TWI755844B - Charge generating layer and method for producing the same, organic electroluminescence device, display device, lighting system, and organic thin film solar cell - Google Patents

Abstract

The subject of the present invention is to provide a charge generation layer that can be produced by co-evaporation and is not easily degraded even in the presence of oxygen or moisture, and the solution is to provide a charge generation layer (10), the charge generation layer ( 10) comprising: a layer (1) comprising a hole-transporting material and an electron-accepting material; and a layer (2) comprising an electron-transporting material and an electron-donating material, the electron-accepting material comprising a material selected from the group consisting of fluorine, Materials for substituents in chlorine, cyano, nitro, and carbonyl groups, wherein the electron-donating material is selected from tertiary amines with an acid dissociation constant pKa of 1 or more, phosphazene compounds, guanidine compounds, and heterocyclic compounds containing an amidine structure A compound, a hydrocarbon compound having a ring structure, a phenanthroline-based compound, a terpyridine-based compound, and a cyclic pyridine-based compound, and the charge generating layer (10) does not contain an alkali metal or a metal oxide.

Description

Charge generation layer and method for producing the same, organic electroluminescent element, display device, lighting device, and organic thin film solar cell

The present invention relates to a charge generation layer and a method for producing the same, organic electroluminescence (hereinafter, electroluminescence (electroluminescence) may be referred to as "EL" in some cases.) element, display device, lighting device, and Organic thin film solar cells.

The organic EL element is a self-luminous type, and has the characteristics of wide viewing angle, excellent visibility, low-voltage driving, thinning and weight reduction by surface emission, and multi-color display. Therefore, the organic EL element can be applied to display devices such as displays and lighting devices. In addition, as a device using an organic thin film, like an organic EL element, an organic thin film solar cell is known.

Recently, assembling a charge generating layer in an organic EL element has been studied (Patent Document 1 to Patent Document 3). By using the charge generating layer, electrons and holes can be injected (generated) into the element without depending on the work function of the electrodes. In addition, as an organic EL element, an organic EL element having a tandem structure including a plurality of light-emitting layers between a cathode and an anode has been studied (Non-Patent Document 1 to Non-Patent Document 6). By fabricating the organic EL element of the tandem structure using the charge generating layer, the current efficiency of the device can be improved and the lifetime of the device can be increased. Conventionally, an organic material, an alkali metal or metal oxide as an inorganic material, or a metal complex containing an alkali metal has been used for the charge generation layer. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 6488082 [Patent Document 2] Japanese Patent No. 6486624 [Patent Document 3] Japanese Patent No. 6479152 [Non-patent literature]

[Non-Patent Document 1] <<Applied Physics Letters>>97, 063303 (2010). [Non-Patent Document 2] <<Applied Physics Express>>11, 022101 (2018). [Non-Patent Document 3] <<Advanced Materials>>, 26, 5864-5868 (2014). [Non-Patent Document 4] <<Advanced Functional Materials>>, 20, 1797-1802 (2010). [Non-Patent Document 5] URL: https://pubs.rsc.org/en/content/articlelanding/2018/TC/c7tc05082h#! divAbstract [Non-Patent Document 6] URL: https://www.sciencedirect.com/science/article/pii/S1566119917305323

[The problem to be solved by the invention] However, when an organic material and an alkali metal as an inorganic material are used for the charge generating layer, in many vacuum apparatuses for device manufacturing, since the vacuum chambers for film formation of the organic material and the inorganic material are different, it is difficult to share the same. Evaporation of organic materials and alkali metals. In addition, when an organic material and an alkali metal are laminated, exchange between vacuum chambers is also required, and the number of steps required for production increases. In addition, since alkali metals are easily degraded in the presence of oxygen or moisture, they are not suitable for device formation on flexible substrates.

In addition, even in the case where an organic material and a metal oxide as an inorganic material are used in the charge generating layer, as described above, in many vacuum apparatuses for device manufacturing, the vacuum for film-forming the organic material and the inorganic material is required. Since the chambers are different, it is also difficult to co-evaporate organic materials and metal oxides. In addition, when an organic material and a metal oxide are laminated, exchange between vacuum chambers is also required, and the number of steps required for production increases.

In addition, when an organic material and a metal complex containing an alkali metal are used in the charge generating layer, the vacuum chamber is common, so co-evaporation is easy, but a film containing a metal complex containing an alkali metal is mixed It is easily degraded in the presence of oxygen or moisture, so it is not suitable for device formation on flexible substrates.

Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a charge generation layer that can be produced by co-evaporation and is not easily degraded even in the presence of oxygen or moisture, and a method for producing the same. In addition, a further object of the present invention is to provide an organic EL element, a display device, a lighting device, and an organic thin-film solar cell that are easy to manufacture and hardly deteriorate even in the presence of oxygen or moisture. [Means of Solving Problems]

The gist of the present invention to solve the above-mentioned problems is structured as follows.

The charge generating layer of the present invention is a charge generating layer including a layer containing a hole transport material and an electron accepting material and a layer containing an electron transport material and an electron donating material, wherein The electron-accepting material is a material containing a substituent selected from the group consisting of fluorine, chlorine, cyano, nitro, and carbonyl, The electron-donating material is selected from the group consisting of tertiary amines with an acid dissociation constant pKa of 1 or more, phosphazene compounds, guanidine compounds, heterocyclic compounds containing an amidine structure, hydrocarbon compounds having a ring structure, phenanthroline compounds, and terpyridines series compounds, cyclic pyridine series compounds, and The charge generation layer does not contain alkali metals and metal oxides. The charge generating layer of the present invention can be produced by co-evaporation, and is not easily degraded even in the presence of oxygen or moisture.

In a preferred example of the charge generation layer of the present invention, the layer containing the hole transport material and the electron accepting material and the layer containing the electron transport material and the electron donating material are directly laminated. In this case, the number of steps required for manufacture can be further reduced.

Preferably, the charge generating layer of the present invention further includes a layer containing only the electron-accepting material or the electron-donating material, The layer containing the hole-transporting material and the electron-accepting material and the layer containing the electron-transporting material and the electron-donating material are laminated via the layer containing only the electron-accepting material or the electron-donating material . In this case, the charge generation layer can also be produced by co-evaporation, and the produced charge generation layer is not easily degraded even in the presence of oxygen or moisture.

In another preferred example of the charge generation layer of the present invention, the free potential of the hole transport material is less than 5.7 eV, The electron-accepting material is an organic substance capable of forming a charge transfer complex by redox reaction with the hole-transporting material, The electron-donating material is an organic substance capable of forming a hydrogen bond with the electron-transporting material. In this case, electrons can be efficiently transferred from the layer containing the hole-transporting material and the electron-accepting material to the layer containing the electron-transporting material and the electron-donating material, and can be efficiently transferred to the layer having the charge generating material inject electrons into the element.

In addition, the method for producing a charge generation layer of the present invention is a method for producing the charge generation layer, comprising: a step of co-evaporating the hole transport material and the electron accepting material to form a layer comprising the hole transport material and the electron accepting material; and A step of co-evaporating an electron transporting material and an electron donating material to form a layer containing the electron transporting material and the electron donating material. According to this method of manufacturing a charge generating layer, the charge generating layer can be efficiently manufactured with a small number of steps.

A preferred form of the organic electroluminescent element of the present invention is an organic electroluminescent element including a cathode, a light-emitting layer and an anode in sequence, wherein including the charge generation layer between the cathode and the light emitting layer, the layer containing the hole transport material and the electron accepting material is arranged on the cathode side, The layer containing the electron-transporting material and the electron-donating material is arranged on the light-emitting layer side. The organic electroluminescent element is easy to manufacture and is not easily degraded even in the presence of oxygen or moisture.

Another preferred form of the organic electroluminescent element of the present invention is an organic electroluminescent element comprising a cathode, a light-emitting layer and an anode in sequence, wherein, including the charge generation layer between the anode and the light emitting layer, the layer containing the hole transport material and the electron accepting material is arranged on the light emitting layer side, The layer containing the electron-transporting material and the electron-donating material is arranged on the anode side. The organic electroluminescent element is also easy to manufacture and is not easily degraded even in the presence of oxygen or moisture.

Another preferred form of the organic electroluminescent element of the present invention includes a cathode and an anode, and includes two or more light-emitting layers between the cathode and the anode, and The charge generation layer is included between one of the light-emitting layers and the other of the light-emitting layers. The organic electroluminescent element is also easy to manufacture and is not easily degraded even in the presence of oxygen or moisture.

The display device of the present invention includes the organic electroluminescent element. The display device is easy to manufacture and does not deteriorate easily even in the presence of oxygen or moisture.

The lighting device of the present invention includes the organic electroluminescent element. The lighting device is easy to manufacture and is not easily degraded even in the presence of oxygen or moisture.

The organic thin film solar cell of the present invention includes the charge generation layer. The organic thin film solar cell is easy to manufacture and is not easily degraded even in the presence of oxygen or moisture. [Effect of invention]

ADVANTAGE OF THE INVENTION According to this invention, it can manufacture by co-evaporation, and can provide the charge generation layer which does not deteriorate easily even in presence of oxygen or moisture, and its manufacturing method. In addition, according to the present invention, it is possible to provide an organic EL element, a display device, a lighting device, and an organic thin-film solar cell which are easy to manufacture and hardly deteriorate even in the presence of oxygen or moisture.

Hereinafter, the charge generating layer and its manufacturing method, organic electroluminescent element, display device, lighting device, and organic thin-film solar cell of the present invention will be described in detail based on embodiments thereof.

<Charge generation layer> 1 is a schematic cross-sectional view for explaining one embodiment of the charge generation layer of the present invention, and FIG. 2 is a schematic cross-sectional view for explaining another embodiment of the charge generation layer of the present invention.

The charge generation layer 10 shown in FIGS. 1 and 2 includes: a layer (hereinafter, sometimes referred to as a “p-doped layer”) 1 containing a hole transport material and an electron accepting material; and an electron transport material and a layer of electron-donating material (hereinafter sometimes referred to as “n-doped layer”) 2, and the charge generating layer 10 shown in FIG. 2 further includes a layer containing only an electron-accepting material or an electron-donating material (hereinafter , sometimes referred to as "dopant layer") 3.

Furthermore, the charge generating layer of the present invention can be directly laminated with the p-doped layer 1 and the n-doped layer 2 like the charge generating layer 10 shown in FIG. Generally, the p-doped layer 1 and the n-doped layer 2 are laminated through the dopant layer 3 . When the p-doped layer 1 and the n-doped layer 2 are directly laminated, the number of steps required for manufacturing can be further reduced. In addition, even in the case where the p-doped layer 1 and the n-doped layer 2 are laminated via the dopant layer 3, the charge generation layer 10 can be produced by co-evaporation, and the produced charge generation layer 10 can be It also does not deteriorate easily in the presence of oxygen or moisture.

Here, in the charge generation layer 10 of the present embodiment, the electron-accepting material is a material containing a highly electronegative substituent selected from the group consisting of fluorine, chlorine, cyano, nitro, and carbonyl. In addition, in the charge generating layer 10 of the present embodiment, the electron-donating material is selected from the group consisting of tertiary amines having an acid dissociation constant pKa of 1 or more, phosphazene compounds, guanidine compounds, heterocyclic compounds containing an amidine structure, Structured hydrocarbon compounds, phenanthroline compounds, terpyridine compounds, and cyclic pyridine compounds. In addition, the charge generation layer 10 of the present embodiment is characterized in that it does not contain an alkali metal or a metal oxide. In addition, "alkali metal-free" includes not only elemental alkali metal, but also an alkali metal-free alloy and an alkali metal compound (for example, an alkali metal-containing complex, etc.).

Since the charge generation layer 10 of the present embodiment contains neither an alkali metal nor a metal oxide, and is formed of only an organic material, for example, when the charge generation layer 10 is fabricated in a vacuum chamber, it is easy to use only an organic vapor deposition chamber. It is easy to use as a material for a layer constituting an organic EL element and the like, with few restrictions on the process. In addition, since the charge generation layer 10 of the present embodiment does not use a complex containing an alkali metal, the resistance to oxygen and moisture is also high, and it can be easily produced on a flexible substrate. In addition, although the charge generation layer 10 of this embodiment can be manufactured by vapor deposition, it can be formed not only by vapor deposition, but also by coating. Therefore, the charge generation layer 10 of the present embodiment can be produced by co-evaporation, and is less likely to deteriorate even in the presence of oxygen or moisture.

Next, referring to FIGS. 3 and 4 , taking electron injection into the organic EL element shown in FIG. 11 as an example, the charge generation mechanism and dopants (electron-accepting materials, electron-donating materials, electron-donating materials) in the charge generating layer 10 of this embodiment will be discussed material) will be explained. Furthermore, the organic EL element shown in FIG. 11 will be described in detail in the item <Organic EL element>.

FIG. 3 is an explanatory diagram of the energy level of the charge generation layer to which the dopant is not added, and FIG. 4 is an explanatory diagram of the energy level of the charge generation layer to which the dopant is added. As shown in FIG. 3 , the behavior of electrons (●) of the hole-transporting material with a small ionization energy of the highest occupied molecular orbital (HOMO) contained in the p-doped layer 1 is used to inject electrons into the element. key. If electrons can be efficiently transferred from the p-doped layer 1 to the n-doped layer 2, electrons can be efficiently injected into the element. A dopant (electron-accepting material, electron-donating material) is required to promote the flow of this charge.

FIG. 4 shows changes in energy when dopants (electron-accepting materials, electron-donating materials) are added to the p-doped layer 1 and the n-doped layer 2 . By adding a dopant (electron-accepting material) to the p-doped layer 1, the energy level of the p-doped layer 1 is shifted upward (the one with the smaller ionization energy), and it becomes easy to do n-doping The Lowest Unoccupied Molecular Orbital (LUMO) of layer 2 transfers the state of electrons. On the other hand, by adding a dopant (electron-donating material) to the n-doped layer 2 , in the n-doped layer 2 , the electron-donating material and the electron-transporting material form hydrogen bonds, whereby electrons are transported. The energy level of the active material is shifted downward (the one with the larger electron affinity), and the LUMO of the n-doped layer 2 is in a state in which electrons are easily accepted. Furthermore, the ionization energy is also increased, whereby the blocking performance of holes transmitted from the light-emitting layer side is also improved, and the light-emitting efficiency is improved. In this way, by utilizing the shift of the energy level by adding the dopant (electron-accepting material, electron-donating material), the charge generating ability in the charge generating layer 10 containing only the organic material is improved.

The free potential of the hole-transporting material is preferably less than 5.7 eV. In this case, since the ionization energy of the HOMO of the p-doped layer 1 is small, it is easy to transfer electrons to the LUMO of the n-doped layer 2 . Here, the free potential of the hole-transporting material is measured by photoelectron spectroscopy or photoelectron yield spectroscopy.

The electron-accepting material is preferably an organic substance capable of forming a charge transfer complex by redox reaction with the hole-transporting material. In this case, the ionization energy of the HOMO of the p-doped layer 1 is reduced, and electrons are easily transferred to the LUMO of the n-doped layer 2 .

The electron-donating material is preferably an organic substance capable of forming a hydrogen bond with the electron-transporting material. In this case, the energy level of the electron-transporting material in the n-doped layer 2 becomes low, and the LUMO of the n-doped layer 2 easily accepts electrons.

"p-doped layer" The p-doped layer 1 includes a hole-transporting material and an electron-accepting material. The p-doped layer 1 of the present embodiment includes a hole transport material and an electron accepting material with small ionization energy, and the electrons of the hole transport material are attracted by the electron accepting material, and the electrons are easily injected into the device. The average thickness of the p-doped layer 1 is preferably 1 nm to 100 nm, more preferably 3 nm to 20 nm. In addition, the mixing ratio (mass ratio) of the hole-transporting material: the electron-accepting material in the p-doped layer 1 is preferably 0.1:9.9 to 9.9:0.1, more preferably 1:9 to 9:1. The average thickness of the p-doped layer 1 can be measured by, for example, a stylus profiler or a spectroscopic ellipsometer.

As the hole-transporting material, various p-type high molecular weight materials (organic polymers) and various p-type low molecular weight materials can be used alone or in combination. Specifically, examples of the hole-transporting material include 4,4',4''-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), 3,3'-bis[1,4]benzoxazino[2,3,4-kl]phenoxazine, N,N'-bis(1-naphthyl)-N,N'-diphenyl -1,1'-biphenyl-4,4'-diamine (α-NPD), N4,N4'-bis(dibenzo[b,d]thiophen-4-yl)-N4,N4'-di Phenylbiphenyl-4,4'-diamine (DBTPB), polyarylamine, fluorene-arylamine copolymer, fluorene-bithiophene copolymer, poly(N-vinylcarbazole), polyvinyl Pyrene, polyvinyl anthracene, polythiophene, polyalkylthiophene, polyhexylthiophene, poly(p-phenylene vinylene), polythiopheneacetylene, pyrene formaldehyde resin, ethylcarbazole formaldehyde resin or derivatives thereof, etc. These hole-transporting materials can also be used as mixtures with other compounds. Among them, materials with low ionization energy, such as triarylamines such as 4,4',4''-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), are particularly preferred. such as phenoxazine derivatives such as 3,3'-bis[1,4]benzoxazino[2,3,4-kl]phenoxazine, etc.

所述電子接受性材料可單獨使用一種，亦可將兩種以上組合使用。The electron-accepting material is a material containing a highly electronegative substituent selected from the group consisting of fluorine, chlorine, cyano, nitro, and carbonyl. As the electron-accepting material, for example, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) represented by the following structural formula (1-1), 1,3,4,5,7,8-hexafluoro-tetracyanonaphthoquinodimethane (F6TCNNQ) represented by the following structural formula (1-2), and represented by the following structural formula (1-3) Hexacyano-trimethylene-cyclopropane (CN6-CP), 1,4,5,8,9,12-hexaazabitriphenylene-2 represented by the following structural formula (1-4), 3,6,7,10,11-hexacarbonitrile (HAT-CN) etc. [hua 1]

The electron-accepting material may be used alone or in combination of two or more.

"n-doped layer" The n-doped layer 2 includes an electron-transporting material and an electron-donating material. The n-doped layer 2 of the present embodiment is composed of an electron-transporting material and an electron-donating material having high electron affinity, and plays a role of receiving electrons from the p-doped layer 1 and transporting them into the element. Due to the existence of the electron-donating material, the electron affinity of the electron-transporting material increases, and it is easy to inject electrons into the device, and the ionization energy of the electron-transporting material increases, for example, it is also effective in preventing holes transported from the light-emitting layer. , which contributes to high efficiency. The average thickness of the n-doped layer 2 is preferably 1 nm to 100 nm, more preferably 3 nm to 20 nm. In addition, the mixing ratio (mass ratio) of the electron-transporting material: the electron-donating material in the n-doped layer 2 is preferably 0.1:9.9 to 9.9:0.1, more preferably 1:9 to 9:1. The average thickness of the n-doped layer 2 can be measured by, for example, a stylus profiler or a spectroscopic ellipsometry.

As the electron-transporting material, any material that can be generally used as a material for an electron-transporting layer of an organic EL element can be used. Specifically, examples of the electron-transporting material include phosphine oxide derivatives such as phenyl-dipyrenylphosphine oxide (POPy ₂ ), tris-1,3,5-(3'-(pyridine-3''- Pyridine derivatives such as phenyl)benzene (TmPhPyB), quinoline derivatives such as 2-(3-(9-carbazolyl)phenyl)quinoline (mCQ), 2-phenyl-4,6-bis Pyrimidine derivatives such as (3,5-dipyridylphenyl)pyrimidine (BPyPPM), pyrazine derivatives, phenanthroline derivatives such as 4,7-diphenyl-1,10-phenanthroline (BPhen), 2, 4-Bis(4-biphenyl)-6-(4'-(2-pyridyl)-4-biphenyl)-[1,3,5]triazine (MPT), 2,4,6- Triazine derivatives such as tris(m-pyridin-3-yl-phenyl)triazine (TmPPyTz), 3-phenyl-4-(1'-naphthyl)-5-phenyl-1,2,4-triazine Triazole derivatives such as azole (TAZ), oxazole derivatives, 2-(4-biphenyl)-5-(4-tert-butylphenyl-1,3,4-oxadiazole (PBD), etc. Oxadiazole derivatives, imidazole derivatives such as 2,2',2''-(1,3,5-benzenetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBI), Aromatic ring tetracarboxylic anhydrides such as naphthalene and perylene, bis[2-(2-hydroxyphenyl)benzothiazole]zinc (Zn(BTZ) ₂ ), tris(8-hydroxyquinoline) aluminum (Alq ₃ ) Various metal complexes such as 2,5-bis(6'-(2',2''-bipyridine))-1,1-dimethyl-3,4-diphenylsilacyclopentadiene Organosilane derivatives represented by silacyclopentadiene (silole) derivatives such as (PyPySPyPy), Japanese Patent Laid-Open No. 2013-239691, International Publication No. 2014/133141, Japanese Patent Laid-Open No. 2016-172728 , boron-containing compounds described in Japanese Patent Laid-Open No. 2016-199507 and Japanese Patent Laid-Open No. 2016-199508, etc., one or more of these can be used. Among these electron-transporting materials, it is particularly preferred to use Triazine derivatives such as TmPPyTz, phosphine oxide derivatives such as POPy ₂ , metal complexes such as Alq ₃ , and pyridine derivatives such as TmPhPyB.

The electron-donating material is selected from the group consisting of tertiary amines with an acid dissociation constant pKa of 1 or more, phosphazene compounds, guanidine compounds, heterocyclic compounds containing an amidine structure, hydrocarbon compounds having a ring structure, phenanthroline compounds, and terpyridines series compounds, cyclic pyridine series compounds. The electron-donating material may be used alone or in combination of two or more. These electron-donating materials are basic compounds having an acid dissociation constant pKa of 1 or more. Furthermore, in the present invention, "pKa" generally refers to "acid dissociation constant in water", and those that cannot be measured in water refer to "acid dissociation constant in dimethyl sulfoxide (DMSO)", and also cannot be measured in water. "Acid dissociation constant in acetonitrile" was measured in DMSO. Preferably, it means "acid dissociation constant in water".

The tertiary amine (tertiary amine derivative) may be a chain or cyclic amine compound, and in the case of being cyclic, a heterocyclic amine compound, or an aliphatic amine or Heterocyclic amine compounds such as aromatic amines. The tertiary amine preferably has 1 to 4 amine groups, and more preferably has 1 or 2 amine groups. Moreover, as an amine compound, the compound which has an alkyl group, an alkylamine group, and an alkoxy group may be sufficient. Specifically, (mono, di, tri) alkylamines; aromatic amines having 1 to 3 alkylamine groups; aromatic amines having 1 to 3 alkoxy groups, etc. are mentioned.

As said tertiary amine, it is preferable that it does not contain a primary amine and a secondary amine. Specifically, as the tertiary amine, dialkylaminopyridines such as dimethylaminopyridine (DMAP) represented by the following structural formula (2-1) or (2-2), An amine having a structure represented by NR ²¹ R ²² R ²³ such as triethylamine represented by the following structural formula (2-3) (wherein R ²¹ , R ²² and R ²³ are the same or different, and represent a hydrocarbon group which may have a substituent ), acridine orange (AOB) represented by the following structural formula (2-4), etc. [hua 2]

The hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms, still more preferably a hydrocarbon group having 1 to 4 carbon atoms, and still more preferably a hydrocarbon group having 1 or 2 carbon atoms. When a hydrocarbon group has a substituent, it is preferable that it also includes the said carbon number of the whole of a substituent. As the hydrocarbon group, an alkyl group, an alkenyl group, and an alkynyl group are exemplified, but an alkyl group is preferred. As a substituent in the hydrocarbon group having a substituent, a halogen atom, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, an amino group and the like can be exemplified. The dimethylaminopyridine is preferably the 2-position (2-DMAP) or the 4-position (4-DMAP) of dimethylamine as an electron donating group based on the bonding position on the pyridine ring. In particular, 4-dimethylaminopyridine in which a dimethylamino group is bonded to the 4-position of the pyridine ring has a high pKa.

As the tertiary amine, alkoxypyridine derivatives such as methoxypyridine derivatives can also be used. The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms, still more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably 1 or 1. 2 of the alkoxy. The alkoxypyridine derivatives also include compounds in which one or more hydrogen atoms of the alkoxypyridine are substituted with a substituent. As a substituent, the same substituent as the substituent of the hydrocarbon group of the said tertiary amine can be illustrated. As the methoxypyridine derivative, 4-MeOP (methoxy pyridine ( )) or 3-methoxypyridine (3-MeOP) represented by the following structural formula (2-6) at the 3-position. In particular, 4-methoxypyridine in which a methoxy group is bonded to the 4-position of the pyridine ring is preferred because of its high pKa. [hua 3]

As the tertiary amine, it is preferable to use one or two or more selected from heterocyclic aromatic amines and trialkylamines having a dialkylamine group and/or an alkoxy group, and it is particularly preferable to use a One or more of dialkylaminopyridine, trialkylamine and alkoxypyridine derivatives.

The phosphazene compound (phosphazene base derivative) is, for example, a compound having a structure represented by the following general formula (3-1). [hua 4]

In the above formula (3-1), R ³¹ represents a hydrogen atom or a hydrocarbon group, and R ³² to R ³⁴ represent a hydrogen atom, a hydrocarbon group, and -NR'R'' (wherein R' and R'' each independently represent hydrogen atom, hydrocarbon group), or a group represented by the following formula (3-2), and n represents a number of 1 to 5. [hua 5]

In the above formula (3-2), R ³⁵ to R ³⁷ represent a hydrogen atom, a hydrocarbon group, or -NR'R'' (wherein R' and R'' each independently represent a hydrogen atom or a hydrocarbon group), and m represents A number from 1 to 5.

As the hydrocarbon group in the above formulae (3-1) and (3-2), a group having 1 to 8 carbon atoms is preferable, and a group having 1 to 4 carbon atoms is more preferable. Moreover, as a hydrocarbon group, an alkyl group is preferable. As the R ³⁴ , a tertiary butyl group is particularly preferred.

Examples of the phosphazene base derivatives include compounds represented by the following structural formula (3-3). [hua 6]

The guanidine compound is a compound containing a structure represented by the following general formula (4-1). [hua 7]

In the formula (4-1), R ⁴¹ to R ⁴⁵ are the same or different, and represent a hydrogen atom or a hydrocarbon group, and two or more of R ⁴¹ to R ⁴⁵ may be bonded to form a cyclic structure. In addition, the guanidine compound may have a plurality of structures represented by the general formula (4-1).

As the guanidine compound, a guanidine cyclic derivative or the like can be used. Examples of guanidine cyclic derivatives include 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) represented by the following structural formula (4-2). ), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) represented by the following structural formula (4-3), represented by the following structural formula (4-4) The compound (Py-hpp2) and so on. [hua 8]

In the heterocyclic compound containing an amidine structure, the amidine structure is a structure represented by R ⁵¹ -C(=NR ⁵² )-NR ⁵³ R ⁵⁴ (wherein R ⁵¹ to R ⁵⁴ are the same or different, and represent a hydrogen atom or hydrocarbon group). As a heterocyclic compound containing an amidine structure, a diazabicyclononene derivative, a diazabicycloundecene derivative, etc. are mentioned.

As the diazabicyclononene derivative, 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and the like represented by the following structural formula (5-1) can be mentioned. Examples of the diazabicycloundecene derivative include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) represented by the following structural formula (5-2). [Chemical 9]

The diazabicyclononene derivatives also include compounds in which one or more hydrogen atoms of the diazabicyclononene are substituted with substituents, and the diazabicycloundecene derivatives also include A compound having a structure in which one or more hydrogen atoms of diazabicycloundecene are substituted with a substituent. As a substituent, the same thing as the substituent of the hydrocarbon group of the said tertiary amine can be illustrated.

The hydrocarbon compound having a ring structure is preferably a compound having a 5-membered ring or a 6-membered ring as a ring structure, and is also preferably a ring structure formed by condensing a 5-membered ring and a 6-membered ring, or a plurality of A compound with a ring structure formed by condensing a 6-membered ring. As a 5-membered ring, a cyclopentane ring, a cyclopentadiene ring, etc. are mentioned, As a 6-membered ring, a benzene ring etc. are mentioned. As the hydrocarbon compound having a ring structure, a compound having only a ring structure and an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 5 carbon atoms, is bonded to the ring structure A compound of the structure, or a compound of a structure in which a plurality of ring structures are bonded directly or via a hydrocarbon linking group having 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 5. As a specific example of the hydrocarbon compound which has a ring structure, the compound of following formula (6-1) - (6-14) is mentioned. In addition, Ph in the formula represents a phenyl group. [Chemical 10]

此處，作為1價有機基，可列舉：可具有取代基的芳基、雜環基、烷基、烯基、炔基、烷氧基、芳氧基、芳基烷氧基、矽烷基、羥基、胺基、烷基胺基、芳基胺基、鹵素原子、羧基、硫醇基、環氧基、醯基、可具有取代基的寡芳基（oligoaryl)、1價寡雜環基、烷硫基、芳硫基、芳基烷基、芳基烷氧基、芳基烷硫基、偶氮基、錫烷基、膦基、可具有取代基的芳基膦基、可具有取代基的烷基膦基、芳基氧膦基、可具有取代基的烷基氧膦基、矽氧基、可具有取代基的芳氧基羰基、可具有取代基的烷氧基羰基、可具有取代基的胺甲醯基、可具有取代基的芳基羰基、可具有取代基的烷基羰基、可具有取代基的芳基磺醯基、可具有取代基的烷基磺醯基、可具有取代基的芳基亞磺醯基、可具有取代基的烷基亞磺醯基、甲醯基、氰基、硝基、芳基磺醯氧基、烷基磺醯氧基；甲磺酸酯基、乙磺酸酯基、三氟甲磺酸酯基等烷基磺酸酯基；苯磺酸酯基、對甲苯磺酸酯基等芳基磺酸酯基；苄基磺酸酯基等芳基烷基磺酸酯基、硼基、鋶甲基（sulfonium methyl）、鏻甲基（Phosphonium methyl）、膦酸酯甲基（phosphonate methyl）、芳基磺酸酯基、醛基、乙腈基等。 另外，作為所述1價有機基所具有的取代基，可列舉氟原子、氯原子、溴原子、碘原子的鹵素原子；氯化甲基、溴化甲基、碘化甲基、氟甲基、二氟甲基、三氟甲基等鹵烷基；甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基等碳數1～20的直鏈狀或分支鏈狀烷基；環戊基、環己基、環庚基等碳數5～7的環狀烷基；甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第三丁氧基、戊氧基、己氧基、庚氧基、辛氧基等碳數1～20的直鏈狀或分支鏈狀烷氧基；羥基；硫醇基；硝基；氰基；胺基；偶氮基；甲基胺基、乙基胺基、二甲基胺基、二乙基胺基等具有碳數1～40的烷基的單或二烷基胺基；二苯基胺基、咔唑基等胺基；乙醯基、丙醯基、丁醯基等醯基；乙烯基、1-丙烯基、烯丙基、丁烯基、苯乙烯基等碳數2～20的烯基；乙炔基、1-丙炔基、炔丙基、苯乙炔基等碳數2～20的炔基；乙烯氧基、烯丙氧基等烯氧基；乙炔氧基、苯基乙醯氧基等炔氧基；苯氧基、萘氧基、聯苯氧基、芘氧基等芳氧基；三氟甲基、三氟甲氧基、五氟乙氧基、全氟苯基等全氟基及更長鏈的全氟基；二苯基硼基、二均三甲苯基硼基、雙(全氟苯基)硼基、4,4,5,5-四甲基-1,3,2-二氧雜硼雜環戊基等硼基；乙醯基、苯甲醯基等羰基；乙醯氧基、苯甲醯氧基等羰氧基；甲氧基羰基、乙氧基羰基、苯氧基羰基等烷氧基羰基；甲基亞磺醯基、苯基亞磺醯基等亞磺醯基；甲基磺醯基、苯基磺醯基等磺醯基；烷基磺醯氧基；芳基磺醯氧基；膦基；二乙基氧膦基、二苯基氧膦基等氧膦基；三甲基矽烷基、三異丙基矽烷基、二甲基第三丁基矽烷基、三甲氧基矽烷基、三苯基矽烷基等矽烷基；矽烷基氧基；錫烷基；可經鹵素原子或烷基、烷氧基等取代的苯基、2,6-二甲苯基、均三甲苯基、2,3,5,6-四甲苯基(duryl)、聯苯基、三聯苯基、萘基、蒽基、芘基、甲苯甲醯基、大茴香基、氟苯基、二苯基胺基苯基、二甲基胺基苯基、二乙基胺基苯基、菲基基等芳基（可經取代的芳香族烴環基)；可經鹵素原子或烷基、烷氧基等取代的噻吩基、呋喃基、矽雜環戊二烯基、噁唑基、噁二唑基、噻唑基、噻二唑基、吖啶基、喹啉基、喹噁啉基、啡啉基、苯並噻吩基、苯並噻唑基、吲哚基、咔唑基、吡啶基、吡咯基、苯並噁唑基、嘧啶基、咪唑基等雜環基（可經取代的芳香族雜環基）；羧基；羧酸酯；環氧基；異氰基；氰酸酯基；異氰酸酯基；硫氰酸酯基；異硫氰酸酯基；胺甲醯基；N,N-二甲基胺甲醯基、N,N-二乙基胺甲醯基等N,N-二烷基胺甲醯基；甲醯基；亞硝基；甲醯氧基等。再者，該些基可經鹵素原子或烷基、芳基等取代。進而，該些基可相互以任意部位鍵結而形成環。The phenanthroline-based compound includes phenanthroline represented by the following structural formula (7-1), and a compound in which one or more hydrogen atoms in the phenanthroline are substituted with a monovalent organic group (hereinafter sometimes referred to as "phenanthroline"). phospholine derivatives"). [Chemical 11]

Here, examples of the monovalent organic group include optionally substituted aryl groups, heterocyclic groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, silyl groups, hydroxyl group, amino group, alkylamine group, arylamine group, halogen atom, carboxyl group, thiol group, epoxy group, acyl group, optionally substituted oligoaryl group, monovalent oligoheterocyclic group, Alkylthio, arylthio, arylalkyl, arylalkoxy, arylalkylthio, azo, stannyl, phosphino, optionally substituted arylphosphino, optionally substituted Alkylphosphino, arylphosphinoyl, optionally substituted alkylphosphinoyl, siloxy, optionally substituted aryloxycarbonyl, optionally substituted alkoxycarbonyl, optionally substituted carboxyl, optionally substituted arylcarbonyl, optionally substituted alkylcarbonyl, optionally substituted arylsulfonyl, optionally substituted alkylsulfonyl, optionally substituted Arylsulfinyl, optionally substituted alkylsulfinyl, carboxyl, cyano, nitro, arylsulfonyloxy, alkylsulfonyloxy; mesylate group , ethanesulfonate, trifluoromethanesulfonate and other alkylsulfonate groups; benzenesulfonate, p-toluenesulfonate and other arylsulfonate groups; benzylsulfonate and other arylsulfonate groups Alkyl sulfonate, boron, sulfonium methyl, Phosphonium methyl, phosphonate methyl, aryl sulfonate, aldehyde, acetonitrile, etc. . In addition, as the substituent which the monovalent organic group has, there may be mentioned halogen atoms of fluorine atom, chlorine atom, bromine atom, and iodine atom; methyl chloride, methyl bromide, methyl iodide, and fluoromethyl group. , difluoromethyl, trifluoromethyl and other haloalkyl groups; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. carbon number 1-20 linear or branched chain alkyl groups; cyclic alkyl groups with 5 to 7 carbon atoms such as cyclopentyl, cyclohexyl, and cycloheptyl; methoxy, ethoxy, propoxy, isopropoxy, Butoxy, isobutoxy, tertiary butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and other linear or branched alkoxy groups with 1 to 20 carbon atoms; hydroxyl; A thiol group; a nitro group; a cyano group; an amino group; an azo group; or dialkylamine; diphenylamine, carbazolyl and other amine groups; acetyl, propionyl, butyryl and other acetyl groups; vinyl, 1-propenyl, allyl, butenyl, benzene Alkenyl groups with 2 to 20 carbon atoms such as vinyl; alkynyl groups with 2 to 20 carbon atoms such as ethynyl, 1-propynyl, propargyl, and phenylethynyl; alkenyl groups such as vinyloxy and allyloxy ; alkynyloxy groups such as acetyleneoxy and phenylacetyloxy; aryloxy groups such as phenoxy, naphthyloxy, biphenyloxy, pyreneoxy; trifluoromethyl, trifluoromethoxy, pentafluoro Perfluoro groups such as ethoxy, perfluorophenyl and longer chain perfluoro groups; diphenylboronyl, dimesitylboronyl, bis(perfluorophenyl)boronyl, 4,4,5 ,5-tetramethyl-1,3,2-dioxaborolyl and other boronyl groups; carbonyl groups such as acetyl and benzyl groups; carbonyl groups such as acetyloxy and benzyloxy groups ; alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl; sulfinyl such as methylsulfinyl, phenylsulfinyl; methylsulfonyl, phenylsulfonyl sulfonyl groups such as alkyl; alkylsulfonyloxy; arylsulfonyloxy; phosphino groups; Silyl silyl group, dimethyl tert-butyl silyl group, trimethoxy silyl group, triphenyl silyl group, etc.; silyloxy group; stannyl group; Substituted phenyl, 2,6-xylyl, mesityl, 2,3,5,6-tetramethylphenyl (duryl), biphenyl, terphenyl, naphthyl, anthracenyl, pyrenyl, Aryl (optionally substituted aromatic thienyl, furanyl, silacyclopentadienyl, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, Acridyl, quinolinyl, quinoxolinyl, phenanthroline, benzothienyl, benzothiazolyl, indolyl, carbazolyl, pyridyl, pyrrolyl, benzoxazolyl, pyrimidinyl, Heterocyclic groups such as imidazolyl groups (aromatic heterocyclic groups which may be substituted); carboxyl groups; carboxylate groups; epoxy groups; isocyano groups; cyanate groups; isocyanate groups; thiocyanate groups; isothiocyanate groups Ester group; carbamoyl; N,N-dimethylaminocarboxy, N, N-diethylamine carboxyl, etc. N,N-dialkylamine carboxyl; carboxyl; nitroso; carboxyloxy and the like. Furthermore, these groups may be substituted with a halogen atom or an alkyl group, an aryl group, or the like. Furthermore, these groups may be bonded to each other at arbitrary positions to form a ring.

The phenanthroline derivative may be a compound having multiple phenanthroline structures in the molecular structure.

Examples of the phenanthroline derivatives include compounds represented by the following structural formulae (7-2) to (7-9). [Chemical 12]

此處，作為1價有機基，可列舉：可具有取代基的芳基、雜環基、烷基、烯基、炔基、烷氧基、芳氧基、芳基烷氧基、矽烷基、羥基、胺基、烷基胺基、芳基胺基、鹵素原子、羧基、硫醇基、環氧基、醯基、可具有取代基的寡芳基（oligoaryl)、1價寡雜環基、烷硫基、芳硫基、芳基烷基、芳基烷氧基、芳基烷硫基、偶氮基、錫烷基、膦基、可具有取代基的芳基膦基、可具有取代基的烷基膦基、芳基氧膦基、可具有取代基的烷基氧膦基、矽氧基、可具有取代基的芳氧基羰基、可具有取代基的烷氧基羰基、可具有取代基的胺甲醯基、可具有取代基的芳基羰基、可具有取代基的烷基羰基、可具有取代基的芳基磺醯基、可具有取代基的烷 基磺醯基、可具有取代基的芳基亞磺醯基、可具有取代基的烷基亞磺醯基、甲醯基、氰基、硝基、芳基磺醯氧基、烷基磺醯氧基；甲磺酸酯基、乙磺酸酯基、三氟甲磺酸酯基等烷基磺酸酯基；苯磺酸酯基、對甲苯磺酸酯基等芳基磺酸酯基；苄基磺酸酯基等芳基烷基磺酸酯基、硼基、鋶甲基、鏻甲基、膦酸酯甲基、芳基磺酸酯基、醛基、乙腈基等。 作為所述1價有機基所具有的取代基，可列舉氟原子、氯原子、溴原子、碘原子的鹵素原子；氯化甲基、溴化甲基、碘化甲基、氟甲基、二氟甲基、三氟甲基等鹵烷基；甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基等碳數1～20的直鏈狀或分支鏈狀烷基；環戊基、環己基、環庚基等碳數5～7的環狀烷基；甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第三丁氧基、戊氧基、己氧基、庚氧基、辛氧基等碳數1～20的直鏈狀或分支鏈狀烷氧基；羥基；硫醇基；硝基；氰基；胺基；偶氮基；甲基胺基、乙基胺基、二甲基胺基、二乙基胺基等具有碳數1～40的烷基的單或二烷基胺基；二苯基胺基、咔唑基等胺基；乙醯基、丙醯基、丁醯基等醯基；乙烯基、1-丙烯基、烯丙基、丁烯基、苯乙烯基等碳數2～20的烯基；乙炔基、1-丙炔基、炔丙基、苯乙炔基等碳數2～20的炔基；乙烯氧基、烯丙氧基等烯氧基；乙炔氧基、苯基乙醯氧基等炔氧基；苯氧基、萘氧基、聯苯氧基、芘氧基等芳氧基；三氟甲基、三氟甲氧基、五氟乙氧基、全氟苯基等全氟基及更長鏈的全氟基；二苯基硼基、二均三甲苯基硼基、雙(全氟苯基)硼基、4,4,5,5-四甲基-1,3,2-二氧雜硼雜環戊基等硼基；乙醯基、苯甲醯基等羰基；乙醯氧基、苯甲醯氧基等羰氧基；甲氧基羰基、乙氧基羰基、苯氧基羰基等烷氧基羰基；甲基亞磺醯基、苯基亞磺醯基等亞磺醯基；甲基磺醯基、苯基磺醯基等磺醯基；烷基磺醯氧基；芳基磺醯氧基；膦基；二乙基氧膦基、二苯基氧膦基等氧膦基；三甲基矽烷基、三異丙基矽烷基、二甲基第三丁基矽烷基、三甲氧基矽烷基、三苯基矽烷基等矽烷基；矽烷基氧基；錫烷基；可經鹵素原子或烷基、烷氧基等取代的苯基、2,6-二甲苯基、均三甲苯基、2,3,5,6-四甲苯基(duryl)、聯苯基、三聯苯基、萘基、蒽基、芘基、甲苯甲醯基、大茴香基、氟苯基、二苯基胺基苯基、二甲基胺基苯基、二乙基胺基苯基、菲基基等芳基（可經取代的芳香族烴環基)；可經鹵素原子或烷基、烷氧基等取代的噻吩基、呋喃基、矽雜環戊二烯基、噁唑基、噁二唑基、噻唑基、噻二唑基、吖啶基、喹啉基、喹噁啉基、啡啉基、苯並噻吩基、苯並噻唑基、吲哚基、咔唑基、吡啶基、吡咯基、苯並噁唑基、嘧啶基、咪唑基等雜環基（可經取代的芳香族雜環基）；羧基；羧酸酯；環氧基；異氰基；氰酸酯基；異氰酸酯基；硫氰酸酯基；異硫氰酸酯基；胺甲醯基；N，N-二甲基胺甲醯基、N,N-二乙基胺甲醯基等N,N-二烷基胺甲醯基；甲醯基；亞硝基；甲醯氧基等。再者，該些基可經鹵素原子或烷基、芳基等取代。進而，該些基可相互以任意部位鍵結而形成環。The terpyridine-based compound is a compound having a terpyridine structure (a structure formed by three pyridine bonds), and includes a terpyridine represented by the following structural formula (8-1) and one or more of the terpyridines A compound in which a hydrogen atom is substituted with a monovalent organic group (hereinafter sometimes referred to as a "terpyridine derivative"). [Chemical 13]

Here, examples of the monovalent organic group include optionally substituted aryl groups, heterocyclic groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, silyl groups, hydroxyl group, amino group, alkylamine group, arylamine group, halogen atom, carboxyl group, thiol group, epoxy group, acyl group, optionally substituted oligoaryl group, monovalent oligoheterocyclic group, Alkylthio, arylthio, arylalkyl, arylalkoxy, arylalkylthio, azo, stannyl, phosphino, optionally substituted arylphosphino, optionally substituted Alkylphosphino, arylphosphinoyl, optionally substituted alkylphosphinoyl, siloxy, optionally substituted aryloxycarbonyl, optionally substituted alkoxycarbonyl, optionally substituted carboxyl, optionally substituted arylcarbonyl, optionally substituted alkylcarbonyl, optionally substituted arylsulfonyl, optionally substituted alkylsulfonyl, optionally substituted Arylsulfinyl, optionally substituted alkylsulfinyl, carboxyl, cyano, nitro, arylsulfonyloxy, alkylsulfonyloxy; mesylate group , ethanesulfonate, trifluoromethanesulfonate and other alkylsulfonate groups; benzenesulfonate, p-toluenesulfonate and other arylsulfonate groups; benzylsulfonate and other arylsulfonate groups Alkyl sulfonate group, boron group, perylene methyl group, phosphonium methyl group, phosphonate methyl group, aryl sulfonate group, aldehyde group, acetonitrile group, etc. Examples of the substituent of the monovalent organic group include a fluorine atom, a chlorine atom, a bromine atom, and a halogen atom of an iodine atom; methyl chloride, methyl bromide, methyl iodide, fluoromethyl, bismuth Haloalkyl such as fluoromethyl and trifluoromethyl; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. Chain or branched alkyl groups; cyclic alkyl groups with 5 to 7 carbon atoms such as cyclopentyl, cyclohexyl, and cycloheptyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy linear or branched alkoxy with 1 to 20 carbon atoms, such as radical, isobutoxy, tertiary butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy; hydroxyl; thiol nitro group; cyano group; amine group; azo; Alkylamino; Diphenylamine, carbazolyl and other amine groups; Acetyl, propionyl, butyryl and other acyl; vinyl, 1-propenyl, allyl, butenyl, styryl Alkenyl with 2 to 20 carbon atoms; alkynyl with 2 to 20 carbon atoms such as ethynyl, 1-propynyl, propargyl, and phenylethynyl; alkenyl groups such as vinyloxy and allyloxy; acetylene alkynyloxy such as oxy, phenylacetyloxy; aryloxy such as phenoxy, naphthyloxy, biphenyloxy, pyreneoxy; trifluoromethyl, trifluoromethoxy, pentafluoroethoxy base, perfluorophenyl and other perfluoro groups and longer-chain perfluoro groups; diphenylboronyl, dimesitylboronyl, bis(perfluorophenyl)boronyl, 4,4,5,5 - Boronyl groups such as tetramethyl-1,3,2-dioxaborolyl; carbonyl groups such as acetyl and benzyl groups; carbonyl groups such as acetyloxy and benzyloxy groups; methyl Oxycarbonyl, ethoxycarbonyl, phenoxycarbonyl and other alkoxycarbonyl groups; methylsulfinyl, phenylsulfinyl and other sulfinyl groups; methylsulfonyl, phenylsulfonyl, etc. Sulfonyl; Alkylsulfonyloxy; Arylsulfonyloxy; Phosphinoyl; Silyl, dimethyl tert-butylsilyl, trimethoxysilyl, triphenylsilyl and other silyl groups; silyloxy; Phenyl, 2,6-xylyl, mesityl, 2,3,5,6-tetramethylphenyl (duryl), biphenyl, terphenyl, naphthyl, anthracenyl, pyrene, toluyl Aryl groups such as acyl group, anisyl group, fluorophenyl group, diphenylaminophenyl group, dimethylaminophenyl group, diethylaminophenyl group, and phenanthryl group (aromatic hydrocarbon ring that may be substituted) base); thienyl, furyl, silacyclopentadienyl, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, acridine which may be substituted by halogen atoms or alkyl, alkoxy, etc. base, quinolinyl, quinoxolinyl, phenanthroline, benzothienyl, benzothiazolyl, indolyl, carbazolyl, pyridyl, pyrrolyl, benzoxazolyl, pyrimidinyl, imidazolyl isoheterocyclic group (aromatic heterocyclic group which may be substituted); carboxyl group; carboxylate group; epoxy group; isocyano group; cyanate group; isocyanate group; thiocyanate group; isothiocyanate group ; Aminocarboxy; N,N-Dimethylcarbamoyl, N,N-bis Ethylamine carboxyl, etc. N,N-dialkylamine carboxyl; carboxyl; nitroso; carboxyloxy, etc. Furthermore, these groups may be substituted with a halogen atom or an alkyl group, an aryl group, or the like. Furthermore, these groups may be bonded to each other at arbitrary positions to form a ring.

As the terpyridine compound, 2,2':6',2''-terpyridine, 1,3-bis(4'-(2,2':6',2''-terpyridine) )) benzene, 6''-(3-(5H-dibenzo[b,d]borol-5-yl)-5-(4',6'-diethyl-[2, 2'-bipyridyl]-6-yl)thiophen-2-yl)-4,6-diethyl-2,2':6'3''-terpyridine) and the like.

The cyclic pyridine-based compound is preferably a compound having a structure in which a plurality of pyridine rings are bonded in a ring, and a plurality of pyridine rings are bonded directly or via a nitrogen atom to form a ring structure. Examples of the cyclic pyridine-based compound include compounds having a structure represented by the following general formula (9-1). [Chemical 14]

In the general formula (9-1), R ⁹ is the same or different, and represents a hydrogen atom or a monovalent organic group. n is the same or different, and is an integer of 0 or 1. m is an integer of 3-10.

When R ⁹ in the general formula (9-1) is a monovalent organic group, examples of the monovalent organic group include an optionally substituted aryl group, heterocyclic group, alkyl group, alkenyl group, Alkynyl group, alkoxy group, aryloxy group, arylalkoxy group, silyl group, hydroxyl group, amino group, alkylamine group, arylamine group, halogen atom, carboxyl group, thiol group, epoxy group, acyl group , oligoaryl (oligoaryl), monovalent oligoheterocyclic group, alkylthio, arylthio, arylalkyl, arylalkoxy, arylalkylthio, azo, tin which may have substituents Alkyl, phosphino, optionally substituted arylphosphino, optionally substituted alkylphosphino, arylphosphinoyl, optionally substituted alkylphosphino, siloxy, optionally substituted aryloxycarbonyl group, optionally substituted alkoxycarbonyl group, optionally substituted carbamoyl, optionally substituted arylcarbonyl, optionally substituted alkylcarbonyl, optionally substituted Arylsulfonyl, optionally substituted alkylsulfonyl, optionally substituted arylsulfinyl, optionally substituted alkylsulfinyl, formyl, cyano, nitro , arylsulfonyloxy, alkylsulfonyloxy; methanesulfonate, ethanesulfonate, trifluoromethanesulfonate and other alkylsulfonate groups; benzenesulfonate, p-toluene Aryl sulfonate groups such as sulfonate groups; aryl alkyl sulfonate groups such as benzyl sulfonate groups, boron groups, perylene methyl groups, phosphonium methyl groups, phosphonate methyl ester groups, aryl sulfonate groups group, aldehyde group, acetonitrile group, etc. Examples of the substituent which the monovalent organic group has include: a fluorine atom, a chlorine atom, a bromine atom, a halogen atom of an iodine atom; methyl chloride, methyl bromide, methyl iodide, fluoromethyl, Difluoromethyl, trifluoromethyl and other haloalkyl groups; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. with a carbon number of 1 to 20 Straight-chain or branched-chain alkyl groups; cyclic alkyl groups with 5 to 7 carbon atoms such as cyclopentyl, cyclohexyl, and cycloheptyl; methoxy, ethoxy, propoxy, isopropoxy, butyl Linear or branched alkoxy with 1 to 20 carbon atoms such as oxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy; hydroxyl; sulfur Alcohol group; nitro group; cyano group; amine group; azo; Dialkylamine; Diphenylamine, carbazolyl and other amine groups; Acetyl, propionyl, butyryl and other acyl groups; vinyl, 1-propenyl, allyl, butenyl, styrene alkenyl with 2 to 20 carbon atoms such as base; alkynyl with 2 to 20 carbon atoms such as ethynyl, 1-propynyl, propargyl, and phenylethynyl; alkenyl groups such as vinyloxy and allyloxy; Acetyloxy, phenylacetyloxy and other alkynyloxy groups; phenoxy, naphthyloxy, biphenyloxy, pyreneoxy and other aryloxy groups; trifluoromethyl, trifluoromethoxy, pentafluoroethyl Oxygen, perfluorophenyl and other perfluoro groups and longer-chain perfluoro groups; diphenylboron, dimesitylboron, bis(perfluorophenyl)boron, 4,4,5, Boronyl such as 5-tetramethyl-1,3,2-dioxaborolyl; carbonyl such as acetyl and benzyl; carbonyloxy such as acetyloxy and benzyloxy; methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl and other alkoxycarbonyl groups; methylsulfinyl, phenylsulfinyl and other sulfinyl groups; methylsulfonyl, phenylsulfonyl Isosulfonyl; alkylsulfonyloxy; arylsulfonyloxy; phosphino; Silyl group, dimethyl tert-butylsilyl group, trimethoxysilyl group, triphenylsilyl group, etc. Silyl group; Silyloxy group; stannyl group; can be substituted by halogen atom or alkyl group, alkoxy group, etc. phenyl, 2,6-xylyl, mesityl, 2,3,5,6-tetramethylphenyl (duryl), biphenyl, terphenyl, naphthyl, anthracenyl, pyrenyl, toluene Carboxylic, anisyl, fluorophenyl, diphenylaminophenyl, dimethylaminophenyl, diethylaminophenyl, phenanthryl and other aryl groups (aromatic hydrocarbons that may be substituted) cyclyl); thienyl, furanyl, silacyclopentadienyl, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, acridine which may be substituted by halogen atoms or alkyl, alkoxy, etc. Peridyl, quinolinyl, quinoxolinyl, phenanthroline, benzothienyl, benzothiazolyl, indolyl, carbazolyl, pyridyl, pyrrolyl, benzoxazolyl, pyrimidinyl, imidazole Heterocyclic group (aromatic heterocyclic group which may be substituted); carboxyl group; carboxylate; epoxy group; isocyano group; cyanate group; isocyanate group; thiocyanate group; isothiocyanate base; aminocarboxy; N,N-dimethylaminocarboxy, N,N- Diethylamine carboxyl, etc. N,N-dialkylamine carboxyl; carboxyl; nitroso; carboxyloxy and the like. Furthermore, it may be substituted with a halogen atom, an alkyl group, an aryl group, or the like. Furthermore, these groups may be bonded to each other at arbitrary positions to form a ring. Among them, the monovalent organic group of R ⁹ is preferably a methyl group, an ethyl group, a phenyl group, an n-propyl group, an isopropyl group, and an isobutyl group.

m in the general formula (9-1) is an integer of 3 to 10, but from the viewpoint of the strength of interaction with hydrogen, it is preferably 3 to 8, more preferably 3 to 6.

n in the general formula (9-1) may be the same or different, and may take an integer of 0 or 1. That is, for example, in the case where the cyclic pyridine-based compound is a compound having 6 pyridine rings, the possible integers of 6 n existing in the structure are from [i](0,0,0,0,0) to [ The combination of xii](1,1,1,1,1,1), since it is a cyclic structure, the others can be [ii](1,0,0,0,0,0), [iii](1 ,1,0,0,0,0), [iv](1,0,1,0,0,0), [v](1,0,0,1,0,0), [vi]( 1,1,1,0,0,0), [vii](1,1,0,1,0,0), [viii](0,0,1,1,1,1), [ix] (0,1,0,1,1,1), [x](0,1,1,0,1,1), [xi](0,1,1,1,1,1), total allowed 12 groups. And all of those are alternates. Among them, the above-mentioned [vi], [vii], and [xii] in which 6 or 3 of these are 1 are preferable. More preferably, the number of 1 in n is the same as m [xii]. That is, as the cyclic pyridine-based compound, among the compounds represented by the general formula (9-1), an azacalipyridine derivative in which all of n in the general formula (9-1) are 1 is preferable.

The cyclic pyridine-based compound having the structure represented by the general formula (9-1) is preferably a compound represented by the following general formulae (9-2) to (9-5). In addition, R ⁹ in general formula (9-2) - (9-5) is synonymous with R ⁹ in general formula (9-1).

[Chemical 15]

The cyclic pyridine-based compound is also preferably a compound in which the para-position hydrogen atom of the pyridine ring in the general formula (9-1) is substituted with a monovalent organic group. Here, as the monovalent organic group, Similarly, the monovalent organic group in R ⁹ can be mentioned. In addition, among the monovalent organic groups, a heterocyclic group is preferable, and a pyrrolidinyl group is particularly preferable.

Specific examples of the cyclic pyridine-based compound include compounds represented by the following structural formulae (9-6) to (9-7), and the like. [Chemical 16]

[Dopant Layer] The dopant layer 3 is composed of only the electron-accepting material or the electron-donating material. Here, as the electron-accepting material, various materials described in the section "p-doped layer" can be used. In addition, as the electron-donating material, various materials described in the section "n-doped layer" can be used.

The charge generating layer of the present embodiment is characterized by not containing alkali metal or metal oxide. In addition, since the charge generation layer of this embodiment does not contain an alkali metal, it does not contain the complex compound containing the alkali metal. Since the charge generation layer of the present embodiment does not contain these materials, it can be produced by co-evaporation, and is not easily deteriorated even in the presence of oxygen or moisture.

<Manufacturing method of charge generating layer> The manufacturing method of the charge generation layer of the present invention is a method of manufacturing the charge generation layer, comprising: Step A, co-evaporating the hole transport material and the electron accepting material to form a layer (p-doped layer) 1 including the hole transport material and the electron accepting material; and Step B, co-evaporating the electron-transporting material and the electron-donating material to form a layer (n-doped layer) 2 including the electron-transporting material and the electron-donating material. In addition, as required, the method for producing a charge generating layer of the present invention may also include step C, in which step C is performed by vapor-depositing only the electron-accepting material or only the electron-donating material to form a material containing only the electron-accepting material. layer or a layer containing only electron donating material (dopant layer) 3 . The sequence of the step A and the step B is not particularly limited, and can be appropriately selected according to the structure of the target device. In addition, the step C is preferably performed between the step A and the step B.

As the hole-transporting material, electron-accepting material, electron-transporting material, and electron-donating material used in the method for producing the charge-generating layer of the present invention, each material described in the section <Charge-generating layer> can be used. In addition, in the said co-evaporation and said vapor deposition, a normal vacuum vapor deposition apparatus can be used. According to the manufacturing method of the charge generation layer of the present invention, since the p-doped layer 1 and the n-doped layer 2 are formed by co-evaporation, the charge generation layer 10 can be efficiently manufactured with a small number of steps.

＜Organic EL element＞ Next, embodiments of the organic electroluminescent element of the present invention will be described in detail with reference to the accompanying drawings. 5 to 10 are schematic cross-sectional views for explaining embodiments of the organic EL element of the present invention.

The organic EL element 100 shown in FIGS. 5 and 6 includes a cathode 30 , a light-emitting layer 60 , and an anode 90 in this order, and further includes a charge generating layer 10 between the cathode 30 and the light-emitting layer 60 . The organic EL element 100 shown in FIG. 5 has a cathode 30 , a charge generation layer 10 , a light-emitting layer 60 , a hole transport layer 70 , and an anode 90 formed in this order on a substrate 20 , and is a so-called reverse structure organic EL element. On the other hand, the organic EL element 100 shown in FIG. 6 has an anode 90 , a hole transport layer 70 , a light-emitting layer 60 , a charge generation layer 10 and a cathode 30 formed in this order on the substrate 20 , and is a so-called forward structure organic EL element. In the organic EL elements 100 shown in FIGS. 5 and 6 , the p-doped layer 1 in the charge generation layer 10 is arranged on the cathode 30 side, and the n-doped layer 2 in the charge generation layer 10 is arranged on the side of the cathode 30 . The light-emitting layer 60 side. The organic EL element 100 of the above-described structure is easy to manufacture, and hardly deteriorates even in the presence of oxygen or moisture.

The organic EL element 100 shown in FIGS. 7 and 8 includes a cathode 30 , a light-emitting layer 60 , and an anode 90 in this order, and includes a charge generating layer 10 between the anode 90 and the light-emitting layer 60 . The organic EL element 100 shown in FIG. 7 has a cathode 30 , an electron transport layer 45 , a light-emitting layer 60 , a charge generation layer 10 , and an anode 90 formed in this order on a substrate 20 , and is a so-called reverse structure organic EL element. On the other hand, the organic EL element 100 shown in FIG. 8 has an anode 90 , a charge generation layer 10 , a light-emitting layer 60 , an electron transport layer 45 , and a cathode 30 formed in this order on the substrate 20 , and is a so-called forward structure organic EL element. In the organic EL elements 100 shown in FIGS. 7 and 8 , the p-doped layer 1 in the charge generation layer 10 is arranged on the light-emitting layer 60 side, and the n-doped layer 2 in the charge generation layer 10 is arranged on the anode 90 side. The organic EL element 100 of the structure is also easy to manufacture and does not easily deteriorate even in the presence of oxygen or moisture.

In the organic EL element 100 shown in FIG. 9, an electrode 39, a charge transport layer 57, a light-emitting layer 60, a charge generation layer 10, a light-emitting layer 60, a charge transport layer 57, and an electrode 39 are sequentially formed on the substrate 20, and has two layers of light-emitting layers. 60 series structure. In the organic EL element 100 shown in FIG. 10 , the electrode 39 , the charge transport layer 57 , the light emitting layer 60 , the charge generation layer 10 , the light emitting layer 60 , the charge generation layer 10 , the light emitting layer 60 , and the charge transport layer are sequentially formed on the substrate 20 . 57 and the electrode 39 have a tandem structure including three light-emitting layers 60 . Furthermore, the organic EL element of the present invention may have a tandem structure having four or more light-emitting layers.

Here, in the organic EL element 100 shown in FIGS. 9 and 10, the electrode 39 may be a cathode or an anode, and the charge transport layer 57 may be an electron transport layer or a hole transport layer. When one electrode 39 is a cathode, the other electrode 39 is an anode. In addition, the charge transport layer 57 adjacent to the electrode 39 serving as a cathode is usually an electron transport layer, and the charge transport layer 57 adjacent to the electrode 39 serving as an anode is usually a hole transport layer, but as shown in FIG. 11 described later, the cathode side The charge transport layer can also be a hole transport layer. The organic EL element 100 shown in FIGS. 9 and 10 is an organic EL element having two electrodes 39 (cathode and anode) and two or more light-emitting layers 60 between the two electrodes 39 (cathode and anode), and The charge generation layer 10 is provided between one layer within the light emitting layer 60 and another layer within the light emitting layer 60 . The organic EL element 100 of the structure is also easy to manufacture and does not easily deteriorate even in the presence of oxygen or moisture. In addition, the organic EL element 100 of the structure has high current efficiency and long life.

11 is a schematic cross-sectional view for explaining an example of the organic EL element of the present invention. The organic EL element 100 of this embodiment shown in FIG. 11 has the light-emitting layer 60 between the cathode 30 and the anode 90 . In addition, the organic EL element 100 shown in FIG. 11 has the charge generation layer 10 including the organic material between the cathode 30 and the light-emitting layer 60 .

The organic EL element 100 of the present embodiment has a cathode 30 , a coating intermediate layer 40 , a hole transport layer 50 , a layer containing a hole transport material and an electron accepting material (p-doped layer) formed in this order on the substrate 20 ) 1. Layer (n-doped layer) 2, light-emitting layer 60, hole-transporting layer 70, hole-injecting layer 80, and anode 90 comprising an electron-transporting material and an electron-donating material. In addition, in FIG. 11 , a layer (dopant layer) 3 containing only an electron-accepting material or an electron-donating material is arranged between the p-doped layer 1 and the n-doped layer 2 . In addition, a layer containing only an electron transport material may be laminated between the charge generation layer 10 and the light emitting layer 60 .

The organic EL element 100 shown in FIG. 11 is an organic EL element of a reverse structure in which the cathode 30 is arranged between the substrate 20 and the light-emitting layer 60 . The organic EL element 100 shown in FIG. 11 may be a top emission type element that extracts light on the side opposite to the substrate 20 or a bottom emission type element that extracts light on the substrate 20 side. In this embodiment, the organic EL element of the reverse structure is described as an example, but the organic EL element of the present invention may have any of the structures described in FIGS. 5 to 10 .

"Substrate" As a material of the substrate 20, a resin material, a glass material, cellulose, etc. are mentioned. Examples of the resin material used for the substrate 20 include polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyether, and polymethyl methacrylate. Ester, polycarbonate, polyarylate, etc. When a resin material is used as the material of the substrate 20 , it is preferable because the organic EL element 100 excellent in flexibility can be obtained. On the other hand, as a glass material used for the substrate 20, quartz glass, soda glass, etc. are mentioned.

When the organic EL element 100 is a bottom emission type element, a transparent substrate is used as the material of the substrate 20 . On the other hand, when the organic EL element 100 is a top emission type element, not only a transparent substrate but also an opaque substrate can be used as the material of the substrate 20 . Examples of the opaque substrate include a substrate made of a ceramic material such as alumina, a substrate in which an oxide film (insulating film) is formed on the surface of a metal plate such as stainless steel, and a substrate made of a resin material.

The average thickness of the substrate 20 may be determined according to the material of the substrate 20 and the like, and is preferably 0.1 mm to 30 mm, more preferably 0.1 mm to 10 mm. Furthermore, the average thickness of the substrate 20 can be measured by a digital multimeter or a vernier caliper.

"Cathode" The cathode 30 is formed on the substrate 20 in direct contact. As the material of the cathode 30, in the case of a bottom emission type element, indium tin oxide (Indium Tin Oxide, ITO), Indium Zinc Oxide (IZO), tin fluoride (Fluorine Oxide, IZO), which are transparent electrodes, are preferable. Tin Oxide (FTO), In ₃ O ₃ , SnO ₂ , Sb-containing SnO ₂ , Al-containing ZnO and other oxide conductive materials, electrons are generated in the charge generating layer 10 , so not only metal oxides but also metal oxides can be used. Any material such as metal, organic conductive film, carbon nanotube, and graphene can be used.

The average thickness of the cathode 30 is not particularly limited, but is preferably 10 nm to 500 nm, more preferably 100 nm to 200 nm. Furthermore, the average thickness of the cathode 30 can be measured by a stylus profiler or a spectroscopic ellipsometry.

"Coating Intermediate Layer" In the organic EL element 100 shown in FIG. 11 , in order to suppress leakage, a coating intermediate layer 40 is provided on the cathode 30 . By providing the coating intermediate layer 40, current leakage (short circuit) due to particles and the like can be suppressed. The coating intermediate layer 40 can be made of a high-conductivity polymer material such as poly(3,4-ethylenedioxythiophene/styrenesulfonic acid) (PEDOT/PSS), for example, manufactured by Heraeus "Clevios HIL1.3". The thickness of the coating intermediate layer 40 is preferably about several tens of nm, more preferably 10 nm˜90 nm. The coating intermediate layer 40 can be formed into a film by spin coating, for example.

"Electric hole transport layer" In the organic EL element 100 shown in FIG. 11 , the hole transport layer 50 is provided on the coating intermediate layer 40 although it does not contribute to direct charge generation. In order to avoid interaction of the electron-accepting material added to the p-doped layer 1 with the cathode 30 , it is preferable to have the hole transport layer 50 . In addition, the hole transport material used for the p-doped layer 1 described above or the material used for the hole transport layer 70 described later can be used for the hole transport layer 50 .

"Charge Generation Layer" As described above, the charge generation layer 10 includes: the layer (p-doped layer) 1 including the hole transport material and the electron accepting material; and the layer (n-doped layer) including the electron transport material and the electron donating material layer) 2. Furthermore, in this embodiment, the p-doped layer 1 and the n-doped layer 2 are laminated via the dopant layer 3, but the dopant layer 3 may or may not be provided.

"Light-emitting layer" As a material for forming the light-emitting layer 60, any material that can be generally used as a material for a light-emitting layer may be used, or a plurality of materials may be mixed and used. For example, in a preferred embodiment, as the light-emitting layer 60, bis[2-(2-benzothiazolyl)phenol]zinc(II) (Zn(BTZ) ₂ ) and tris[1-phenyl Isoquinoline]iridium(III) (Ir(piq) ₃ ). In addition, the material for forming the light-emitting layer 60 may be a low molecular compound or a high molecular compound. In addition, in the present invention, the low molecular weight material refers to a material that is not a high molecular material (polymer), and does not necessarily mean an organic compound with a low molecular weight.

Examples of polymer materials that form the light-emitting layer 60 include trans-polyacetylene, cis-polyacetylene, poly(di-Phenylacetylene) (PDPA), poly(alkylphenylacetylene) (Poly(alkylphenylacetylene) (alkyl Phenylacetylene), PAPA) and other polyacetylene compounds; poly(para-phenylene vinylene) (PPV), poly(2,5-dialkoxy-p-phenylene vinylene) (RO-PPV) ), cyano-substituted-poly(p-phenylene vinylene) (cyano-poly(para-phenylene vinylene), CN-PPV), poly(2-dimethyloctylsilyl-p-phenylene vinylene) (DMOS-PPV) , poly(2-methoxy, 5-(2'-ethylhexyloxy)-p-phenylene vinylene) (MEH-PPV) and other poly-p-phenylene vinylene compounds; poly(3-alkylthiophene) (Ploy (3 -alkyl thiophene), PAT), poly(oxy propylene) triol (Poly(oxy propylene) triol, POPT) and other polythiophene compounds; Octylfluorene-alternating-benzothiadiazole) (F8BT), α,ω-bis[N,N'-bis(methylphenyl)aminophenyl]-poly[9,9-bis(2- Ethylhexyl)fluorene-2,7-diyl] (PF2/6am4), poly(9,9-dioctyl-2,7-divinylfluorenyl-alternating-copoly(anthracene-9,10-) Diyl)) and other polyfluorene compounds; poly (para-phenylene) (Poly (para-phenylene), PPP), poly (1,5-dialkoxy-para-phenylene) (RO-PPP) and other poly-para-phenylene compounds ; Poly(N-vinylcarbazole) (PVK) and other polycarbazole-based compounds; Poly(methyl phenyl silane) (Poly(methyl phenyl silane), PMPS), naphthyl phenyl silane), PNPS), poly(biphenylyl phenyl silane) (Poly(biphenylyl phenyl silane), PBPS) and other polysilane-based compounds; further can include Japanese Patent Laid-Open No. 2011-184430, Japanese Patent Laid-Open No. 2011-184430 The boron compound-based polymer material and the like described in Gazette 2012-151148.

As the low molecular weight material forming the light-emitting layer 60, for example, a tri-coordinate iridium complex having - Phenylpyridine) iridium (Ir(ppy) ₃ ), tris(8-hydroxyquinoline) aluminum (Alq ₃ ), tris(4-methyl-8-hydroxyquinoline) aluminum (III) (Almq ₃ ), Zinc 8-hydroxyquinoline (Znq ₂ ), (1,10-phenanthroline)-tris-(4,4,4-trifluoro-1-(2-thienyl)-1,3,-butanedione) Various metal complexes such as europium (III) (Eu(TTA) ₃ (phen)), 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum (II) benzene-based compounds such as Distyryl benzenes (DSB) and Di Amino Distyryl benzenes (DADSB); naphthalene-based compounds such as naphthalene and Nile red; phenanthrenes such as phenanthrene Series compounds; 1,2-triphenylene compounds such as 1,2-triphenylene (chrysene) and 6-nitrobiphenyl (6-mtrochrysene); perylene, N,N'-bis(2,5-diphenylene) - tertiary butylphenyl)-3,4,9,10-perylene-dicarboxyimide (BPPC) and other perylene compounds; coronine and other perylene compounds; anthracene, bis-styryl anthracene and other anthracene compounds; Pyrene series compounds such as pyrene; pyran series compounds such as 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM); acridine Isoacridine series compounds; Stilbene series compounds such as stilbene; Thiophene series compounds such as 2,5-dibenzoxazole thiophene; Benzoxazole series compounds such as benzoxazole; Benzimidazole series compounds such as benzimidazole; 2 ,2'-(p-phenylene vinylene)-bisbenzothiazole and other benzothiazole-based compounds; distyryl (1,4-diphenyl-1,3-butadiene), tetraphenyl Butadiene-based compounds such as butadiene; naphthalene-based compounds such as naphthalimide; coumarin-based compounds such as coumarin; perone-based compounds such as perone; oxadiazoles oxadiazole-based compounds; aldazine-based compounds; cyclopentadiene-based compounds such as 1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene (PPCP); quinacridone , quinacridone red and other quinacridone compounds; pyrrolopyridine, thiadiazolopyridine and other pyridine compounds; 2,2',7,7'-tetraphenyl-9,9'-spirobifluorene and other spiro compounds; phthalocyanine compounds such as metals such as phthalocyanine (H ₂ Pc) and copper phthalocyanine, or metal-free phthalocyanine compounds; further, Japanese Patent Laid-Open No. 2009-155325, Japanese Patent Laid-Open No. 2011-184430, and The boron compound material and the like described in Japanese Patent Laid-Open No. 2012-151149.

The average thickness of the light-emitting layer 60 is not particularly limited, but is preferably 10 nm to 150 nm, more preferably 20 nm to 100 nm. In addition, the average thickness of the light-emitting layer 60 may be measured by a stylus profiler, or may be measured by a crystal oscillator film thickness meter at the time of film formation of the light-emitting layer 60 .

"Electric hole transport layer" As the hole-transporting organic material used in the hole-transporting layer 70 , various p-type high molecular materials (organic polymers) and various p-type low molecular weight materials can be used alone or in combination. Specifically, as a material of the hole transport layer 70, for example, N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4,4 '-Diamine (α-NPD), N4,N4'-bis(dibenzo[b,d]thiophen-4-yl)-N4,N4'-diphenylbiphenyl-4,4'-di Amine (DBTPB), polyarylamine, fluorene-arylamine copolymer, fluorene-bithiophene copolymer, poly(N-vinylcarbazole), polyvinylpyrene, polyvinyl anthracene, polythiophene, polyalkylene thiophene, polyhexylthiophene, poly(p-phenylene vinylene), polythiophene acetylene, pyrene formaldehyde resin, ethylcarbazole formaldehyde resin or derivatives thereof, etc. The materials of the hole transport layer 70 can also be used in the form of a mixture with other compounds. As an example, poly(3,4-ethylenedioxythiophene/styrenesulfonic acid) (PEDOT/PSS) etc. are mentioned as a polythiophene-containing mixture used as a material of the hole transport layer 70 .

The average thickness of the hole transport layer 70 is not particularly limited, but is preferably 10 nm to 150 nm, and more preferably 20 nm to 100 nm. In addition, the average thickness of the hole transport layer 70 can be measured by, for example, a stylus profiler or a spectroscopic ellipsometry.

"Hole Injection Layer" The hole injection layer 80 may be composed of inorganic materials or organic materials. Inorganic materials are more stable than organic materials, and therefore, higher resistance to oxygen or water is easily obtained than in the case of using organic materials. The inorganic material is not particularly limited, and for example, one or more metal oxides such as vanadium oxide (V ₂ O ₅ ), molybdenum oxide (MoO ₃ ), and ruthenium oxide (RuO ₂ ) can be used. On the other hand, as the organic material, 1,4,5,8,9,12-hexaazabitriphenylene-2,3,6,7,10,11-hexacarbonitrile (HAT-CN), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), etc.

The average thickness of the hole injection layer 80 is not particularly limited, but is preferably 1 nm to 1000 nm, more preferably 5 nm to 50 nm. In addition, the average thickness of the hole injection layer 80 can be measured at the time of film formation with a crystal oscillator film thickness meter.

"anode" As a material used for the anode 90, ITO, IZO, Au, Pt, Ag, Cu, Al, alloys containing these, etc. are mentioned. Among them, as the material of the anode 90, ITO, IZO, Au, Ag, and Al are preferably used.

The average thickness of the anode 90 is not particularly limited, but is preferably 10 nm to 1000 nm, more preferably 30 nm to 150 nm. In addition, even when an opaque material is used as the material of the anode 90, it can be used as a transparent anode in a top emission type organic EL element by, for example, making the average thickness about 10 nm to 30 nm. In addition, the average thickness of the anode 90 can be measured at the time of film formation of the anode 90 by a crystal oscillator film thickness meter.

"seal" The organic EL element 100 shown in FIG. 11 may be sealed as necessary. For example, the organic EL element 100 shown in FIG. 11 can be sealed by an airtight container (not shown) having a concave space for accommodating the organic EL element, and an adhesive for bonding the edge of the airtight container to the substrate 2 . Alternatively, the organic EL element may be housed in an airtight container, and the sealing material may be filled with a sealing material made of an ultraviolet (ultraviolet, UV) curable resin or the like. In addition, for example, the organic EL element 100 shown in FIG. 11 may also use a plate member (not shown) arranged on the anode 90 and a frame member (not shown) arranged along the edge portion of the plate member on the side facing the anode 90 . The sealing member constituted by the figure) and the adhesive for bonding between the plate member and the frame member and between the frame member and the substrate 20 are sealed.

When an organic EL element is sealed using a sealed container or a sealing member, a drying material that absorbs moisture can be arranged in the sealed container or inside the sealing member. In addition, as the sealed container or the sealing member, a material that absorbs moisture can be used. In addition, a space may be formed in the sealed airtight container or the inner side of the sealing member.

As a material of the sealing container or sealing member used when the organic EL element 100 shown in FIG. 11 is sealed, a resin material, a glass material, or the like can be used. The resin material and glass material used for the sealed container or the sealing member are the same as those used for the substrate 20 .

"Manufacturing method of organic EL element" Next, the manufacturing method of the organic EL element shown in FIG. 11 is demonstrated as an example of the manufacturing method of the organic EL element of this invention. When manufacturing the organic EL element 100 shown in FIG. 11 , first, the cathode 30 is formed on the substrate 20 . The cathode 30 can be formed by sputtering method, vacuum evaporation method, sol-gel method, spray thermal decomposition (Spray Pyrolysis Deposition, SPD) method, atomic layer deposition (atomic layer deposition, ALD) method, vapor deposition method, Liquid-phase film formation method, etc. When forming the cathode 30, a method of bonding metal foils can be used.

Next, on the cathode 30, a coating intermediate layer 40 and a hole transport layer 50 are formed as appropriate, and then the charge generation layer 10 is formed. The charge generation layer 10 is mainly composed of two or more layers as described above. Next, the light emitting layer 60 and the hole transport layer 70 are sequentially formed on the charge generation layer 10 .

The formation methods of the charge generation layer 10 , the light emitting layer 60 , and the hole transport layer 70 are not particularly limited, and various conventionally known formation methods can be appropriately adopted according to the characteristics of the materials used for each. Specifically, as a method of forming each of the charge generation layer 10 , the light emitting layer 60 , and the hole transport layer 70 , an organic compound containing an organic compound to become the charge generation layer 10 , the light emitting layer 60 , and the hole transport layer 70 can be applied. Compound solution coating method, vacuum evaporation method, Evaporative Spray Deposition from Ultra-dilute Solution (ESDUS), etc.

Next, the hole injection layer 80 and the anode 90 are sequentially formed on the hole transport layer 70 . When the hole injection layer 80 is made of an organic material, the hole injection layer 80 can be formed in the same manner as the charge generation layer 10 , the light emitting layer 60 , and the hole transport layer 70 , for example. In addition, the anode 90 can be formed similarly to the cathode 30, for example. Through the above steps, the organic EL element 100 shown in FIG. 11 is obtained.

"Sealing method" When the organic EL element 100 shown in FIG. 11 is sealed, the sealing can be performed using a method generally used for sealing organic EL elements.

The organic EL element 100 of the present embodiment has the layer (n-doped layer) 2 including the electron-transporting material and the electron-donating material. Therefore, by changing the energy level of the electron-transporting material by the electron-donating material, it is possible to Electrons are efficiently absorbed from the adjacent layer (p-doped layer) 1 containing a hole-transporting material and an electron-accepting material, and the resistance to holes transmitted from the light-emitting layer 60 side is also high. Therefore, electrons are efficiently generated in the charge generation layer 10 and an organic EL element with a low driving voltage is obtained, or the blocking performance of holes transmitted from the light emitting layer 60 is improved, and an organic EL element with high luminous efficiency is obtained.

"Other Examples" The organic EL element of the present invention is not limited to the organic EL element described in the above embodiments. Specifically, in the above-described embodiments, the case where the charge generation layer functions as an electron injection layer has been described as an example, but the organic EL element of the present invention only has the charge described in the present invention between two electrodes. layer can be generated. Therefore, the structures shown in FIGS. 5 to 10 also fall within the scope of the present invention.

In addition, in the organic EL element 100 shown in FIG. 11 , the intermediate layer 40 , the hole transport layer 50 , the hole transport layer 70 , and the hole injection layer 80 may be formed as needed, or not provided. In addition, each of the cathode 30 , the coating intermediate layer 40 , the hole transport layer 50 , the light emitting layer 60 , the hole transport layer 70 , the hole injection layer 80 , and the anode 90 may be formed by one layer, or may include two or more layers.

In addition, the organic EL element 100 shown in FIG. 11 may have other layers between the layers shown in FIG. 11 . Specifically, in order to further improve the characteristics and the like of the organic EL element, an electron blocking layer and the like may be provided as necessary.

In addition, in the above-mentioned embodiment, the organic EL element of the reverse structure in which the cathode 30 is arranged between the substrate 20 and the light-emitting layer 60 has been described as an example, but the organic EL element of any structure as shown in FIGS. 6 to 10 may be used as an example. EL element.

The organic EL element of the present invention can change the emission color by appropriately selecting the material of the light-emitting layer and the like, and can also obtain a desired emission color by using a color filter or the like in combination. Therefore, the organic EL element of the present invention can be preferably used as a light-emitting portion of a display device or a lighting device.

<Display device> The display device of the present invention is characterized by including the organic electroluminescent element. The display device of the present invention includes the organic EL element of the present invention having a charge generating layer between the cathode and the anode, excellent productivity, high luminous efficiency, and excellent driving stability. Therefore, the display device of the present invention is easy to manufacture, hardly deteriorates even in the presence of oxygen or moisture, and is excellent in light emission characteristics.

＜Lighting device＞ The lighting device of the present invention is characterized by including the organic electroluminescent element. The lighting device of the present invention includes the organic EL element of the present invention which is excellent in productivity, high in luminous efficiency, and excellent in driving stability. Therefore, the lighting device of the present invention is easy to manufacture, hardly deteriorates even in the presence of oxygen or moisture, and is excellent in light emission characteristics.

＜Organic thin film solar cells＞ The organic thin film solar cell of the present invention is characterized by including the charge generation layer. For example, in the case of using a charge generation layer in an organic thin film solar cell, it is particularly preferable to use a photoelectric conversion layer instead of the light emitting layer shown in FIGS. conversion layer. Thereby, light in a wide wavelength range can be efficiently converted into electric charges, and high power generation efficiency can be obtained. In addition, the organic thin-film solar cell of the present invention is easy to manufacture and hardly deteriorates even in the presence of oxygen or moisture.

The present invention is not limited to the above-described embodiments, and the charge generating layer of the present invention can be used in devices such as sensors, for example. [Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples at all. Here, a charge generation layer was formed on ITO with a large work function generally used as an anode, and electron generation (electron injection) from the ITO side was verified.

(Example 1) <Organic EL element production> The organic EL element 100 shown in FIG. 11 was manufactured and evaluated by the method shown below.

[step 1] As the substrate 20 , a commercially available transparent glass substrate having an average thickness of 0.7 mm and having an electrode (cathode 30 ) made of ITO and patterned to a width of 3 mm was prepared. Next, the substrate 20 having the cathode 30 was ultrasonically cleaned in acetone and isopropanol for 10 minutes, respectively, and boiled in isopropanol for 5 minutes. Then, the substrate 20 having the cathode 30 was taken out from isopropyl alcohol, dried by blowing nitrogen, and UV ozone cleaning was performed for 20 minutes.

[Step 2] On the ITO electrode (cathode 30 ) prepared in the above [Step 1], a 30 nm “Clevios” manufactured by Heraeus was formed as the coating intermediate layer 40 by spin coating. ) HIL1.3" (conductive polymer).

Next, the substrate 20 on which the coating intermediate layer 40 and the following layers are formed is fixed to the substrate holder of the vacuum vapor deposition apparatus. In addition, 4,4',4''-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA, free potential) represented by the following structural formula (10-1) =5.1 eV); 2,4,6-tris(m-pyridin-3-yl-phenyl)triazine (TmPPyTz) represented by the following structural formula (10-2); By the following structural formula (10-3 A compound (Py-hpp2) represented by ); Bis[2-(2-benzothiazolyl)phenol]zinc(II)(Zn(BTZ) ₂ ) represented by the following structural formula (10-4); from the following Tris[1-phenylisoquinoline]iridium (III) (Ir(piq) ₃ ) represented by the structural formula (10-5); N,N′-bis() represented by the following structural formula (10-6) 1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine (α-NPD); 1, represented by the following structural formula (10-7) 4,5,8,9,12-hexaazabitriphenylene-2,3,6,7,10,11-hexacarbonitrile (HAT-CN); and Al were placed in an alumina crucible and set as Evaporation source. [Chemical 17]

Then, the pressure in the chamber of the vacuum evaporation device was reduced to a pressure of 1×10 ⁻⁵ Pa, and the charge generation layer 10 , the light emitting layer 60 , and the hole transport layer 70 were successively formed by the vacuum evaporation method using resistance heating. , the hole injection layer 80 , and the anode 90 .

[Step 3] 10 nm m-MTDATA was formed on the coating intermediate layer 40 by vacuum evaporation as the hole transport layer 50 .

[Step 4] Next, a film obtained by co-evaporating m-MTDATA as a hole transport material and HAT-CN as an electron accepting material at a mass ratio of 1:1 is formed on the hole transport layer 50 as the p-doped layer 1 . The average film thickness is 10 nm.

[Step 5] Next, a 10 nm HAT-CN was formed as a dopant layer 3 on the p-doped layer 1 by a vacuum evaporation method.

[Step 6] Next, a film obtained by co-evaporating TmPPyTz as an electron transport material and Py-hpp2 as an electron donating material at a mass ratio of 7:3 was formed on the dopant layer 3 as the n-doped layer 2 . The average film thickness is 10 nm.

[Step 7] Next, the light-emitting layer 60 was formed by co-evaporation for 30 nm using Zn(BTZ) ₂ as a host and Ir(piq) ₃ as a dopant. At this time, the doping concentration was set so that Ir(piq) ₃ was 6 mass % with respect to the entire light-emitting layer 60 . Next, on the substrate 20 on which the light-emitting layer 60 was formed, a film of α-NPD having a thickness of 40 nm was formed to form the hole transport layer 70 . Further, HAT-CN was formed to a thickness of 10 nm to form a hole injection layer 80 . Next, on the substrate 20 on which the hole injection layer 80 was formed, the anode 90 made of aluminum with a film thickness of 100 nm was formed by a vacuum deposition method.

In addition, the anode 90 was formed into a strip shape with a width of 3 mm using a deposition mask made of stainless steel, and the light emitting area of the produced organic EL element was set to 9 mm ² .

[Step 8] Next, the substrate 2 on which the layers including the anode 90 and below are formed is housed in a glass cover (sealed container) having a concave space, and a sealing material made of an ultraviolet (UV) curing resin is filled to seal it. The organic EL element of Example 1 was obtained.

(Example 2) In [Step 6], the same procedures as in Example 1 were performed except that the phenanthroline compound (Phenan-OMe) represented by the following structural formula (10-8) was used as the electron donating material. The organic EL element was fabricated under the conditions. [Chemical 18]

(Example 3) In [Step 6], the same procedure as in Example 1 was carried out, except that the cyclic pyridine-based compound (AzPy) represented by the following structural formula (10-9) was used as the electron donating material. The organic EL element was fabricated under the conditions. [Chemical 19]

(Example 4) An organic EL element was produced under the same conditions as in Example 1 except that [Step 5] was omitted.

(Example 5) An organic EL element was produced under the same conditions as in Example 1, except that tris(8-quinoline)aluminum (Alq ₃ ) was used as the light-emitting layer 60 in [Step 7].

(Comparative Example 1) An organic EL element was produced under the same conditions as in Example 1, except that Py-hpp2 as an electron-donating material was not co-evaporated in [Step 6].

(Comparative Example 2) In [Step 6], 8-quinolinolatolithium (Liq) was used as the electron-donating material instead of Py-hpp2 as the lithium complex, and Alq ₃ was used as the light-emitting layer 60 . An organic EL element was produced under the same conditions as in Example 1.

(Measurement of Light Emitting Characteristics of Organic EL Elements) A voltage was applied to the produced organic EL element using a "2400 type power meter" manufactured by Kdthley, and the relationship between the applied voltage and the current density was investigated. Furthermore, the luminance was measured using "LS-100" manufactured by Konica Minolta, and the relationship between the current density and the external quantum efficiency was calculated from the obtained correlation of luminance-voltage-current value. These results are shown in Table 1.

[Table 1] Components Element Characteristics (Applied Voltage 6 V) Coating the intermediate layer 40 hole transport layer 50 p-doped layer 1 dopant layer 3 n-doped layer 2 Light-emitting layer 60 hole transport layer 70 hole injection layer 80 Anode 90 Current density (mA/cm ² ) Brightness (cd/m ² ) External quantum efficiency (%) Comparative Example 1 Clevios HIL1.3 m-MTDATA m-MTDATA +HAT-CN HAT-CN TmPPyTz Zn(BTZ) ₂ +Ir(piq) ₃ alpha-NPD HAT-CN Al 4.5 167 4.9 Example 1 Clevios HIL1.3 m-MTDATA m-MTDATA +HAT-CN HAT-CN TmPPyTz +Py-hpp2 Zn(BTZ) ₂ +Ir(piq) ₃ alpha-NPD HAT-CN Al 4.98 319 8.29 Example 4 Clevios HIL1.3 m-MTDATA m-MTDATA +HAT-CN without TmPPyTz +Py-hpp2 Zn(BTZ) ₂ +Ir(piq) ₃ alpha-NPD HAT-CN Al 1.38 127 12.2 Example 2 Clevios HIL1.3 m-MTDATA m-MTDATA +HAT-CN HAT-CN TmPPyTz + Phenan-OMe Zn(BTZ) ₂ +Ir(piq) ₃ alpha-NPD HAT-CN Al 0.7 52 9.0 Example 3 Clevios HIL1.3 m-MTDATA m-MTDATA +HAT-CN HAT-CN TmPPyTz +AzPy Zn(BTZ) ₂ +Ir(piq) ₃ alpha-NPD HAT-CN Al 3.4 337 12.3 Example 5 Clevios HIL1.3 m-MTDATA m-MTDATA +HAT-CN HAT-CN TmPPyTz +Py-hpp2 Alq ₃ alpha-NPD HAT-CN Al 0.19 4 0.7 Comparative Example 2 Clevios HIL1.3 m-MTDATA m-MTDATA +HAT-CN HAT-CN TmPPyTz +Liq Alq ₃ alpha-NPD HAT-CN Al 0.01 0 0

The comparison between Example 1 and Comparative Example 1 shows that the organic EL element composed of the charge generation layer containing Py-hpp2 and the electron transport material shows a higher display value than the organic EL element composed of the charge generation layer composed of only the electron transport material. Low driving voltage and high luminous efficiency. This is considered to be the result of the change in the energy level of the electron-transporting material by Py-hpp2 (alkali material, dopant), and the improvement of the electron-injecting property and the hole-blocking property.

From the comparison between Example 2 and Comparative Example 1, it can be seen that the organic EL element composed of the charge generation layer containing Phenan-OMe and the electron transport material also has a higher efficiency than the organic EL element composed of the charge generation layer composed of the electron transport material alone. Shows high luminous efficiency. This is considered to be a result of the improvement of the hole resistance due to the change in the energy level of the electron transport material by Phenan-OMe (alkali material, dopant).

From the comparison between Example 3 and Comparative Example 1, it was found that the organic EL element composed of the charge generation layer containing AzPy and the electron transport material also exhibited higher Low driving voltage and high luminous efficiency. This is considered to be a result of the change in the energy level of the electron-transporting material by AzPy (alkali material, dopant), and the improvement of the electron-injecting property and the hole-blocking property.

From the comparison between Example 1 and Example 4, it can be seen that the presence or absence of the dopant layer 3 has no great influence on the generation of electric charges.

From the comparison between Example 5 and Comparative Example 2, compared with the organic EL element in which Liq, which is a complex containing an alkali metal widely used for charge generation, is used in the n-doped layer 2, the n-doped layer 2 An organic EL element using Py-hpp2 as an alkali material in the layer 2 achieves high luminous efficiency at a low driving voltage, and an alkali material is preferable as the electron donating material. [Industrial Availability]

The charge generation layer of the present invention can be used in organic electroluminescent elements, display devices, lighting devices, organic thin film solar cells, and the like.

10: Charge generation layer 1: A layer containing a hole transport material and an electron accepting material (p-doped layer) 2: Layer containing electron-transporting material and electron-donating material (n-doped layer) 3: Layer containing only electron-accepting material or electron-donating material (dopant layer) 100: Organic EL (electroluminescence) element 20: Substrate 30: Cathode 40: Coating the intermediate layer 50: hole transport layer 60: Light-emitting layer 70: hole transport layer 80: hole injection layer 90: Anode 45: Electron Transport Layer 39: Electrodes 57: Charge transport layer

FIG. 1 is a schematic cross-sectional view for explaining one embodiment of the charge generation layer of the present invention. 2 is a schematic cross-sectional view for explaining another embodiment of the charge generation layer of the present invention. FIG. 3 is an explanatory diagram of energy levels of a charge generation layer to which no dopant is added. FIG. 4 is an explanatory diagram of energy levels of a dopant-added charge generation layer. 5 is a schematic cross-sectional view for explaining one embodiment of the organic EL element of the present invention. 6 is a schematic cross-sectional view for explaining another embodiment of the organic EL element of the present invention. 7 is a schematic cross-sectional view for explaining another embodiment of the organic EL element of the present invention. 8 is a schematic cross-sectional view for explaining another embodiment of the organic EL element of the present invention. 9 is a schematic cross-sectional view for explaining another embodiment of the organic EL element of the present invention. 10 is a schematic cross-sectional view for explaining another embodiment of the organic EL element of the present invention. 11 is a schematic cross-sectional view for explaining an example of the organic EL element of the present invention.

10: Charge generation layer

1: Layer (p-doped layer) containing a hole-transporting material and an electron-accepting material

2: Layer containing electron-transporting material and electron-donating material (n-doped layer)

Claims (11)

A charge generation layer comprising: a layer containing a hole transport material and an electron accepting material, and a layer containing an electron transport material and an electron donating material, wherein the electron accepting material is a layer containing a selected A material containing a substituent in fluorine, chlorine, cyano, nitro, and carbonyl, the electron-donating material is selected from tertiary amines with an acid dissociation constant pKa of 1 or more, phosphazene compounds, guanidine compounds, and amidine-containing compounds Heterocyclic compounds, hydrocarbon compounds having a ring structure, phenanthroline-based compounds, terpyridine-based compounds, and cyclic pyridine-based compounds, wherein the charge generating layer does not contain an alkali metal or metal oxide, and the charge generating layer contains a hole transport property The layer of the material and the electron-accepting material is directly laminated with the layer containing the electron-transporting material and the electron-donating material. The charge generating layer according to claim 1, wherein the free potential of the hole-transporting material is less than 5.7 eV, and the electron-accepting material is capable of undergoing a redox reaction with the hole-transporting material. An organic substance that forms a charge transfer complex, and the electron-donating material is an organic substance capable of forming a hydrogen bond with the electron-transporting material. A charge generating layer comprising: a layer containing a hole transport material and an electron accepting material, a layer containing an electron transport material and an electron donating material, and a layer containing only the electron accepting material or the Electron donating A layer of materials, wherein the electron-accepting material is a material containing a substituent selected from fluorine, chlorine, cyano, nitro, and carbonyl, and the electron-donating material is selected from an acid dissociation constant pKa of 1 or more Tertiary amines, phosphazene compounds, guanidine compounds, heterocyclic compounds containing an amidine structure, hydrocarbon compounds having a ring structure, phenanthroline-based compounds, terpyridine-based compounds, and cyclic pyridine-based compounds, the charge generating layer does not contain Alkali metal, metal oxide, and the layer including the hole transport material and the electron accepting material and the layer including the electron transport material and the electron donating material by including only the electron accepting material or the The layers of the electron donating material are stacked. The charge generating layer according to claim 3, wherein the free potential of the hole-transporting material is less than 5.7 eV, and the electron-accepting material is capable of undergoing a redox reaction with the hole-transporting material. An organic substance that forms a charge transfer complex, and the electron-donating material is an organic substance capable of forming a hydrogen bond with the electron-transporting material. A method for manufacturing a charge generating layer, characterized in that it is a method for manufacturing the charge generating layer as described in any one of claim 1 to claim 4, comprising: co-evaporating a hole transport material and an electron accepting material , forming a layer comprising a hole transport material and an electron accepting material; and co-evaporating the electron transport material and the electron donating material to form a layer comprising an electron transport material A step of layering a transporting material and an electron donating material. An organic electroluminescent element, characterized by comprising a cathode, a light-emitting layer and an anode in sequence, wherein the charge according to any one of claim 1 to claim 4 is included between the cathode and the light-emitting layer A generation layer, the layer including the hole transport material and the electron accepting material is disposed on the cathode side, and the layer including the electron transport material and the electron donating material is disposed on the light emitting layer side. An organic electroluminescent element, characterized by comprising a cathode, a light-emitting layer and an anode in sequence, wherein the charge according to any one of claim 1 to claim 4 is included between the anode and the light-emitting layer A generation layer, the layer including the hole transport material and the electron accepting material is arranged on the side of the light emitting layer, and the layer including the electron transport material and the electron donating material is arranged on the side of the anode. An organic electroluminescent element, characterized in that it comprises a cathode and an anode, and between the cathode and the anode, there are two or more light-emitting layers, wherein one of the light-emitting layers and the light-emitting layer The charge generation layer according to any one of claim 1 to claim 4 is included between another layer of the . A display device, characterized in that it includes, such as request item 6 to request The organic electroluminescent element according to any one of Item 8. A lighting device, characterized by comprising the organic electroluminescent element according to any one of claim 6 to claim 8. An organic thin film solar cell characterized by comprising the charge generation layer according to any one of claim 1 to claim 4.

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