using the material for the photoelectric conversion element of the imaging element of the present invention, compared with the elements of the element comparative examples, the dark current was suppressed and a high external quantum efficiency was obtained.

[0412] The organic electronic element of the present invention can improve the hole transport ability by containing a compound having the partial structure represented by the above formula (1), and more specifically, by containing the compound represented by the above formula (2). When used in a photoelectric conversion element, photoelectric conversion can be performed more effectively. In addition, the organic electronic element of the present invention can suppress the dark current and has a high external quantum efficiency by containing a compound having the partial structure represented by the above formula (1), and more specifically, by containing the compound represented by the above formula (2).

[0413] Explanation of Reference Numerals

[0414] 1. Photoelectric conversion element

[0415] 11. First electrode

[0416] 12. Hole transport promoting layer

[0417] 13. Hole transport layer

[0418] 14. Light-receiving layer

[0419] 15. Electron transport layer

[0420] 16. Second electrode.

Claims

1. An organic electronic component, characterized in that, Comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, The organic layer includes a hole transport layer and a hole transport promoting layer containing a compound having a partial structure represented by the following formula (1), or a layer formed by mixing a hole transport material and a compound having the partial structure represented by the formula (1), The organic electronic element includes a light-receiving layer, ， In formula (1), represents a bonding key, and formula (1) forms a cyclic imide structure; Ar 1 represents an aromatic hydrocarbon group of a monocyclic or fused ring, which may or may not have a substituent, or a heteroaromatic group of a monocyclic or fused ring, which may or may not have a substituent; the aromatic hydrocarbon group is a group formed by directly connecting or connecting via a linking group multiple aromatic hydrocarbon groups, and the heteroaromatic group is a group formed by directly connecting or connecting via a linking group multiple heteroaromatic groups; further, Ar 1 is a group formed by connecting the aromatic hydrocarbon group and the heteroaromatic group, As the substituent that substitutes in the aromatic hydrocarbon group or the heteroaromatic group, it is a cyano group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethyl group, a methyl group, 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.

2. The organic electronic component according to claim 1, wherein, The hole transport layer and the hole transport promoting layer are adjacently disposed between the first electrode and the second electrode.

3. The organic electronic component according to claim 1, wherein, The compound having the partial structure represented by the formula (1) is a compound represented by the following formula (2), ， In formula (2), Ar 1 represents the same group as Ar in the formula (1), one Ar 1 and the other Ar 1 are the same group, 1 ​ Ring A represents a monocyclic or polycyclic aromatic hydrocarbon ring, and the aromatic hydrocarbon ring is a group formed by directly connecting or connecting via a linking group multiple aromatic hydrocarbon rings.

4. The organic electronic component according to claim 3, wherein, In the formula (2), ring A is represented by any one of the following (A-1) to (A-9), 。 5. The organic electronic component according to claim 4, wherein, In the formula (2), ring A is the formula (A-1) or formula (A-2).

6. The organic electronic component according to claim 1, wherein, In the formula (1), the Ar 1 is an electron-withdrawing substituent.

7. The organic electronic component according to claim 1, wherein, In the formula (1), Ar 1 is phenyl, pyridyl, pyrazinyl or pyrimidinyl substituted with at least one group selected from a cyano group, a fluoro group and a trifluoromethyl group.

8. An imide compound represented by the following formula (3), , In formula (3), Ar 2 represents a pyridyl, pyrazinyl or pyrimidinyl group substituted by at least one group selected from a cyano group, a fluoro group and a trifluoromethyl group, one Ar 2 and another Ar 2 are the same group, Ring A represents any one of the following (A-1) to (A-9), .

9. The imide compound according to claim 8, wherein, In the formula (3), ring A is the formula (A-1) or formula (A-2).

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