Condensed ring compound, material for organic electronic device, and organic electronic device

Abstract

To provide a material for an organic electronic device capable of forming an excellent electron transport layer, and an organic electronic device using the material.SOLUTION: Provided is a charge transport material for an organic electronic device, comprising a condensed ring compound represented by formula (1). In the formula (1), R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 each independently represent a hydrogen atom or a substituent, and adjacent R1 to R16 may bond to each other to form a ring.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a fused ring compound having a specific structure, a material for an organic electronic device containing the compound, and an organic electronic device using the material for an organic electronic device. [Background technology]

[0002] Currently, there are active attempts to create new high-performance devices using organic materials, and in particular, research and development of organic electronic elements such as photoelectric conversion elements and organic electroluminescence (EL) elements is being actively conducted, and material and device design is being promoted with the aim of improving device performance. For example, in photoelectric conversion elements used for video recording, if the speed at which carriers (electrons and holes) generated in the light-receiving layer are transported to the electrode is slow, this causes a problem of afterimages. In organic EL elements, if the speed at which carriers are transported from the electrode to the light-emitting layer is slow, this causes a problem of an increase in driving voltage. Therefore, in order to improve the performance of devices, highly efficient movement of carriers within the element is required.

[0003] Incidentally, π-conjugated compounds having various skeletons and methods for synthesizing the same have been disclosed for the purpose of providing novel π-conjugated compounds (see Non-Patent Document 1). However, the compounds described in Non-Patent Document 1 are limited to use as light-emitting materials for coating-type organic EL devices. In addition, long alkyl chains are introduced to improve solubility, making them difficult to apply to deposition materials, and there is no description of using these compounds in deposition-type organic electronic devices. On the other hand, in the field of organic electronic devices, further improvements are required to achieve higher performance. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Chem. Eur. J. 2018, 24, 6968-6974. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a material for an organic electronic device capable of forming a good electron transport layer, an organic electronic device using the material for an organic electronic device, a fused ring compound having a specific structure for use in the material for an organic electronic device, and a method for producing the fused ring compound. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems and have found that a fused ring compound having a specific structure can form a good electron transport layer in an organic electronic element such as a photoelectric conversion element or an organic EL element, thereby completing the present invention.

[0007] That is, the present invention includes the following aspects. [1] A fused ring compound represented by the following formula (1): [ka] (In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom or a substituent, and adjacent R 1 ~R 12 may be bonded to each other to form a ring. [2] R 1 , R 4 , R 5 and R 8 is a hydrogen atom. [3] The combination which may be bonded to each other to form a ring is R 2 and R 3 , R 6 and R7 , R 9 and R 10 , and R 11 and R 12 The fused ring compound according to [1] or [2], which is a combination of one or more pairs selected from the group consisting of: [4] The substituents are each independently Deuterium atom; Fluorine, chlorine, bromine, and iodine atoms; Trifluoromethyl group, pentafluoroethyl group; Cyano group; Nitro group; Hydroxyl groups; Thiol groups; an optionally substituted aromatic hydrocarbon group; optionally substituted heteroaromatic groups; an optionally substituted arylamino group; an optionally substituted phosphine oxide group; a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms; A linear or branched alkyl group having 1 to 18 carbon atoms; A linear or branched alkoxy group having 1 to 18 carbon atoms; or The fused ring compound according to any one of [1] to [3], wherein the group is a trifluoromethylsulfonyloxy group. [5] A fused ring compound represented by the following formula (2), (3) or (4): [ka] (In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom or a substituent, and adjacent R 1 ~R 12 do not combine with each other to form a ring.a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R о , and R p each independently represents a hydrogen atom or a substituent, and adjacent R b and R c and R f and R g may be bonded to each other to form a ring. [6] The fused ring compound according to [5], wherein the fused ring compound represented by the formula (2) is any one of the following formulae (2A), (2B) and (2C): [ka] (In formulas (2A) to (2C), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R a , R d , R e , R h , R q , R r , R s , R t , R u , R v , R w and R x each independently represents a hydrogen atom or a substituent. [7] A method for producing a fused ring compound represented by formula (1), comprising reacting a compound represented by formula (A) below with either or both of compounds represented by formulas (B) and (C) below: [ka] (In formulas (A) to (C), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom or a substituent, and adjacent R 1 ~R 12 may be bonded to each other to form a ring. [8] The method according to [7], wherein the compounds represented by the formulae (A), (B) and (C) are represented by the following formulae (A1), (B1) and (C1), respectively. [ka] (In the formula, R 1 , R 4 , R 5 and R 8 each independently represents a hydrogen atom or a substituent; R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R о and R p each independently represents a hydrogen atom or a substituent, and adjacent R b and R c , and R f and R g may be bonded to each other to form a ring. [9] A charge transport material for an organic electronic device, comprising a fused ring compound represented by the following formula (1): [ka] (In formula (1), R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom or a substituent, and adjacent R 1 ~R 12 may be bonded to each other to form a ring.

[10] R 1 , R 4 , R 5 and R 8 [9] The charge transport material for an organic electronic device according to [9], wherein

[11] The combination which may be bonded to each other to form a ring is R 2 and R 3 , R 6 and R 7 , R 9 and R 10 , and R 11 and R 12 The charge transport material for an organic electronic device according to [9] or

[10] , which is a combination of one or more groups selected from the group consisting of:

[12] The substituents are each independently Deuterium atom; Fluorine, chlorine, bromine, and iodine atoms; Trifluoromethyl group, pentafluoroethyl group; Cyano group; Nitro group; Hydroxyl groups; Thiol groups; an optionally substituted aromatic hydrocarbon group; optionally substituted heteroaromatic groups; an optionally substituted arylamino group; an optionally substituted phosphine oxide group; a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms; A linear or branched alkyl group having 1 to 18 carbon atoms; A linear or branched alkoxy group having 1 to 18 carbon atoms; or The charge transport material for an organic electronic device according to any one of [9] to

[11] , which is a trifluoromethylsulfonyloxy group.

[13] The charge transport material for an organic electronic device according to any one of [9] to

[12] , which is a material for a photoelectric conversion device or an organic EL device.

[14] The charge transport material for an organic electronic device according to

[13] , which is a vapor deposition material.

[15] An organic electronic device comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, the organic layer containing the charge transport material for organic electronic devices according to any one of [9] to

[12] .

[16] The organic electronic device according to

[15] , which is a photoelectric conversion element or an organic EL element. Effect of the Invention

[0008] The present invention can provide a material for an organic electronic device capable of forming a good electron transport layer, an organic electronic device using the material for an organic electronic device, a fused ring compound having a specific structure used in the material for an organic electronic device, and a method for producing the fused ring compound. [Brief description of the drawings]

[0009] [Figure 1] 1 is a schematic cross-sectional view showing an example of a layered structure of a photoelectric conversion element according to the present invention. [Diagram 2] FIG. 1 is a schematic cross-sectional view showing an example of a layered structure of an organic EL element according to the present invention. [Diagram 3] FIG. 2 is a schematic cross-sectional view showing a layered structure of an organic EL element produced in an example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] <Fused ring compounds> The fused ring compound of the present embodiment is a fused ring compound represented by the following formula (1). [ka] In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom or a substituent; adjacent R 1 ~R 12 may be bonded to each other to form a ring.

[0011] <R 1 ~R 12 About > In formula (1), R 1 ~R 12 Each of the substituents represented by the formula: Deuterium atom; Fluorine, chlorine, bromine, and iodine atoms; Trifluoromethyl group, pentafluoroethyl group; Cyano group; Nitro group; Hydroxyl groups; Thiol groups; an optionally substituted aromatic hydrocarbon group; optionally substituted heteroaromatic groups; an optionally substituted arylamino group; an optionally substituted phosphine oxide group; a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms; A linear or branched alkyl group having 1 to 18 carbon atoms; A linear or branched alkoxy group having 1 to 18 carbon atoms; or Trifluoromethylsulfonyloxy group It is preferable that:

[0012] In formula (1), R 1 ~R 12The substituent represented by the formula (I) is preferably an alkyl group, a fluorine atom, a cyano group, an aromatic hydrocarbon group, or a heteroaromatic group, and more preferably a fluorine atom, a cyano group, an aromatic hydrocarbon group, or a heteroaromatic group.

[0013] The alkyl group is preferably a straight-chain, branched, or cyclic alkyl group having a carbon number of 1 to 18. Examples of such an alkyl group include a methyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, a cyclohexyl group, and a 1-adamantyl group.

[0014] In the formula (1), the aromatic hydrocarbon group is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having a carbon number of 6 to 30. Examples of such aromatic hydrocarbon groups include a phenyl group, a biphenyl group, and a naphthyl group. Examples of the substituent in the aromatic hydrocarbon group include an alkyl group, a fluorine atom, a cyano group, an aromatic hydrocarbon group, and a heteroaromatic group, and a fluorine atom, a cyano group, an aromatic hydrocarbon group, or a heteroaromatic group is more preferable. The alkyl group as a substituent is preferably a linear, branched, or cyclic alkyl group having a carbon number of 1 to 4. Examples of such an alkyl group include a methyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group.

[0015] The aromatic hydrocarbon group as a substituent is preferably a monocyclic, linked, or condensed aromatic hydrocarbon group having a carbon number of 6 to 30. Examples of such aromatic hydrocarbon groups include a phenyl group, a biphenyl group, and a naphthyl group. The heteroaromatic group as a substituent is preferably a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms. Examples of such heteroaromatic groups include a pyridyl group, a pyrimidyl group, a triazyl group, a dibenzofuranyl group, a dibenzothiophenyl group, and a carbazolyl group.

[0016] In the formula (1), the heteroaromatic group is preferably a monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms. Examples of such heteroaromatic groups include a pyrrolyl group, a thienyl group, a furyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridyl group, a phenylpyridyl group, a pyridylphenyl group, a pyrimidyl group, a pyrazyl group, a 1,3,5-triazyl group, a 1,3,5-triazylphenyl group, a 1,3,5-triazylbiphenylyl group, a 4,6-diphenyl-1,3,5-triazyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzimidazolyl group, an isopropyl group, a phenylpyridyl ... Examples of the heteroaromatic group include an aryl group, an aryl group, and a heteroaryl group. ... Examples of the substituent on the heteroaromatic group include the same substituents as those described above for the aromatic hydrocarbon group.

[0017] R 1 , R 4 , R 5 and R 8 is preferably a hydrogen atom from the viewpoint of obtaining the fused ring compound in good yield.

[0018] Adjacent R 1 ~R 12 When they are bonded together to form a ring, R 2 and R 3 , R 6 and R 7 , R 9 and R 10 , and R 11 and R 12It is preferable that the ring formed here is, for example, benzene, naphthalene, anthracene, phenazine, oxanthrene, or thianthrene, and benzene, naphthalene, or phenazine is more preferable.

[0019] <Preferred embodiments of fused ring compounds> The fused ring compound is preferably the fused ring compound (2), (3) or (4) described below. [ka] In formulas (2) to (4), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom or a substituent, and adjacent R 1 ~R 12 do not combine with each other to form a ring. a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R о , and R p each independently represents a hydrogen atom or a substituent, and adjacent R b and R c and R f and R g may be bonded to each other to form a ring.

[0020] <R 1 ~R 12 About > R in formulas (2) to (4) 1 ~R 12 is the same as formula (1).

[0021] <R a ~R p About > R in formulas (2) to (4) a ~R p The substituents represented by the formula (I) and their preferred ranges are as described above for R 1 ~R 12 The same can be mentioned. R 1 , R 4 , R 5 and R 8 is preferably a hydrogen atom from the viewpoint of obtaining the fused ring compound in good yield.

[0022] Adjacent R b and R c and R f and R g may be bonded to each other to form a ring, and examples of the fused ring compounds forming the above ring include the following formulae (2A) to (2C). [ka]

[0023] <R 1 ~R 8 and R a ~R h About > R in formulas (2A) to (2C) 1 ~R 8 and R a ~R h is the same as equation (2).

[0024] <R q ~R x About > R in formulas (2A) to (2C) q ~R x The substituents represented by the formula (I) and their preferred ranges are as described above for R 1 ~R 12The same can be mentioned.

[0025] Specific examples of the fused ring compound represented by formula (1) include the fused ring compounds represented by the following formulas (1-1) to (4-3).

[0026] [ka]

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] <Method for producing fused ring compound> The fused ring compound represented by formula (1) can be produced, for example, by the method shown in the following synthetic route 1. 1 ~R 12 , and R a ~R p The definition and the preferred range of the substituents are the same as described above.

[0031] <Synthetic Route> A compound represented by the following formula (A) and either or both of the compounds represented by the following formulas (B) and (C) are subjected to a dehydration condensation reaction using an acid to obtain a fused ring compound represented by formula (1). From the viewpoint of obtaining formula (1) in good yield, it is preferable to react either one of the compounds represented by the following formulas (B) and (C), and R 9 , R 10 , R 11 , and R 12 It is more preferable that all are the same. [ka]

[0032] In formulas (A) to (C), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom or a substituent, and adjacent R 1 ~R 12 may be bonded to each other to form a ring.

[0033] The compounds represented by the formulae (A), (B) and (C) may be represented by the following formulae (A1), (B1) and (C1), respectively, as necessary. [ka] In the formula, R 1 , R 4 , R 5 and R 8 each independently represents a hydrogen atom or a substituent; R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R о and R p each independently represents a hydrogen atom or a substituent, and adjacent R b and R c , and R f and R g may be bonded to each other to form a ring.

[0034] <Charge transport material for organic electronic devices> The fused ring compound represented by the following formula (1) can be used as a charge transport material for an organic electronic device. That is, the charge transport material for an organic electronic device of this embodiment contains the fused ring compound represented by the following formula (1) of this embodiment. In the following charge transport material for an organic electronic device, R 1 ~R 12 The definition and the preferred range of the substituents are the same as described above. [ka] In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom or a substituent; adjacent R 1 ~R 12 may be bonded to each other to form a ring.

[0035] The charge transport material for organic electronic devices containing the fused ring compound represented by the above formula (1) can function as an electron transport material or a hole blocking material for a photoelectric conversion device or an organic EL device. The charge transport material for organic electronic devices containing the fused ring compound represented by the above formula (1) is preferably used by vapor deposition.

[0036] <<Action and effect of the compound represented by formula (1)>> The compound represented by formula (1) has a highly condensed ring skeleton and has a high glass transition temperature (Tg). By having a high Tg, it is possible to prevent changes in the film state, such as crystallization, caused by annealing when manufacturing an organic electronic device. This makes it possible to suppress deterioration of dark current, external quantum efficiency, response time and driving voltage, luminous efficiency, and device life in, for example, a photoelectric conversion device and an organic EL device formed from the charge transport material for organic electronic devices. Therefore, the charge transport material for organic electronic devices of the present invention can be suitably used as a charge transport material for organic electronic devices that requires resistance to annealing.

[0037] The present inventors have found that the compound represented by formula (1) can be effectively used as an electron transport material in an organic electronic device. In addition, when the compound represented by formula (1) is actually used as an electron transport material in a photoelectric conversion device or an organic EL device, the carrier transport in the organic electronic device is promoted, and for example, in the photoelectric conversion device and the organic EL device of an imaging device, excellent dark current, external quantum efficiency, response time, and excellent driving voltage, luminous efficiency, and device life can be realized, respectively. Therefore, the charge transport material for organic electronic devices of the present invention can be suitably used as an electron transport material in organic electronic devices, more specifically, in photoelectric conversion devices such as imaging devices and organic EL devices.

[0038] <Organic electronic elements> One embodiment of the present invention is directed to an organic electronic element comprising a photoelectric conversion element or an organic electroluminescent element (organic EL element), and provides an organic electronic element having an electron transport layer that exhibits good performance by incorporating a charge transport material for organic electronic elements having a specific structure into the organic electronic element.

[0039] An embodiment of the organic electronic device of the present invention includes a photoelectric conversion device and an organic EL device. The photoelectric conversion device is a device that converts light energy into electric energy or an electric signal, and includes an image sensor, a photosensor, a solar cell, and the like.

[0040] One embodiment of the organic electronic element is, for example, an organic electronic element including a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, in which the organic layer contains the charge transport material for organic electronic elements described above.

[0041] <<Photoelectric conversion element>> The photoelectric conversion element of the present embodiment includes the charge transport material for organic electronic devices described above. The photoelectric conversion element of the present embodiment may include an upper electrode, a lower electrode, and one or more organic layers disposed between the upper electrode and the lower electrode, and at least one of the organic layers includes the charge transport material for organic electronic devices described above. Each of the organic layers in the photoelectric conversion element of the present embodiment may be regarded as an organic thin film.

[0042] The configuration of the photoelectric conversion element for an imaging device of this embodiment is not particularly limited, but examples thereof include the following configurations (i) to (v). (i) Lower electrode / photoelectric conversion layer / upper electrode (ii) Lower electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / upper electrode (iii) Lower electrode / photoelectric conversion layer / hole transport layer (electron blocking layer) / upper electrode (iv) Lower electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / upper electrode (v) Lower electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / buffer layer / upper electrode

[0043] If necessary, the buffer layer may be replaced with a layer having another name or function, such as a work function adjustment layer.

[0044] Hereinafter, the photoelectric conversion element according to this embodiment will be described in more detail by taking the above configuration (v) as an example with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of the layered structure of the photoelectric conversion element according to this embodiment.

[0045] 1 includes, in this order, a substrate 1, a lower electrode 2, an electron transport layer 3, a photoelectric conversion layer 4, a hole transport layer 5, a buffer layer 6, and an upper electrode 7. Note that, in the photoelectric conversion element of this embodiment, some of these layers may be omitted, and other layers may be added.

[0046] In the photoelectric conversion element 100, light is incident from below the transparent lower electrode 2. Furthermore, a voltage is applied to the photoelectric conversion element 100 so that, of the charges (holes and electrons) generated in the photoelectric conversion layer 4, the electrons move to the lower electrode 2 and the holes move to the upper electrode 7. That is, in the photoelectric conversion element 100, the lower electrode 2 serves as an electron collecting electrode and the upper electrode 7 serves as a hole collecting electrode.

[0047] The photoelectric conversion element 100 contains a charge transport material for an organic electronic device in at least one layer selected from the group consisting of an electron transport layer 3, a photoelectric conversion layer 4, a hole transport layer 5, and a buffer layer 6. The photoelectric conversion element 100 preferably contains a charge transport material for an organic electronic device in the photoelectric conversion layer 4 and / or the electron transport layer 3, and more preferably contains a charge transport material for an organic electronic device in the electron transport layer 3. The charge transport material for an organic electronic device may be contained in multiple layers of the photoelectric conversion element 100.

[0048] Hereinafter, the details of each layer will be described taking as an example the photoelectric conversion element 100 in which the electron transport layer 3 contains a charge transport material for an organic electronic element.

[0049] [Substrate 1] The substrate 1 is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate, etc. In a configuration in which light is incident from the substrate 1 side, the substrate 1 preferably has high transmittance (for example, a transmittance of 80% or more, preferably a transmittance of 90% or more) for the wavelength of the incident light.

[0050] [Lower electrode 2] A lower electrode 2 is provided on a substrate 1 . In the case of a photoelectric conversion element for an imaging device in which light passes through the lower electrode 2 and enters the photoelectric conversion layer, it is preferable that the lower electrode 2 has high transmittance to the wavelength of the incident light (e.g., a transmittance of 80% or more, preferably a transmittance of 90% or more).

[0051] There is no particular limitation on the material constituting the lower electrode 2. From the viewpoint of excellent light transmittance, the material constituting the lower electrode 2 may be, for example, 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, metal sulfides such as zinc sulfide, and the like.

[0052] In the case of a photoelectric conversion element for an imaging device in which light is incident on the photoelectric conversion layer only from the upper electrode 7 side, the transmission characteristics of the lower electrode 2 are not important. Therefore, the material constituting the lower electrode 2 in this case may be, for example, gold, iridium, molybdenum, palladium, platinum, or the like.

[0053] [Electron transport layer (hole blocking layer) 3] Between the lower electrode 2 and a photoelectric conversion layer 4 described later, an electron transport layer (hole blocking layer) 3 is provided. The electron transport layer 3 has a role of transporting electrons generated in the photoelectric conversion layer 4 to the lower electrode 2, and a role of blocking holes generated in the photoelectric conversion layer 4 from moving to the lower electrode 2. In addition, depending on the application, the electron transport layer 3 may also have a role of preventing hole injection from the lower electrode 2.

[0054] The electron transport layer 3 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. The electron transport layer 3 may have a two-layer structure including, for example, a layer adjacent to the photoelectric conversion layer 4 made of a material specialized in hole blocking properties, and a layer adjacent to the lower electrode 2 made of a material specialized in electron transport properties.

[0055] The electron transport layer 3 may be a layer containing a conventionally known electron transport material in addition to the charge transport material for an organic electronic device described above. Examples of conventionally known electron transport materials include bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (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.

[0056] [Photoelectric conversion layer 4] The photoelectric conversion layer 4 is provided between the electron transport layer 3 and a hole transport layer 5 described below. The photoelectric conversion layer 4 contains a material having a photoelectric conversion function.

[0057] The photoelectric conversion layer 4 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.

[0058] Examples of photoelectric conversion layers having a single-layer structure made of one type of material include photoelectric conversion layers made of materials such as coumarin and its derivatives, quinacridone and its derivatives, and phthalocyanine and its derivatives.

[0059] An example of a photoelectric conversion layer having a single layer structure made of two or more materials is a photoelectric conversion layer containing (I) a first material selected from the group consisting of coumarin and its derivatives, quinacridone and its derivatives, and phthalocyanine and its derivatives, and (II) a second material selected from the group consisting of fullerene and its derivatives. The photoelectric conversion layer may further contain (III) a hole transport material. The photoelectric conversion layer 4 made of these materials may be formed, for example, by deposition using a mixed powder obtained by mixing powders of each material, or may be formed by co-deposition of each material in any ratio.

[0060] (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).

[0061] (II) Specific examples of fullerenes and derivatives thereof include

[60] fullerene,

[70] fullerene, and [6,6]-phenyl-C61-methylbutyrate (

[60] PCBM).

[0062] (III) hole transport material may be a known hole transport material.As the hole transport material, for example, aromatic tertiary amine compound, naphthalene compound, anthracene compound, tetracene compound, pentacene compound, phenanthrene compound, pyrene compound, perylene compound, chrysene compound, benzochrysene compound, dibenzochrysene compound, fluorene compound, carbazole compound, indole compound, pyrrole compound, picene compound, thiophene compound, benzotrifuran compound, benzotrithiophene compound, naphthodithiophene compound, naphthothienothiophene compound, benzodifuran compound, benzodithiophene compound, benzothiophene compound, naphthobisbenzothiophene compound, chrysenodithiophene compound, benzothienobenzothiophene compound, indolocarbazole compound, etc. can be mentioned. Among these, chrysene compounds, benzochrysene compounds, dibenzochrysene compounds, fluorene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like are preferred, and benzochrysene compounds, dibenzochrysene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are more preferred.

[0063] Specific examples of hole transport materials include 9,9'-(9,9'-spirobi[9H-fluorene]-2,7'-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b':5,6-b'']trifuran compounds, benzo[1,2-b:3,4-b':5,6-b'']trithiophene compounds, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2',3 ':4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b']dithiophene, benzo[1,2-b:4,5-b']bis[1]benzothiophene, naphtho[1,2-b:5,6-b']bis[1]benzothiophene, chryseno[1,2-b:8,7-b']dithiophene, [1]benzothieno[3,2-b][1]benzothiophene, and compounds represented by the following formulas (ic-1), (ic-2) and (ic-3). [ka]

[0064] The material having the above-mentioned photoelectric conversion function may be contained only in the photoelectric conversion layer 4, or may be contained in layers other than the photoelectric conversion layer 4. For example, layers adjacent to the photoelectric conversion layer 4 (electron transport layer 3, hole transport layer 5) may contain a material having a photoelectric conversion function.

[0065] [Hole transport layer (electron blocking layer) 5] Between the photoelectric conversion layer 4 and a buffer layer 6 described later, a hole transport layer (electron blocking layer) 5 is provided.

[0066] The hole transport layer 5 has a role of transporting holes generated in the photoelectric conversion layer 4 to the upper electrode 7 side, and a role of blocking the movement of electrons generated in the photoelectric conversion layer 4 to the upper electrode 7 side. Depending on the application, the hole transport layer 5 may also have a role of blocking electron injection from the upper electrode 7.

[0067] The hole transport layer 5 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. The hole transport layer 5 may have a two-layer structure including, for example, a layer adjacent to the photoelectric conversion layer 4 made of a material specialized for electron blocking properties, and a layer adjacent to the buffer layer 6 made of a material specialized for hole transport properties.

[0068] The hole transport layer 5 may contain a conventionally known hole transport material. Preferred compounds and specific examples of the conventionally known hole transport material include the same compounds as the hole transport material described in the section on the photoelectric conversion layer 4.

[0069] [Buffer layer 6] A buffer layer 6 is provided between the hole transport layer 5 and the upper electrode 7 described later. When the upper electrode 7 is formed by a sputtering method, the buffer layer 6 serves to reduce damage to an organic layer (e.g., the hole transport layer 5) during sputtering. In addition, by adjusting the work function of the buffer layer 6, the charge balance of the entire photoelectric conversion element can be controlled, and the buffer layer 6 is also called a work function adjustment layer.

[0070] The material constituting the buffer layer 6 may be a known material, such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA) or 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN).

[0071] [Top electrode 7] An upper electrode 7 is provided on the buffer layer 6 . The material of the upper electrode 7 is not particularly limited, and may be, for example, sodium, a sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, silver, a magnesium / silver mixture, aluminum, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al2O3) mixture, indium, a lithium / aluminum mixture, a rare earth metal, or the like.

[0072] [How each layer is formed] Each layer other than the lower electrode 2 and the upper electrode 7 can be formed by forming the material of each layer (and, if necessary, a binder resin, a solvent, etc.) into a thin film by a known method such as a vacuum deposition method, a spin coating method, a casting method, or a LB (Langmuir-Blodgett) method.

[0073] The thickness of each layer other than the lower electrode 2 and the upper electrode 7 is not particularly limited and can be appropriately selected depending on the situation. The thickness of each layer other than the lower electrode 2 and the upper electrode 7 is usually in the range of 5 nm to 5 μm.

[0074] The lower electrode 2 and the upper electrode 7 can be formed by thinning an electrode material by a method such as vapor deposition or sputtering.

[0075] When the lower electrode 2 and the upper electrode 7 have a pattern, the pattern can be formed, for example, by performing deposition, sputtering, etc. through a mask of a desired shape. Alternatively, after forming a thin film by deposition, sputtering, etc., a pattern of a desired shape may be formed by photolithography.

[0076] The thickness of the lower electrode 2 and the upper electrode 7 may be, for example, 1 μm or less, and is preferably 10 nm or more and 200 nm or less.

[0077] The materials constituting the lower electrode 2 and the upper electrode 7 may be interchanged as necessary (also called an inverted structure). In this case, a photoelectric conversion element for an imaging device is formed in which light passes through the upper electrode 7 and enters the photoelectric conversion layer 4.

[0078] The photoelectric conversion element of this embodiment can be applied to, for example, organic solar cells, imaging elements such as digital cameras and digital video cameras, imaging elements built into mobile phones, and the like.

[0079] <Organic electroluminescent device> The organic electroluminescent device of the present embodiment contains the charge transport material for organic electronic devices described above. Hereinafter, an organic electroluminescent device (hereinafter, sometimes simply referred to as an organic EL device) containing the charge transport material for organic electronic devices will be described.

[0080] The configuration of the organic electroluminescent device is not particularly limited, but examples thereof include the following configurations (i) to (v). (i): Anode / Emitting layer / Cathode (ii): anode / hole transport layer / light emitting layer / cathode (iii): anode / light-emitting layer / electron transport layer / cathode (iv): anode / hole transport layer / light emitting layer / electron transport layer / cathode (v): anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

[0081] The charge transport material for an organic electronic device may be contained in any of the layers described above. However, in terms of excellent light-emitting properties of the organic electroluminescent device, it is preferable that the charge transport material for an organic electronic device be contained in one or more layers selected from the group consisting of the light-emitting layer and the layer between the light-emitting layer and the cathode.

[0082] Therefore, in the case of the above configurations (i) to (v), the charge transport material for an organic electronic device is preferably contained in one or more layers selected from the group consisting of a light-emitting layer, an electron transport layer, and an electron injection layer.

[0083] Hereinafter, an organic electroluminescent device according to one embodiment of the present invention will be described in more detail with reference to FIG. 2, taking the above configuration (v) as an example.

[0084] 2 has a so-called bottom-emission type element configuration, the organic electroluminescent element according to one embodiment of the present invention is not limited to the bottom-emission type element configuration. That is, the organic electroluminescent element according to one embodiment of the present invention may have another known element configuration, such as a top-emission type.

[0085] FIG. 2 is a schematic cross-sectional view showing an example of a laminate structure of an organic electroluminescent device including a charge transport material for an organic electronic device according to one embodiment of the present invention.

[0086] The organic electroluminescent device 200 includes a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an emitting layer 105, an electron transport layer 106, an electron injection layer 107, and a cathode 108 in this order. However, some of these layers may be omitted, or other layers may be added. For example, a hole blocking layer may be provided between the emitting layer 105 and the electron transport layer 106, or the hole injection layer 103 may be omitted, and the hole transport layer 104 may be provided directly on the anode 102.

[0087] Alternatively, a single layer having the functions of the multiple layers, such as an electron injection / transport layer having both the functions of the electron injection layer and the electron transport layer, may be provided instead of the multiple layers. Furthermore, the single-layer hole transport layer 104 and the single-layer electron transport layer 106 may each be made up of multiple layers.

[0088] <<Layer containing charge transport material for organic electronic device>>

[0089] 2, the organic electroluminescent device 200 contains a charge transport material for an organic electronic device in one or more layers selected from the group consisting of the light-emitting layer 105, the electron transport layer 106, and the electron injection layer 107. It is preferable that the electron transport layer 106 contains a charge transport material for an organic electronic device. The charge transport material for an organic electronic device may be contained in multiple layers of the organic electroluminescent device.

[0090] The following describes an organic electroluminescent device 200 in which the electron transport layer 106 includes a charge transport material for organic electronic devices.

[0091] [Substrate 101] The substrate 101 is not particularly limited as long as it is a commonly used substrate, and examples thereof include a glass plate, a quartz plate, a plastic plate, a plastic film, etc. Among these, a glass plate, a quartz plate, and a light-transmitting plastic film are preferable.

[0092] Examples of light-transmitting plastic films include films made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), etc.

[0093] In addition, in the case of a configuration in which light is extracted from the substrate 101 side, the substrate 101 is transparent to the wavelength of the emitted light.

[0094] [Anode 102] An anode 102 is provided on the substrate 101 (on the hole injection layer 103 side).

[0095] Examples of the anode material include metals, alloys, electrically conductive compounds, and mixtures thereof, each having a large work function (e.g., 4 eV or more).Specific examples of the anode material include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO2, and ZnO.

[0096] In the case of an organic electroluminescent device in which light is extracted through the anode, the anode is formed of a conductive transparent material that is transparent or substantially transparent to the emitted light.

[0097] [Hole injection layer 103, hole transport layer 104] Between the anode 102 and the light-emitting layer 105, a hole injection layer 103 and a hole transport layer 104 are provided in this order from the anode 102 side.

[0098] The hole injection layer 103 and the hole transport layer 104 have the function of transporting holes injected from the anode to the light-emitting layer. By interposing the hole injection layer 103 and the hole transport layer 104 between the anode 102 and the light-emitting layer 105, a large number of holes are injected into the light-emitting layer 105 with a lower electric field.

[0099] The hole injection layer 103 and the hole transport layer 104 also function as electron barrier layers. That is, the electrons injected from the cathode 108 and transported from the electron injection layer 107 and / or the electron transport layer 106 to the light emitting layer 105 are prevented from leaking to the hole injection layer 103 and / or the hole transport layer 104 by the electron barrier present at the interface between the light emitting layer 105 and the hole injection layer 103 and / or the hole transport layer 104. As a result, the electrons are accumulated at the interface in the light emitting layer 105, which brings about effects such as improved light emitting efficiency, and an organic electroluminescent device with excellent light emitting performance is obtained.

[0100] The material of the hole injection layer 103 and the hole transport layer 104 has at least one of hole injection property, hole transport property, and electron barrier property. The material of the hole injection layer 103 and the hole transport layer 104 may be either an organic compound or an inorganic substance.

[0101] Specific examples of materials for the hole injection layer 103 and the hole transport layer 104 include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers, conductive polymer oligomers (particularly thiophene oligomers), porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds.

[0102] Among these, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred in terms of good performance of the organic electroluminescent device, and aromatic tertiary amine compounds are particularly preferred.

[0103] Specific examples of aromatic tertiary amine compounds and styrylamine compounds include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'-bis(m-tolyl)-[1,1'-biphenyl]-4,4'-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N'-diphenyl-N,N'- Examples of such compounds include di(4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis(diphenylamino)quadriphenyl, N,N,N-tri(p-tolyl)amine, 4-(di-p-tolylamino)-4'-[4-(di-p-tolylamino)styryl]stilbene, 4-N,N-diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylaminostilbene, N-phenylcarbazole, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD), and 4,4',4''-tris[N-(m-tolyl)-N-phenylamino]triphenylamine (MTDATA).

[0104] Furthermore, inorganic compounds such as p-type Si and p-type SiC can also be given as examples of materials for the hole injection layer 103 and the hole transport layer 104 .

[0105] The hole injection layer 103 and the hole transport layer 104 may have a single structure made of one or more materials, or may have a laminate structure made of multiple layers of the same composition or different compositions.

[0106] [Light-emitting layer 105] Between the hole transport layer 104 and the electron transport layer 106, a light emitting layer 105 is provided.

[0107] Examples of the material of the light-emitting layer 105, that is, the light-emitting material, include phosphorescent materials, fluorescent materials, and thermally activated delayed fluorescent materials. In the light-emitting layer 105, electron-hole pairs are recombined, resulting in light emission.

[0108] The light-emitting layer 105 may consist of a single small molecule or single polymeric material, but more commonly consists of a host material doped with a guest compound. Emission comes primarily from the dopant and can be of any color.

[0109] Examples of the host material include compounds having a biphenylyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, and an anthryl group. More specifically, examples of the compound include DPVBi (4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl), BCzVBi (4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl), TBADN (2-tertiarybutyl-9,10-di(2-naphthyl)anthracene), ADN (9,10-di(2-naphthyl)anthracene), CBP (4,4'-bis(carbazol-9-yl)biphenyl), CDBP (4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl), 2-(9-phenylcarbazol-3-yl)-9-[4-(4-phenylphenylquinazolin-2-yl)carbazole, 9,10-bis(biphenyl)anthracene, and the like.

[0110] Examples of the fluorescent dopant include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium, thiapyrylium compound, fluorene derivative, periflanthene derivative, indenoperylene derivative, bis(azinyl)amine boron compound, bis(azinyl)methane compound, carbostyril compound, boron compound, cyclic amine compound, etc. The fluorescent dopant may be a combination of two or more selected from these.

[0111] Phosphorescent dopants include, for example, complexes of metals such as iridium, platinum, palladium, and osmium.

[0112] Specific examples of fluorescent dopants and phosphorescent dopants include Alq3 (tris(8-quinolinolato)aluminum), DPAVBi (4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl), perylene, bis[2-(4-n-hexylphenyl)quinoline](acetylacetonate)iridium(III), Ir(PPy)3 (tris(2-phenylpyridine)iridium(III)), FIrPic (bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III))), and the like.

[0113] It is also possible to use materials that emit delayed fluorescence, such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, as light-emitting materials.

[0114] Moreover, the light-emitting material is not limited to being contained only in the light-emitting layer 105. For example, the light-emitting material may be contained in a layer adjacent to the light-emitting layer 105 (the hole transport layer 104 or the electron transport layer 106). This can further increase the light-emitting efficiency of the organic electroluminescent device 200.

[0115] The light emitting layer 105 may be a single layer structure made of one or more materials, or may be a laminate structure made of multiple layers of the same composition or different compositions.

[0116] [Electron transport layer 106] Between the light-emitting layer 105 and the electron injection layer 107, an electron transport layer 106 is provided.

[0117] The electron transport layer 106 has a function of transporting electrons injected from the cathode 108 to the light-emitting layer. By interposing the electron transport layer 107 between the cathode 108 and the light-emitting layer 105, electrons are injected into the light-emitting layer 105 at a lower electric field.

[0118] As described above, the electron transport layer 106 preferably contains a charge transport material for an organic electronic device. The electron transport layer 106 may further contain one or more types of electron transport materials selected from conventionally known electron transport materials in addition to the charge transport material for an organic electronic device.

[0119] In addition, when the charge transport material for an organic electronic device is not contained in the electron transport layer 106 but is contained in another layer, one or more types selected from conventionally known electron transport materials can be used as the electron transport material constituting the electron transport layer 106.

[0120] Examples of conventionally known electron transporting materials include alkali metal compounds, alkaline earth metal compounds, transition metal compounds, zinc group element compounds, earth metal compounds, etc. Examples of alkali metal compounds, alkaline earth metal compounds, transition metal compounds, zinc group element compounds, earth metal compounds, etc. include 8-hydroxyquinolinato lithium (Liq), bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, bis(8-hydroxyquinolinato) manganese, tris(8-quinolinolato) aluminum (Alq3), tris(2-methyl-8-hydroxyquinolinato) aluminum, tris( ... bis(2-methyl-8-quinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolate)gallium, bis(2-methyl-8-quinolinato)-1-naphtholatealuminum, and bis(2-methyl-8-quinolinato)-2-naphtholategallium are examples of chelate-type aryloxides.

[0121] Examples of the electron transporting material include triazine derivatives, pyrimidine derivatives, pyridine derivatives, fluoranthene derivatives, fluorenone derivatives, anthraquinodimethane derivatives, diphenoquinone derivatives, thiopyran dioxide derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, perylene tetracarboxylic acid derivatives, fluorenylidenemethane derivatives, anthraquinodimethane derivatives, anthrone derivatives, etc. Among these, a specific example of the triazine derivative is 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine (T2T).

[0122] The electron transport layer 106 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.

[0123] In the organic electroluminescent device 200, an electron injection layer 107 may be provided for the purpose of improving the electron injection property and improving the device characteristics (for example, luminous efficiency, low-voltage driving, or high durability).

[0124] [Electron injection layer 107] An electron injection layer 107 is provided between the electron transport layer 106 and the cathode 108. The electron injection layer 107 has a function of transporting electrons injected from the cathode to the light-emitting layer 105. By providing the electron injection layer between the cathode 108 and the light-emitting layer 105, electrons are injected into the light-emitting layer 105 at a lower electric field.

[0125] Examples of materials for the electron injection layer 107 include organic compounds such as fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, and anthrone.

[0126] Examples of materials for the electron injection layer 107 include inorganic compounds such as various oxides, fluorides, nitrides, and oxynitrides, such as SiO, AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, LiF, C, and Yb.

[0127] [Cathode 108] A cathode 108 is provided on the electron injection layer 107. In the case of an organic EL element configured so that only light emitted through the anode 108 is extracted, the cathode 108 can be formed from any conductive material.

[0128] Examples of materials for the cathode 108 include metals with a small work function (hereinafter also referred to as electron injecting metals), alloys, electrically conductive compounds, and mixtures thereof. Here, the metals with a small work function are, for example, metals with a work function of 4 eV or less.

[0129] Specific examples of materials for the cathode 108 include sodium, sodium-potassium alloys, magnesium, lithium, magnesium / copper mixtures, magnesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al2O3) mixtures, indium, lithium / aluminum mixtures, rare earth metals, and the like.

[0130] Among these, from the standpoint of electron injectability and durability against oxidation, etc., mixtures of an electron injecting metal and a second metal which has a larger and more stable work function than the electron injecting metal, such as a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al2O3) mixture, and a lithium / aluminum mixture, are preferred.

[0131] [How each layer is formed] Each layer except for the electrodes (anode, cathode) described above can be formed into a thin film by a known method such as vacuum deposition, spin coating, casting, LB (Langmuir-Blodgett) method, etc. The material of each layer may be used alone or, if necessary, together with a material such as a binder resin or a solvent.

[0132] There are no particular limitations on the film thickness of each layer thus formed, and it can be appropriately selected depending on the situation, but it is usually in the range of 5 nm to 5 μm.

[0133] The anode 101 and the cathode 108 can be formed by forming an electrode material into a thin film by a method such as vapor deposition, sputtering, etc. 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 or the like after forming a thin film by vapor deposition, sputtering, or the like.

[0134] The film thickness of the anode 101 and the cathode 108 is preferably 1 μm or less, and more preferably 10 nm or more and 200 nm or less.

[0135] In addition, the layer containing the charge transport material for organic electronic devices may be formed in combination with the above-mentioned conventionally known electron transport material. Thus, for example, the charge transport material for organic electronic devices and the conventionally known electron transport material may be co-deposited, or a layer of the conventionally known electron transport material may be laminated on the layer of the charge transport material for organic electronic devices.

[0136] The organic electroluminescent device according to one embodiment of the present invention may be used as a kind of lamp for illumination or exposure light source, or as a projection device that projects an image onto a screen or the like, or as a display device (display) that directly recognizes still images or moving images.

[0137] When the organic electroluminescent element according to one embodiment of the present invention is used as a display device for playing moving images, the driving method may be a simple matrix (passive matrix) method or an active matrix method. In addition, by using two or more kinds of organic electroluminescent elements having different emission colors, a full-color display device can be produced. EXAMPLES

[0138] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0139] [Synthesis Example 1: Synthesis of compound (2-1)] Compound (2-1) was synthesized by the following method. [ka]

[0140] In a 500 mL two-necked round bottom flask equipped with a magnetic stirrer, o-phthalaldehyde (1) (1.07 g, 8.0 mmol), 1,4-Dibenzyl-1H-1,2,4-triazol-4-ium bromide (pre NHC, 528 mg, 1.60 mmol), and 1,2-dichloroethane (DCE, 120 mL) were added under a nitrogen stream. 1,8-Diazabicyclo[5.4.0]-7-undecene (DBU, 0.24 mL, 1.6 mL) was added to the mixture, and the mixture was heated and stirred at 60 °C for 6 hours, after which the solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate / methanol = 10:10:1) to obtain the grayish triol compound (2) as a solid (859 mg, 80% yield). Compound (2) 1 The H-NMR spectrum was identical to that reported in the literature (J. Org. Chem. 2011, 76, 1844.).

[0141] [ka]

[0142] In a 200 mL two-necked round bottom flask equipped with a magnetic stir bar, triol compound (2) (1.02 g, 3.80 mmol), AZADOL (5.9 mg, 0.038 mmol), and CHCl (19 mL) were added under air. To the mixture, a solution of KBr (45.3 mg, 0.400 mmol) dissolved in saturated aqueous NaHCO (3.8 mL) was added at room temperature, and a mixture of 5% aqueous NaOCl (9.5 mL) and saturated aqueous NaHCO (7.6 mL) was added dropwise at 0 °C. A mixture of 5% aqueous NaOCl (9.5 mL) and saturated aqueous NaHCO (7.6 mL) was added dropwise at 0 °C. The mixture was stirred at 0 °C for 30 min, and the reaction was quenched by the addition of saturated aqueous NaSO at 0 °C. After separation of the CHCl layer, the product was extracted from the aqueous layer three times with EtOAc and a minimum amount of THF. The organic layer and the CH2Cl2 layer were combined, the mixture was dried over Na2SO4, and the solvent was removed under reduced pressure on a rotary evaporator. The crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 1:1) to give compound (3) as a white solid (908 mg, yield 90%). 1 HNMR(400MHz,acetone-d6)δ(ppm):7.91(d,J=8.0Hz,2H),7.81(td,J=7.6,1.6Hz,2H),7.68(d,J=7.6Hz,2H),7.61(td,J=7.6,0.8Hz,2H),5.71(brs,2H) 13 CNMR(600MHz,acetone-d6)δ(ppm):201.83,151.17,137.12,134.08,131.90,127.32,124.84,83.25 HRMS(ESI+)m / zcalcd for C 16 H 10 O4Na [M+Na] + : 289.0471, found: 265.0469

[0143] [ka]

[0144] Compound (3) (333 mg, 1.25 mmol) and THF (12.5 mL) were added to a 100 mL two-necked round-bottom flask equipped with a magnetic stir bar under a nitrogen stream. To the mixture, an aqueous solution of NaIO4 (401 mg, 1.89 mmol) dissolved in deionized water (3.8 mL) was added, and the mixture was stirred at room temperature for 1 h. The organic layer was washed with saturated brine, dried over Na2SO4, and the solvent was removed under reduced pressure on a rotary evaporator. The crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 1:1) to obtain bicyclohemiacetal compound (A1) as a white solid (288 mg, 81% yield). 1 HNMR(400MHz,acetone-d6)δ(ppm):7.91(dd,J=8.0,0.8Hz,2H),7.75(td,J=8.4, 1.2Hz,2H),7.68(dd,J=8.4,0.8Hz,2H),7.59(td,J=8.0,1.2Hz,2H),7.26(s,2H) 13 CNMR(600MHz,acetone-d6)δ(ppm):190.14,141.96,135.81,131.34,128.65,127.68,127.43,98.89 HRMS(ESI+)m / z calcd for C 16 H 10 O5Na [M+Na] + :305.0420,found:305.0420

[0145] [ka]

[0146] Bicyclohemiacetal compound (A1) (28.2 mg, 0.100 mmol), o-diaminobenzene (26.0 mg, 0.240 mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 3.8 mg, 0.02 mmol) were added to a screw-top test tube containing a magnetic stirrer, and the tube was closed with a perforated cap with a Teflon septum. The tube was then evacuated and replaced with nitrogen. 1,4-dioxane (1.0 mL) was added to the test tube, and the mixture was heated and stirred at 110 °C in an oil bath for 24 hours. The mixture was then neutralized with a few drops of triethylamine (Et3N) and transferred to a vial using CHCl2. The solvent was removed under reduced pressure using a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 3:2) to obtain compound (2-1) as a pale orange solid (38.6 mg, yield 94%). The sublimation temperature of compound (2-1) was 250°C, and compound (2-1) after sublimation was a colorless powder. 1 HNMR(400MHz,CDCl3)δ(ppm):8.12-8.10(m,4H),7.75-7.72(m,4H),7.56-7.49(m,8H) 13 CNMR(600MHz,CDCl3)δ(ppm):153.46,141.89,138.53,130.46,129.82,129.70,129.53 HRMS(ESI+)m / z calcd for C 28 H 17 N4[M+H] + :409.1448, found 409.1450.

[0147] [Synthesis Example 2: Synthesis of compound (2-2)] [ka]

[0148] In a 100mL two-necked round-bottom flask containing a magnetic stirrer, bicyclohemiacetal compound (A1) (297.4mg, 1.05mmol), 4,5-difluoro-1,2-phenylenediamine (356.8mg, 2.40mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 40.7mg, 0.21mmol) were added, and the flask was closed with a septum, evacuated, and then replaced with nitrogen. 1,4-dioxane (10mL) was added to the flask, and the mixture was heated and stirred at 110℃ in an oil bath for 22 hours. Next, the mixture was neutralized with a few drops of triethylamine (Et3N) and transferred to a 100mL eggplant flask using chloroform. The solvent was removed under reduced pressure using a rotary evaporator, toluene was added, the insoluble matter was filtered, and the filtrate was concentrated again. The crude product was then purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10:1 → 5:1) to obtain compound (2-2) as a pale orange solid (359.8 mg, yield 71%). The sublimation temperature of compound (2-1) was 250°C, and compound (2-2) after sublimation was a colorless powder. 1 HNMR(600Hz,CDCl3):δ(ppm):7.86-7.83.(t,4H),7.58-7.55(m,4H),7.49-7.46(m,4H) 13 CNMR(600MHz,CDCl3)δ(ppm):153.51,152.91(dd,J=259.42,18Hz),139.32(t,J=5.8Hz),137.93,129.96,129.84,115.10(dd,J=13.74,4.98Hz) HRMS(ESI+)m / z calcd for C 28 H 13 F4N4[M+H] + :481.1071,found:481.1078.

[0149] [Synthesis Example 3: Synthesis of compound (2-3)] [ka]

[0150] Bicyclohemiacetal compound (A1) (118.8 mg, 0.42 mmol), 4,5-dichloro-1,2-phenylenediamine (173.7 mg, 0.96 mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 15.1 mg, 0.078 mmol) were added to a screw-top test tube containing a magnetic stirrer, and the tube was closed with a perforated cap with a Teflon septum, and the inside of the tube was evacuated and replaced with nitrogen. 1,4-Dioxane (4.0 mL) was added to the test tube, and the mixture was heated and stirred at 110 °C in an oil bath for 24 hours. The mixture was then neutralized with a few drops of triethylamine (Et3N) and transferred to a vial using chloroform. The solvent was removed under reduced pressure using a rotary evaporator, and ethyl acetate was added to the resulting crude product to dissolve impurities and filter to obtain compound (2-3) as a pale orange solid (151.1 mg, yield 66%). 1 HNMR(600Hz,CDCl3):δ(ppm):8.22(s,4H),7.59-7.56(m,4H),7.48-7.46(m,4H) 13 CNMR(600MHz,CDCl3)δ(ppm):154.27,140.62,137.83,135.34,130.09(2C),129.81 HRMS(ESI+)m / z calcd for C 28 H 13 Cl4N4[M+H] + :544.9889, found:544.9890.

[0151] [Synthesis Example 4: Synthesis of compound (2-4)] [ka]

[0152] Bicyclohemiacetal compound (A1) (119.1 mg, 0.422 mmol), 4,5-dibromo-1,2-phenylenediamine (260.7 mg, 0.961 mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 15.9 mg, 0.082 mmol) were added to a screw-top test tube containing a magnetic stirrer, and the tube was closed with a perforated cap with a Teflon septum. The tube was then evacuated and replaced with nitrogen. 1,4-Dioxane (4.0 mL) was added to the test tube, and the mixture was heated and stirred at 110°C in an oil bath for 24 hours. The mixture was then neutralized with a saturated aqueous solution of sodium bicarbonate, ethyl acetate was added, and the aqueous layer and the organic layer containing impurities were filtered to obtain compound (2-4) as a pale pink solid (176.3 mg, 58% yield). 1 HNMR(600Hz,CDCl3):δ(ppm):8.41(s,4H),7.58-7.56(m,4H),7.48-7.45(m,4H) 13 CNMR(600MHz,CDCl3)δ(ppm):154.34,141.08,137.83,133.52,130.09,129.78,127.42 HRMS(ESI+)m / z calcd for C 28 H 13 Br4N4[M+H] + :720.7868,found:720.7867.

[0153] [Synthesis Example 5: Synthesis of compound (2-7)] [ka]

[0154] Bicyclohemiacetal compound (A1) (29.9 mg, 0.10 mmol) and 4,5-diaminophthalonitrile (39.4 mg, 0.24 mmol) were added to a screw-top test tube containing a magnetic stirrer, and the tube was closed with a perforated cap with a Teflon (registered trademark) septum. The tube was then evacuated and replaced with nitrogen. A 1,4-dioxane solution (1.0 mL) of p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 4.0 mg, 0.21 mmol) was added to the test tube, and the mixture was heated and stirred at 110°C for 46 hours in an oil bath. The precipitated solid was washed with 1,4-dioxane to obtain compound (2-7) as an ocher solid (29.7 mg, 55% yield). 1 HNMR(400Hz,CDCl3):δ(ppm):8.59(s,4H),7.69-7.66(m,4H),7.54-7.50(m,4H) HRMS(ESI+)m / z calcd for C 32 H 12 N8Na [M+Na] + :531.1077,found:531.1079.

[0155] [Synthesis Example 6: Synthesis of compound (2-16)] [ka]

[0156] Bicyclohemiacetal compound (A1) (28.2 mg, 0.100 mmol), 2,3-diaminonaphthalene (38.0 mg, 0.240 mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 3.8 mg, 0.020 mmol) were added to a screw-top test tube containing a magnetic stir bar, and the tube was closed with a perforated cap with a Teflon septum. The tube was then evacuated and replaced with nitrogen. 1,4-dioxane (1.0 mL) was added to the test tube, and the mixture was heated and stirred at 110 °C in an oil bath for 24 hours. The mixture was then neutralized with a few drops of triethylamine (Et3N) and transferred to a vial using CHCl2. The solvent was removed under reduced pressure using a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 7:3) to obtain compound (2-16) as a pale green solid (28.2 mg, yield 55%). 1 HNMR(400Hz,CDCl3):δ(ppm):8.68(s,4H),8.05-8.03(m,4H),7.59(s,8H),7.54-7.50(m,4H) 13 CNMR(600MHz,CDCl3)δ(ppm):154.12,138.63,138.39,129.89,129.81,128.62,128.01,127.07 HRMS(ESI+)m / z calcd for C 36 H 21 N4[M+H] + :509.1761,found:509.1764.

[0157] [Synthesis Example 7: Synthesis of compound (2-17)] [ka]

[0158] Bicyclohemiacetal compound (A3) (36.4 mg, 0.0498 mmol), 2,3-diaminonaphthalene (19.3 mg, 0.120 mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 2.2 mg, 11 μmol) were placed in a screw-top test tube containing a magnetic stirrer, and the tube was closed with a perforated cap with a Teflon septum. The tube was then evacuated and replaced with nitrogen. 1,4-Dioxane (0.50 mL) was placed in the test tube and heated and stirred at 110°C in an oil bath for 24 hours. The mixture was then transferred to a vial using chloroform. The solvent was removed under reduced pressure using a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 19:1) to obtain compound (2-17) as a yellow solid (18.1 mg, 38% yield). 1 HNMR(400Hz,CDCl3):δ(ppm):8.66(s,4H),8.03-8.01(m,4H),7.51-7.49(m,4H),7.32( s,4H),2.72-2.65(m,8H),1.67-1.63(m,8H),1.40-1.28(m,40H),0.88(t,J=5.7Hz,12H) HRMS(ESI+)m / z calcd for C 68 H 84 N4Na [M+Na] + :979.6588,found:979.6584.

[0159] [Synthesis Example 8: Synthesis of compound (2-18)] [ka]

[0160] Bicyclohemiacetal compound (A3) (36.7 mg, 0.0502 mmol), o-diaminobenzene (13.6 mg, 0.122 mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 2.0 mg, 10 μmol) were placed in a screw-top test tube with a magnetic stirrer, and the tube was closed with a perforated cap with a Teflon septum. The tube was evacuated and then replaced with nitrogen. 1,4-dioxane (0.50 mL) was placed in the test tube and heated and stirred at 110°C in an oil bath for 24 hours. The mixture was then transferred to a vial using chloroform. The solvent was removed under reduced pressure using a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 19:1) to obtain compound (2-18) as a pale yellow solid (34.3 mg, 80% yield). 1 HNMR(400Hz,CDCl3):δ(ppm):8.10-8.07(m,4H),7.70-7.67(m,4H),7.24(s,4H), 2.70-2.62(m,8H),1.63-1.60(m,8H),1.37-1.27(m,40H),0.87(t,J=6.1Hz,12H) HRMS(ESI+)m / z calcd for C 60 H 84 N4Na [M+Na] + :879.6275,found:879.6265.

[0161] [Synthesis Example 9: Synthesis of compound (2-19)] [ka]

[0162] Bicyclohemiacetal (A3) (36.2 mg, 0.0495 mmol), 4,5-difluoro-1,2-phenylenediamine (18.0 mg, 0.121 mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 2.1 mg, 11 μmol) were placed in a screw-top test tube with a magnetic stir bar, and the tube was closed with a perforated cap with a Teflon septum. The tube was then evacuated and replaced with nitrogen. 1,4-Dioxane (0.50 mL) was placed in the test tube and heated and stirred at 110°C in an oil bath for 24 hours. The mixture was then transferred to a vial using chloroform. The solvent was removed under reduced pressure using a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 9:1 to 4:1) to obtain compound (2-19) as a yellow viscous oil (40.3 mg, yield 88%). 1 HNMR(400Hz,CDCl3):δ(ppm):7.82(t,J=9.3Hz,4H),7.22(s,4H),2.70-2.59(m,8H),1.63-1.59(m,8H),1.38-1.27(m,40H),0.88(t,J=5.7Hz,12H) HRMS(ESI+)m / z calcd for C 60 H 76 N4Na [M+Na] + :951.5898,found:951.5896.

[0163] [Synthesis Example 10: Synthesis of compound (2C-1)] [ka]

[0164] Compound (2-2) (120.4 mg, 0.251 mmol) synthesized in Synthesis Example-2, a dimethylformamide (5.0 mL) solution of 1,2-benzenedithiol (205.8 mg, 1.375 mmol), and potassium carbonate (138.5 mg, 1.002 mmol) were placed in a microwave reaction vessel containing a magnetic stirrer, and the vessel was closed with a Teflon septum-equipped cap for microwave reaction. The vessel was heated and stirred at 120°C for 1.5 hours under microwave irradiation. Next, the mixture was transferred to a vial using chloroform, and the solvent was distilled off under reduced pressure using a rotary evaporator. Water and chloroform were added for extraction, and the organic layer was extracted using ethyl acetate. Sodium sulfate was then added, filtered, and the solvent was distilled off under reduced pressure using a rotary evaporator. The resulting crude product was washed with hexane and then purified by silica gel column chromatography (eluent: hexane / chloroform=4:1 to chloroform) to obtain compound (2C-1) as a yellow solid (157.8 mg, yield 92%). 1 HNMR(400Hz, acetone-d6): δ(ppm):8.13(s,4H),7.62-7.53(m,12H),7.40-7.35(m,4H) HRMS(ESI+)m / z calcd for C 40 H 20 N4S4Na [M+Na] + :707.0463,found:707.0463.

[0165] [Synthesis Example 11: Synthesis of compound (4-1)] [ka]

[0166] Bicyclohemiacetal compound (A2) (152.8 mg, 0.40 mmol) and o-diaminobenzene (106.8 mg, 0.96 mmol) were added to a screw-top test tube containing a magnetic stirrer, and the tube was closed with a perforated cap with a Teflon septum. The tube was then evacuated and replaced with nitrogen. A 1,4-dioxane solution (4.0 mL) of p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 15.4 mg, 0.079 mmol) was added to the test tube, and the mixture was heated and stirred at 110°C for 24 hours in an oil bath. The mixture was then neutralized with saturated aqueous sodium bicarbonate and extracted with ethyl acetate. The organic layer was dried over Na2SO4, the solvent was removed under reduced pressure using a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 3:2) to obtain compound (4-1) as a pale orange solid (187.6 mg, yield 92%). 1 HNMR(600Hz,CDCl3):δ(ppm):8.18-8.15(m,4H),8.00(s,4H),7.88-7.86(m,4H),7.79-7.76(m,4H),7.52-7.50(m,4H) 13 C NMR(600MHz,CDCl3)δ(ppm):153.84,142.03,136.20,133.45,130.54,129.62,129.57,128.32,127.39 HRMS(ESI+)m / z calcd for C 36 H 21 N4[M+H] + :509.1761,found:509.1764.

[0167] [Synthesis Example 12: Synthesis of compound (4-2)] [ka]

[0168] Bicyclohemiacetal compound (A2) (153.1 mg, 0.400 mmol), 4,5-difluoro-1,2-phenylenediamine (142.4 mg, 0.958 mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 23.1 mg, 0.119 mmol) were placed in a screw-top test tube containing a magnetic stirrer, and the tube was closed with a perforated cap with a Teflon septum. The tube was then evacuated and replaced with nitrogen. 1,4-dioxane (4.0 mL) was placed in the test tube and heated and stirred in an oil bath at 110°C for 24 hours. The mixture was then neutralized with a saturated aqueous solution of sodium bicarbonate and extracted with ethyl acetate. Sodium sulfate was added and filtered, the solvent was removed under reduced pressure using a rotary evaporator, chloroform was added, insoluble matter was filtered, and the filtrate was concentrated again. The crude product was then purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10:1 to 6:1) to obtain compound (4-2) as a pale yellow solid (184.7 mg, yield 80%). 1 HNMR(400Hz,CDCl3):δ(ppm):7.97(s,4H),7.92-7.86(m,8H),7.55-7.52(m,4H)HRMS(ESI+)m / z calcd for C 36 H 16 F4N4Na [M+Na] + :603.1203,found:603.1207.

[0169] [Synthesis Example 13: Synthesis of compound (4-4)] [ka]

[0170] Bicyclohemiacetal compound (A2) (152.9 mg, 0400 mmol), 2,3-diaminonaphthalene (152.0 mg, 0.942 mmol), and p-toluenesulfonic acid monohydrate (p-TsOH·H2O, 16.0 mg, 82 μmol) were placed in a screw-top test tube containing a magnetic stirrer, and the tube was closed with a perforated cap with a Teflon septum. The tube was then evacuated and replaced with nitrogen. 1,4-dioxane (4.0 mL) was placed in the test tube and heated and stirred at 110°C in an oil bath for 24 hours. The mixture was then neutralized with a saturated aqueous solution of sodium bicarbonate and ethyl acetate was added. At that time, a portion of compound (4-4) that precipitated as an insoluble solid was filtered off, and the majority of compound (4-4) dissolved in the organic layer was extracted with ethyl acetate. Thereafter, sodium sulfate was added and the mixture was filtered, the solvent was removed under reduced pressure using a rotary evaporator, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 6:1 to 3:2) and combined with the previously precipitated solid to obtain compound (4-4) as a yellow solid (113.6 mg, yield 47%). 1 HNMR(400Hz,CDCl3):δ(ppm):8.73(s,4H),8.08(s,4H),8.08-8.05(m,4H),7.92-7.89(m,4H),7.55-7.52(m,8H) HRMS(ESI+)m / z calcd for C 44 H 24 N4Na [M+Na] + :631.1893,found:631.1895.

[0171] [Element Example 1: Preparation of an organic electroluminescent element using compound (2-1)] As shown in FIG. 3 , an organic electroluminescent device 300 was fabricated having a layered structure consisting of a substrate 101, an anode 102, a hole injection layer 103, a first hole transport layer 1041, a second hole transport layer 1042, an emitting layer 105, a first electron transport layer 1061, a second electron transport layer 1062, an electron injection layer 107, and a cathode 108. As the luminescent characteristics of the organic electroluminescent device, the current efficiency and the device lifetime were evaluated.

[0172] (Preparation of substrate 101 and anode 102) A glass substrate with an indium-tin oxide (ITO) transparent electrode, on which a 2 mm wide ITO film (thickness: 110 nm) was patterned in stripes, was prepared as a substrate with an anode on its surface. The substrate was then washed with isopropyl alcohol and then subjected to surface treatment with ozone ultraviolet cleaning.

[0173] (Preparation for vacuum deposition) After cleaning and surface treatment, each layer was deposited by vacuum deposition on the substrate by vacuum deposition, so that each layer was laminated. First, the glass substrate was placed in a vacuum deposition chamber and 1.0×10 -4 The pressure was reduced to 10 Pa. Then, each layer was formed according to the film formation conditions in the following order.

[0174] (Fabrication of Hole Injection Layer 103) Sublimation-purified N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (α-NPD) and NDP-9 (Novaled) were mixed in a ratio of 97:3 (mass ratio) to form a 10 nm film, thereby producing a hole injection layer 103. The film formation rate was 0.18 nm / sec.

[0175] (Preparation of the first hole transport layer 1041) Sublimation-purified α-NPD was formed into a film of 30 nm at a rate of 0.15 nm / sec to form a first hole transport layer 1041 .

[0176] (Preparation of second hole transport layer 1042) Sublimation-purified 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) was formed into a film of 10 nm at a rate of 0.15 nm / sec to prepare a second hole transport layer 1042 .

[0177] (Fabrication of the light-emitting layer 105) Sublimation-purified CBP and (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) were mixed in a ratio of 95:5 (mass ratio) to form a 20 nm film, thereby producing the light-emitting layer 105. The film formation rate was 0.18 nm / sec.

[0178] (Preparation of the first electron transport layer 1061) A first electron transport layer 1061 was prepared by depositing 2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine (T2T) purified by sublimation at a rate of 0.15 nm / sec to a thickness of 10 nm.

[0179] (Preparation of second electron transport layer 1062) The synthesized compound (2-1) and 8-hydroxyquinolinato lithium (Liq) were mixed in a ratio of 50:50 (mass ratio) to form a film of 25 nm, thereby producing a second electron transport layer 1062. The film formation rate was 0.15 nm / sec.

[0180] (Fabrication of Electron Injection Layer 107) Liq was deposited at a rate of 0.05 nm / sec to a thickness of 2 nm to form the electron injection layer 107 . (Preparation of cathode 108) Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and the cathode 108 was formed. The cathode had a two-layer structure, with silver / magnesium (mass ratio 1 / 9) and silver being formed in that order to thicknesses of 80 nm and 20 nm, respectively. The silver / magnesium film formation rate was 0.5 nm / sec, and the silver film formation rate was 0.2 nm / sec.

[0181] As a result, the light-emitting area of ​​4 mm2 shown in Figure 3 2 Thus, an organic electroluminescent device 300 was produced. The thickness of each film was measured using a stylus film thickness measuring instrument (DEKTAK, manufactured by Bruker).

[0182] Furthermore, this element was sealed in a nitrogen atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less by sealing a glass sealing cap and the film-formed substrate (element) with bisphenol F type epoxy resin (manufactured by Nagase ChemteX Corporation).

[0183] A direct current was applied to the organic electroluminescent device fabricated as described above, and the light-emitting characteristics were evaluated using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse). 2 The current efficiency (cd / A) was measured when current was passed through the device, and the device life (h) was measured when the device was continuously lit. The device life (h) was measured when the device was lit at an initial brightness of 2000 cd / m 2 The luminance decay time was measured when the device was continuously lit when driven at 1000 Hz, and the luminance (cd / m 2 The time required for the value of the concentration to decrease by 10% was measured.

[0184] The voltage, current efficiency, and element life are relative values ​​with the results of element comparative example 1 taken as the reference value (100). The obtained measurement results are shown in Table 1.

[0185] [Comparative element example 1] Organic EL devices were prepared in the same manner as in Device Example 1, except that tris(8-quinolinolato)aluminum (Alq3) was used instead of compound (2-1) in Device Example 1, and were evaluated. The measurement results are shown in Table 1.

[0186] [ka]

[0187] [Table 1]

[0188] The fused ring compound (1) according to one embodiment of the present invention can be suitably used not only for thermally activated delayed fluorescence (TADF) but also for conventional fluorescent device applications and organic electroluminescent devices using phosphorescent devices.

[0189] [Element Example 2: Preparation of a photoelectric conversion element for an image sensor using compound (2-1)] As shown in FIG. 1, a photoelectric conversion element 100 for an imaging device was fabricated having a layered structure consisting of a substrate 1, a lower electrode 2, an electron transport layer (hole blocking layer) 3, a photoelectric conversion layer 4, a hole transport layer (electron blocking layer) 5, a buffer layer 6, and an upper electrode 7, and the dark current and external quantum efficiency of the photoelectric conversion element were evaluated.

[0190] (Preparing substrate 1 and lower electrode 2) A glass substrate with an indium-tin oxide (ITO) transparent electrode, on which a 2 mm wide ITO film (thickness 110 nm) was patterned in stripes, was prepared as a substrate with a lower electrode on its surface. The substrate was then washed with isopropyl alcohol and then subjected to surface treatment by ozone ultraviolet cleaning.

[0191] (Preparation for vacuum deposition) After cleaning and surface treatment, each layer was deposited by vacuum deposition on the substrate by vacuum deposition, so that each layer was laminated. First, the glass substrate was placed in a vacuum deposition chamber and 7.0×10 -5 The pressure was reduced to 10 Pa. Then, each layer was formed according to the film formation conditions in the following order.

[0192] (Preparation of Electron Transport Layer (Hole Blocking Layer) 3) The sublimation-purified compound (2-1) was formed into a film having a thickness of 15 nm at a speed of 0.10 nm / sec to prepare an electron transport layer (hole blocking layer) 3.

[0193] (Fabrication of Photoelectric Conversion Layer 4) A film of 120 nm was formed by mixing N,N-dimethylquinacridone and C60 in a ratio of 4:1 (mass ratio) to prepare photoelectric conversion layer 4. The film formation rate was 0.15 nm / sec.

[0194] (Preparation of Hole Transport Layer (Electron Blocking Layer) 5) The sublimation purified compound (ic-3) was formed into a film of 10 nm at a rate of 0.10 nm / sec to prepare a hole transport layer 5.

[0195] (Fabrication of Buffer Layer 6) A sublimation-purified compound, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), was deposited to a thickness of 10 nm at a rate of 0.10 nm / sec to form a buffer layer 6.

[0196] (Fabrication of upper electrode 7) Finally, a metal mask was placed so as to be perpendicular to the ITO stripes on the substrate, and the upper electrode 7 was formed. Specifically, a silver film was formed to a thickness of 80 nm at a speed of 0.1 nm / sec, to fabricate the upper electrode 7.

[0197] As a result, the area of ​​4 mm2 shown in Fig. 1 2 The photoelectric conversion element 100 for an imaging device was produced. The film thickness of each film was measured using a stylus film thickness meter (DEKTAK, manufactured by Bruker).

[0198] Furthermore, this element was sealed in a nitrogen atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less by sealing a glass sealing cap and the film-formed substrate (element) with bisphenol F type epoxy resin (manufactured by Nagase ChemteX Corporation).

[0199] The current in the dark (dark current) and external quantum efficiency were evaluated when a voltage of 2.6 V was applied to the photoelectric conversion element for image sensors fabricated as described above. The dark current was measured using a Keithley Source Measure Unit 2636B. The external quantum efficiency was measured using a solar cell spectral response measurement device (Soma Optical Co., Ltd.). The wavelength of the irradiated light was 560 nm, and the intensity was 50 μW / cm. 2 The results are shown in Table 2.

[0200] [Comparative element example 2] In the preparation of the electron transport layer (hole blocking layer) 3 of the element example 2, except that 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine (ETM-1) was used instead of the compound (2-1), the photoelectric conversion element for the image pickup element of the element comparative example 2 was prepared in the same manner as in the element example 2, and the dark current and external quantum efficiency were measured in the same manner as in the element example 2. The results are shown in Table 2.

[0201] In Table 2, the dark current and external quantum efficiency of Element Example 1 are relative values ​​when the dark current and external quantum efficiency of Element Comparative Example 2 are set as reference values ​​(1.0) and (100), respectively.

[0202] [Table 2]

[0203] As can be seen from Table 2, the material for a photoelectric conversion element for an imaging element containing the Example compound according to one embodiment of the present invention exhibited a smaller dark current than the material for a photoelectric conversion element containing the Comparative Example compound. [Explanation of symbols]

[0204] 1 Board 2 Lower electrode 3 Electron transport layer (hole blocking layer) 4 Photoelectric conversion layer 5 Hole transport layer (electron blocking layer) 6 Buffer layer 7 Upper electrode 100 Photoelectric conversion element 101 Substrate 102 Anode 103 Hole injection layer 104 Hole transport layer 105 Light-emitting layer 106 Electron transport layer 107 Electron injection layer 108 Cathode 200 Organic electroluminescent device 1041 First hole transport layer 1042 Second hole transport layer 1061 First electron transport layer 1062 Second electron transport layer 300 Organic electroluminescent device

Claims

1. A fused ring compound represented by the following formula (1): 【Chemistry 1】 (In formula (1), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents a hydrogen atom or a substituent, and adjacent R １ ~R １２ may be bonded to each other to form a ring.)

2. The R １ , R ４ , R ５ and R ８ The fused ring compound according to claim 1 , wherein is a hydrogen atom.

3. The combination which may be bonded to each other to form a ring is R ２ and R ３ , R ６ and R ７ , R ９ and R １０ , and R １１ and R １２ The fused ring compound according to claim 1 or 2, which is a combination of one or more pairs selected from the group consisting of:

4. The substituents each independently represent Deuterium atom; fluorine atom, chlorine atom, bromine atom, iodine atom; A trifluoromethyl group, a pentafluoroethyl group; Cyano group; Nitro group; Hydroxyl group; Thiol group; an optionally substituted aromatic hydrocarbon group; an optionally substituted heteroaromatic group; an optionally substituted arylamino group; an optionally substituted phosphine oxide group; a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms; A linear or branched alkyl group having 1 to 18 carbon atoms; A linear or branched alkoxy group having 1 to 18 carbon atoms; or The fused ring compound according to claim 1 or 2, which is a trifluoromethylsulfonyloxy group.

5. A fused ring compound represented by the following formula (2), (3) or (4): 【Chemistry 2】 (In formulas (2) to (4), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents a hydrogen atom or a substituent, and adjacent R １ ~R １２ do not combine with each other to form a ring. ａ , R ｂ , R ｃ , R ｄ , R ｅ , R ｆ , R ｇ , R ｈ , R ｉ , R ｊ , R ｋ , R ｌ , R ｍ , R ｎ , R о , and R ｐ each independently represents a hydrogen atom or a substituent, and adjacent R ｂ and R ｃ and R ｆ and R ｇ may be bonded to each other to form a ring.)

6. The fused ring compound according to claim 5 , wherein the fused ring compound represented by formula (2) is any one of the following formulas (2A), (2B) and (2C): 【Chemistry 3】 (In formulas (2A) to (2C), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ａ , R ｄ , R ｅ , R ｈ , R ｑ , R ｒ , R ｓ , R ｔ , R ｕ , R ｖ , R ｗ and R ｘ each independently represents a hydrogen atom or a substituent.

7. A method for producing a fused ring compound represented by formula (1), comprising reacting a compound represented by formula (A) below with either or both of compounds represented by formulas (B) and (C) below: 【Chemistry 4】 (In formulas (A) to (C), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents a hydrogen atom or a substituent, and adjacent R １ ~R １２ may be bonded to each other to form a ring.)

8. The method according to claim 7, wherein the compounds represented by formulae (A), (B) and (C) are represented by the following formulae (A1), (B1) and (C1), respectively. 【Chemistry 5】 (In the formula, R １ , R ４ , R ５ and R ８ each independently represents a hydrogen atom or a substituent; R ａ , R ｂ , R ｃ , R ｄ , R ｅ , R ｆ , R ｇ , R ｈ , R ｉ , R ｊ , R ｋ , R ｌ , R ｍ , R ｎ , R о and R ｐ each independently represents a hydrogen atom or a substituent, and adjacent R ｂ and R ｃ , and R ｆ and R ｇ may be bonded to each other to form a ring.)

9. A charge transport material for an organic electronic device, comprising a fused ring compound represented by the following formula (1): 【Chemistry 6】 (In formula (1), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ and R １２ each independently represents a hydrogen atom or a substituent, and adjacent R １ ~R １２ may be bonded to each other to form a ring.)

10. The R １ , R ４ , R ５ and R ８ The charge transport material for an organic electronic device according to claim 9 , wherein is a hydrogen atom.

11. The combination which may be bonded to each other to form a ring is R ２ and R ３ , R ６ and R ７ , R ９ and R １０ , and R １１ and R １２ The charge transport material for an organic electronic device according to claim 10, which is a combination of one or more groups selected from the group consisting of:

12. The substituents each independently represent Deuterium atom; fluorine atom, chlorine atom, bromine atom, iodine atom; A trifluoromethyl group, a pentafluoroethyl group; Cyano group; Nitro group; Hydroxyl group; Thiol group; an optionally substituted aromatic hydrocarbon group; an optionally substituted heteroaromatic group; an optionally substituted arylamino group; an optionally substituted phosphine oxide group; a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms; A linear or branched alkyl group having 1 to 18 carbon atoms; A linear or branched alkoxy group having 1 to 18 carbon atoms; or The charge transport material for an organic electronic device according to claim 9, which is a trifluoromethylsulfonyloxy group.

13. The charge transport material for an organic electronic device according to any one of claims 9 to 12, which is a material for a photoelectric conversion device or an organic EL device.

14. The charge transport material for an organic electronic device according to claim 13, which is a vapor deposition material.

15. An organic electronic device comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, the organic layer comprising the charge transport material for organic electronic devices according to any one of claims 9 to 12.

16. The organic electronic device according to claim 15 , which is a photoelectric conversion device or an organic EL device.

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