WO2022018577A1 - 有機金属錯体の製造方法 - Google Patents

有機金属錯体の製造方法 Download PDF

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WO2022018577A1
WO2022018577A1 PCT/IB2021/056319 IB2021056319W WO2022018577A1 WO 2022018577 A1 WO2022018577 A1 WO 2022018577A1 IB 2021056319 W IB2021056319 W IB 2021056319W WO 2022018577 A1 WO2022018577 A1 WO 2022018577A1
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substituted
carbon atoms
unsubstituted
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French (fr)
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山口知也
高畑正利
吉住英子
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table

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  • One aspect of the present invention relates to a method for producing an organometallic complex.
  • the present invention relates to a method for producing an organometallic complex capable of converting energy in a triplet excited state into light emission.
  • Light-emitting devices also called organic EL elements
  • organic EL elements that have an organic compound that is a light-emitting substance between a pair of electrodes have characteristics such as thinness, light weight, high-speed response, and low-voltage drive. It is being advanced over.
  • the light emitting device recombines electrons and holes injected from the electrode, whereby the luminescent substance becomes an excited state, and when the excited state returns to the ground state, it emits light.
  • There are two types of excited states: singlet excited state (S * ) and triplet excited state (T * ). Emission from the singlet excited state is fluorescence, and emission from the triplet excited state is phosphorescence. being called. Further, their statistical generation ratio in the light emitting device is considered to be S * : T * 1: 3.
  • a compound capable of converting energy in a singlet excited state into light emission is called a fluorescent compound (fluorescent material), and it is possible to convert energy in a triplet excited state into light emission.
  • fluorescent compound fluorescent material
  • Compounds are called phosphorescent compounds (phosphorescent materials).
  • the theoretical limit of the internal quantum efficiency (ratio of photons generated to the injected carriers) in the light emitting device using each of the above luminescent substances is the case where a fluorescent material is used. Is 25%, and 75% when a phosphorescent material is used.
  • a light emitting device using a phosphorescent material can obtain higher efficiency than a light emitting device using a fluorescent material. Therefore, in recent years, various types of phosphorescent materials have been actively developed.
  • an organometallic complex having iridium or the like as a central metal has attracted attention in terms of practical use (for example, Patent Document 1).
  • a novel method for producing an organometallic complex is provided. Further, another aspect of the present invention provides a production method for obtaining an organometallic complex in a high yield.
  • the description of these issues does not preclude the existence of other issues. Moreover, one aspect of the present invention does not necessarily have to solve all of these problems.
  • problems other than these are naturally clarified from the description of the description, drawings, claims, etc., and it is possible to extract problems other than these from the description of the description, drawings, claims, etc. Is.
  • One aspect of the present invention is a method for producing an organic metal complex in which a dinuclear complex containing a cyano group crosslinked with chlorine and ⁇ -diketone are reacted in the presence of an aprotic solvent having a boiling point of 80 ° C. or higher and a base. ..
  • an aprotic solvent having a boiling point of 80 ° C. or higher and a base.
  • the aprotic solvent an ether solvent, a nitrile solvent, an amide solvent and the like are preferable.
  • Another aspect of the present invention is a method for producing an organic metal complex in which a dinuclear complex containing a cyano group crosslinked with chlorine and ⁇ -diketone are reacted in the presence of an amide compound having a boiling point of 80 ° C. or higher and a base.
  • an amide compound having a boiling point of 80 ° C. or higher and a base.
  • the amide compound N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like are preferable.
  • the dinuclear complex preferably has pyrazine. Further, in the above configuration, it is preferable that the dinuclear complex has pyrazine and the central metal is iridium.
  • Another aspect of the present invention is a method for producing a cyclometal complex in which a dinuclear complex containing a cyano group crosslinked with chlorine and ⁇ -diketone are reacted in the presence of an aprotic solvent having a boiling point of 80 ° C. or higher and a base.
  • an aprotic solvent having a boiling point of 80 ° C. or higher and a base.
  • the aprotic solvent an ether solvent, a nitrile solvent, an amide solvent and the like are preferable.
  • Another aspect of the present invention is a method for producing a cyclometal complex in which a dinuclear complex containing a cyano group crosslinked with chlorine and ⁇ -diketone are reacted in the presence of an amide compound having a boiling point of 80 ° C. or higher and a base.
  • an amide compound having a boiling point of 80 ° C. or higher and a base.
  • the amide compound N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like are preferable.
  • the dinuclear complex preferably has pyrazine.
  • a dinuclear complex containing a cyano group represented by the general formula (Gp) and a ⁇ -diketone represented by the general formula (L1) are aprotic with a boiling point of 80 ° C. or higher. It is a method for producing an organic metal complex to be reacted in the presence of a solvent and a base.
  • a 1 to A 4 independently represent substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms
  • R 1 to R 6 are independently hydrogen, substituted or substituted, respectively. It represents any of an unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • R 20 to R 22 are independently hydrogen or substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, halogen group, vinyl group, substituted or unsubstituted carbon number 1 to 1 to 6, respectively.
  • another aspect of the present invention is an amide compound having a dinuclear complex containing a cyano group represented by the general formula (Gp) and a ⁇ -diketone represented by the general formula (L1) having a boiling point of 80 ° C. or higher. It is a method for producing an organic metal complex to be reacted in the presence of a base.
  • a 1 to A 4 independently represent substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms
  • R 1 to R 6 are independently hydrogen, substituted or substituted, respectively. It represents any of an unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • R 20 to R 22 are independently hydrogen or substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, halogen group, vinyl group, substituted or unsubstituted carbon number 1 to 1 to 6, respectively.
  • an organometallic complex represented by the following general formula (G1) can be obtained.
  • a 1 to A 4 independently represent substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms
  • R 1 to R 6 are independently hydrogen and substituted, respectively.
  • it represents any of an unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • L represents a monoanionic ligand having a ⁇ -diketone structure.
  • R 7 to R 11 is an alkyl group having 1 to 6 carbon atoms. Further, in particular, in order to prevent the emission spectrum peak from going too far to a long wavelength and to maintain the luminosity factor, it is preferable that at least one of R 7 or R 11 is an alkyl group having 1 to 6 carbon atoms. That is, this configuration is particularly suitable for obtaining a deep red color with high color purity and high efficiency.
  • the organometallic complex represented by the above general formula (G1) can emit phosphorescence, that is, it can obtain and emit light from a triplet excited state, it can be used as a light emitting device. By applying it, high efficiency can be achieved and it is very effective. Therefore, a light emitting device using an organometallic complex obtained by the production method according to one aspect of the present invention (for example, used for an EL layer between a pair of electrodes) is included in one aspect of the present invention.
  • one aspect of the present invention also includes a light emitting device having the above-mentioned light emitting device and a lighting device having a light emitting device. Therefore, the light emitting device in the present specification refers to an image display device or a light source (including a lighting device).
  • a module in which a connector for example, an FPC (Flexible printed circuit) or TCP (Tape Carrier Package) is attached to the light emitting device, a module in which a printed wiring board is provided at the end of the TCP, or a COG (Chip On Glass) in the light emitting device. All modules in which an IC (integrated circuit) is directly mounted by the method shall be included in the light emitting device.
  • FIG. 1A and 1B are diagrams illustrating the structure of the light emitting element.
  • 2A and 2B are diagrams illustrating the structure of the light emitting element.
  • FIG. 3 is a 1 H-NMR chart of the organometallic complex represented by the structural formula (100).
  • FIG. 4 is a diagram showing the relationship between the heating temperature and the yield.
  • Synthetic method of pyrazine derivative represented by general formula (G0) >> The pyrazine derivative represented by the following general formula (G0) used for the synthesis of the organometallic complex represented by the above general formula (G1) has the following three types of synthesis schemes (A1) and (A2). It can be synthesized by the synthesis method shown in (A3).
  • a 1 to A 4 each independently represent a substituted or substituted alkyl group having 1 to 6 carbon atoms
  • R 1 to R 6 are independently hydrogen, substituted or absent, respectively. It represents any of a substituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • the halogenated benzene derivative (a1-1) is lithiolated with an alkyllithium or the like to diphenylpyrazine (a2-1). It can be obtained by reacting with.
  • Z represents a halogen
  • a 1 ⁇ A 4 each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms
  • R 1 ⁇ R 6 is Independently, any of hydrogen, an substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms. Represents.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • the pyrazine derivative represented by the general formula (G0) includes a benzene derivative boronic acid (a1-2), a halide of diphenylpyrazine (a2-2), and a halide of diphenylpyrazine (a2-2), as shown in the following synthesis scheme (A2). Can be obtained by coupling.
  • X represents a halogen
  • a 1 to A 4 each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms
  • R 1 to R 6 independently represent each.
  • Hydrogen substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, substituted or unsubstituted aryl group having 6 to 13 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms. ..
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • the pyrazine derivative represented by the general formula (G0) is obtained by reacting the benzene derivative-substituted diketone (a1-3) with the diamine (a2-3) as shown in the following synthesis scheme (A3).
  • G0 benzene derivative-substituted diketone
  • A3 diamine
  • a 1 to A 4 each independently represent a substituted or substituted alkyl group having 1 to 6 carbon atoms, and R 1 to R 6 are independently hydrogen, substituted or absent, respectively. It represents any of a substituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • the organometallic complex which is one aspect of the present invention is characterized by having abundant variations of its ligand.
  • the heating means is not particularly limited, and an oil bath, a sand bath, an aluminum block, or the like can be used. It is also possible to use microwaves as a heating means.
  • X represents a halogen
  • a 1 to A 4 each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms
  • R 1 to R 6 represent each.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • the dinuclear complex (Gp) obtained by the above synthesis scheme (B-1) and the ⁇ -diketone (HL) are reacted in an inert gas atmosphere.
  • L which is the desorption of the proton of HL, coordinates with the central metal iridium, so that an organic metal complex represented by the general formula (G1) can be obtained.
  • an aprotonic solvent is preferable from the viewpoint of yield, and ether solvents such as 1,4-dioxane, anisole, 1,2-dimethoxyethane and diethylene glycol dimethyl ether, acetonitrile, propionitrile and the like.
  • a nitrile-based solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like can be used. Since an aprotic solvent hinders the generation of protons more than a protonic solvent, for example, a cyano group is formed by reacting a proton as an electrophile with a cyano group having a high electron density contained in an organic metal complex. Can suppress side reactions such as desorption. Thereby, the yield in the above reaction can be improved.
  • the heating means is not particularly limited, and an oil bath, a sand bath, an aluminum block, or the like can be used. It is also possible to use microwaves as a heating means.
  • L represents a ⁇ -diketone desorbed from a proton
  • X represents a halogen
  • a 1 to A 4 are independently substituted or unsubstituted alkyls having 1 to 6 carbon atoms.
  • R 1 to R 6 are independently hydrogen, substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, substituted or unsubstituted aryl group having 6 to 13 carbon atoms, substituted or unsubstituted.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • the organic metal complex synthesized in the present embodiment has a central metal, iridium, and a ligand, the ligand has a pyrazine skeleton, and iridium and nitrogen at the 1-position of the pyrazine skeleton are bonded.
  • a phenyl group is attached to the pyrazine skeleton at the 2, 3, and 5 positions, respectively, and each of the phenyl groups bonded to the 2 and 3 positions has an alkyl group as a substituent and is bonded to the 5 position.
  • the phenyl group is an organic metal complex having a cyano group as a substituent.
  • the organic metal complex shown in the present embodiment has a first ligand and a second ligand that bind to iridium, which is a central metal, and the first ligand is pyrazine. It has a skeleton, and iridium and nitrogen at the 1-position of the pyrazine skeleton are bonded, and phenyl groups are bonded to the pyrazine skeleton at the 2, 3, and 5-positions, respectively, and phenyl groups bonded to the 2- and 3-positions are bonded to the pyrazine skeleton.
  • Each has an alkyl group as a substituent
  • the phenyl group bonded to the 5-position has a cyano group as a substituent
  • the second ligand is a monoanionic bidentate chelate having a ⁇ -diketone structure. It is an organic metal complex that is a ligand.
  • a phenyl group having an alkyl group as a substituent is bonded to the 2-position and the 3-position of the pyrazine skeleton contained in the ligand, respectively, and the phenyl group having an alkyl group as a substituent is bonded to the 5-position of the pyrazine skeleton.
  • a phenyl group having a cyano group as a substituent is bonded.
  • the phenyl group bonded to the 2-position of the pyrazine skeleton is orthometalized with respect to iridium.
  • the phenyl group bonded to the 2-position and the 3-position of the pyrazine skeleton each has an alkyl group as a substituent, carbonization due to the reaction between the organometallic complexes during sublimation occurs. It can be prevented and the sublimation temperature can be further reduced. Further, by having a cyano group as a substituent of the phenyl group bonded to the 5-position of the pyrazine skeleton, the sublimation temperature is higher than that in the case of not having the cyano group, but the treatment is performed at a high temperature during sublimation. Also, it is possible to prevent the generation of low molecular weight decomposition products derived from the above alkyl group, that is, the generation of desorbed gas due to the generation.
  • the organic metal complex shown in the present embodiment has the effect of lengthening the emission spectrum of the organic metal complex by having the above cyano group, it has high color purity and exhibits deep red emission.
  • it exhibits deep red emission it usually has a spectrum in the near infrared region, so that the luminosity factor deteriorates, but the above-mentioned alkyl group (alkyl group possessed by a phenyl group bonded to the 2-position and 3-position of the pyrazine skeleton).
  • the organometallic complex can obtain high efficiency even in deep red with high color purity.
  • the phenyl group bonded to the 5-position of the pyrazine skeleton has not only a cyano group but also an alkyl group in order to suppress carbonization due to the reaction between the organic metal complexes.
  • the alkyl group at the 2-position of the phenyl group bonded to the 5-position of the pyrazine skeleton it is possible to prevent the emission spectrum peak from going too far to a long wavelength and maintain the luminosity factor. That is, it is particularly suitable for obtaining a deep red color having high color purity and high efficiency.
  • the organometallic complex shown in this embodiment is an organometallic complex represented by the following general formula (G1).
  • a 1 to A 4 independently represent substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, and R 1 to R 6 are independently hydrogen and substituted, respectively. Alternatively, it represents any of an unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • L represents a monoanionic ligand having a ⁇ -diketone structure.
  • the organometallic complex shown in this embodiment is an organometallic complex represented by the following general formula (G2).
  • a 1 to A 4 each independently represent a substituted or substituted alkyl group having 1 to 6 carbon atoms
  • R 6 is hydrogen, substituted or unsubstituted carbon number 1
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • L represents a monoanionic ligand having a ⁇ -diketone structure.
  • the monoanionic ligand having the ⁇ -diketone structure is represented by the following general formula (L1).
  • R 71 to R 73 are independently hydrogen or substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, halogen group, vinyl group, substituted or unsubstituted carbon number 1 to 1 to 6, respectively.
  • organometallic complex shown in this embodiment is an organometallic complex represented by the following general formula (G3).
  • a 1 to A 4 independently represent substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, and R 1 to R 6 are independently hydrogen and substituted, respectively. Alternatively, it represents any of an unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number. It represents any of 3 to 12 heteroaryl groups and cyano groups, and at least one represents a cyano group.
  • R 71 and R 73 are independently hydrogen or substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, halogen group, vinyl group, substituted or unsubstituted haloalkyl group having 1 to 6 carbon atoms, substituted or substituted. It represents an unsubstituted alkoxy group having 1 to 6 carbon atoms or an substituted or unsubstituted alkylthio group having 1 to 6 carbon atoms.
  • organometallic complex shown in this embodiment is an organometallic complex represented by the following general formula (G4).
  • a 1 to A 4 each independently represent a substituted or substituted alkyl group having 1 to 6 carbon atoms
  • R 6 is hydrogen, substituted or unsubstituted carbon number 1
  • R 7 to R 11 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms substituted or unsubstituted, an aryl group having 6 to 13 carbon atoms substituted or unsubstituted, and a substituted or unsubstituted carbon number.
  • R 71 and R 73 are independently hydrogen or substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, halogen group, vinyl group, substituted or unsubstituted haloalkyl group having 1 to 6 carbon atoms, substituted or substituted. It represents an unsubstituted alkoxy group having 1 to 6 carbon atoms or an substituted or unsubstituted alkylthio group having 1 to 6 carbon atoms.
  • a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, a substituted or unsubstituted alkyl group.
  • the substituents include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and a pentyl.
  • An alkyl group having 1 to 6 carbon atoms such as a group and a hexyl group, a cycloalkyl group having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-norbornyl group and a 2-norbornyl group, and a cycloalkyl group having 5 to 7 carbon atoms.
  • Examples thereof include an aryl group having 6 to 12 carbon atoms such as a phenyl group and a biphenyl group.
  • alkyl group having 1 to 6 carbon atoms in any of A 1 to A 4 and R 1 to R 11 in the above general formulas (G1) to (G4) include a methyl group, an ethyl group, and a propyl group.
  • aryl group having 6 to 13 carbon atoms in any of A 1 to A 4 and R 1 to R 11 in the above general formulas (G1) to (G4) include a phenyl group and a tolyl group (o).
  • the above-mentioned substituents may be bonded to each other to form a ring.
  • the carbon at the 9-position of the fluorenyl group has two phenyl groups as substituents, and the phenyl group is used. Examples thereof include the case where a spirofluorene skeleton is formed by binding the groups to each other.
  • heteroaryl group having 3 to 12 carbon atoms in any of A 1 to A 4 and R 1 to R 11 in the above general formulas (G1) to (G4) include an imidazolyl group and a pyrazolyl group.
  • examples thereof include a pyridyl group, a pyridadyl group, a triazil group, a benzoimidazolyl group, and a quinolyl group.
  • this alkyl group has such an effect, it produces a small amount of low molecular weight degradation products with sublimation, which reduces the life of the light emitting device.
  • the sublimation temperature is higher than that in the case of not having a cyano group. Even if the treatment is carried out at a high temperature during sublimation, it is possible to prevent the generation of low molecular weight decomposition products derived from the above alkyl group, that is, the generation of desorbed gas due to the generation.
  • the organometallic complex has an alkyl group as a substituent in each of A 1 to A 4 in the general formulas (G1) to (G4), and a cyano group is substituted in at least one of R 7 to R 11. It is characterized by having it as a base. Therefore, when a device is manufactured by vacuum vapor deposition using this organometallic complex, it is possible to suppress the mixing of decomposition products into the device, so that a device having good life characteristics can be obtained.
  • the organometallic complex may have an alkyl group in one of A 1 or A 2 and one of A 3 or A 4 and a cyano group in at least one of R 7 to R 11. This configuration is necessary to suppress carbonization due to the reaction between organometallic complexes and generation of low molecular weight desorbed gas.
  • the cyano group possessed by at least one of R 7 to R 11 has an effect of lengthening the emission spectrum of the organometallic complex. That is, the organometallic complex shown in this embodiment has high color purity and exhibits deep red emission. Incidentally, in the case shown a deep red emission, usually visibility because it has a spectrum in the near infrared region is deteriorated, an alkyl group introduced into A 1 ⁇ A 4 also has effect of Semasen the emission spectrum Therefore, the decrease in visual sensitivity can be suppressed to the maximum. Therefore, the organometallic complex can obtain high efficiency even in deep red with high color purity.
  • the phenyl group bonded to the 5-position of the pyrazine skeleton has not only a cyano group but also an alkyl group due to the reaction between the organic metal complexes during sublimation. It is more preferable in suppressing carbonization. Therefore, in the above general formulas (G1) to (G4), it is preferable that at least one of R 7 to R 11 is an alkyl group having 1 to 6 carbon atoms. In particular, when at least one of R 7 or R 11 is an alkyl group having 1 to 6 carbon atoms, it is possible to prevent the emission spectrum peak from going too far to a long wavelength and maintain visibility. That is, in the above-mentioned organometallic complex, a deep red color having high color purity and high efficiency can be obtained.
  • the organometallic complex represented by the structural formulas (100) to (125) is a novel substance capable of emitting phosphorescence. These substances may have geometric isomers and steric isomers depending on the type of ligand, but the organic metal complex shown here also includes all of these isomers.
  • the organometallic complex synthesized by the above-mentioned synthesis method can emit phosphorescence, it can be used as a light emitting material or a light emitting substance of a light emitting device.
  • the organic metal complex produced by the production method according to one aspect of the present invention it is possible to realize a light emitting device, a light emitting device, an electronic device, or a lighting device having high luminous efficiency. Further, it is possible to realize a light emitting device, a light emitting device, an electronic device, or a lighting device having low power consumption.
  • an EL layer 102 including a light emitting layer 113 is sandwiched between a pair of electrodes (a first electrode (anode) 101 and a second electrode (cathode) 103), and the EL layer is formed.
  • the 102 is formed to include a hole (or hole) injection layer 111, a hole transport layer 112, an electron transport layer 114, an electron injection layer 115, and the like in addition to the light emitting layer 113.
  • the holes injected from the first electrode 101 side and the electrons injected from the second electrode 103 side are recombinated in the light emitting layer 113, whereby the holes are recombinated in the light emitting layer 113. Due to the generated energy, a light emitting substance such as an organic metal complex contained in the light emitting layer 113 emits light.
  • the hole injection layer 111 in the EL layer 102 is a layer capable of injecting holes into the hole transport layer 112 or the light emitting layer 113, and is, for example, a substance having a high hole transport property and an acceptor substance. Can be formed by. In this case, holes are generated by extracting electrons from the substance having high hole transport property by the acceptor substance. Therefore, holes are injected from the hole injection layer 111 into the light emitting layer 113 via the hole transport layer 112.
  • a substance having a high hole injecting property can also be used for the hole injecting layer 111. For example, molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, manganese oxide and the like can be used.
  • phthalocyanine compounds such as phthalocyanine (abbreviation: H 2 Pc) and copper phthalocyanine (CuPc), 4,4'-bis [N- (4-diphenylaminophenyl) -N-phenylamino] biphenyl (abbreviation:: DPAB), N, N'-bis ⁇ 4- [bis (3-methylphenyl) amino] phenyl ⁇ -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine (abbreviation:
  • the hole injection layer 111 can also be formed by an aromatic amine compound such as DNTPD) or a polymer such as poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonic acid) (PEDOT / PSS).
  • DNTPD aromatic amine compound
  • PEDOT poly(styrenesulfonic acid)
  • Metals, alloys, electrically conductive compounds, mixtures thereof, and the like can be used for the first electrode (anode) 101 and the second electrode (cathode) 103.
  • indium oxide-tin oxide, silicon or indium oxide containing silicon oxide-tin oxide, indium oxide-zinc oxide (Indium Zinc Oxide), tungsten oxide and indium oxide containing zinc oxide can be used for the first electrode (anode) 101 and the second electrode (cathode) 103.
  • the first electrode (anode) 101 and the second electrode (cathode) 103 can be formed by, for example, a sputtering method, a vapor deposition method (including a vacuum vapor deposition method), or the like.
  • Examples of the highly hole-transporting substance used for the hole injection layer 111 and the hole transport layer 112 include aromatic amine compounds, carbazole derivatives, aromatic hydrocarbons, and polymer compounds (oligomers, dendrimers, polymers, etc.).
  • Various organic compounds can be used.
  • the organic compound used for the composite material is preferably an organic compound having a high hole transport property. Specifically, it is preferably a substance having a hole mobility of 1 ⁇ 10 -6 cm 2 / Vs or more.
  • the layer made of a substance having a high hole transport property may be not only a single layer but also a laminated layer of two or more layers.
  • the organic compounds that can be used as hole-transporting substances are specifically listed below.
  • examples of the aromatic amine compound include N, N'-di (p-tolyl) -N, N'-diphenyl-p-phenylenediamine (abbreviation: DTDPPA), 4,4'-bis [N- (4- (4-).
  • Diphenylaminophenyl) -N-phenylamino] biphenyl (abbreviation: DPAB), DNTPD, 1,3,5-tris [N- (4-diphenylaminophenyl) -N-phenylamino] benzene (abbreviation: DPA3B), 4 , 4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPB or ⁇ -NPD) and N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine (abbreviation: TPD), 4,4', 4''-tris (carbazole-9-yl) triphenylamine (abbreviation: TCTA), 4,4 ', 4''-Tris (N, N-diphenylamino) triphenylamine (abbre
  • carbazole derivative examples include 3- [N- (9-phenylcarbazole-3-yl) -N-phenylamino] -9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis [ N- (9-Phenylcarbazole-3-yl) -N-Phenylamino] -9-Phenylcarbazole (abbreviation: PCzPCA2), 3- [N- (1-naphthyl) -N- (9-Phenylcarbazole-3-3) Il) Amino] -9-Phenylcarbazole (abbreviation: PCzPCN1) and the like can be mentioned.
  • PCzPCA1 3- [N- (9-phenylcarbazole-3-yl) -N-phenylamino] -9-phenylcarbazole
  • PCzPCA2 3,6-bis [ N- (9-Phenylcarbazole-3-yl) -
  • CBP 4,4'-di (N-carbazolyl) biphenyl
  • TCPB 1,3,5-tris [4- (N-carbazolyl) phenyl] benzene
  • CzPA 9- [4 -(10-Phenyl-9-anthryl) phenyl] -9H-carbazole
  • CzPA 1,4-bis [4- (N-carbazolyl) phenyl] -2,3,5,6-tetraphenylbenzene, etc.
  • aromatic hydrocarbons examples include 2-tert-butyl-9,10-di (2-naphthyl) anthracene (abbreviation: t-BuDNA) and 2-tert-butyl-9,10-di (1-).
  • pentacene, coronene and the like can also be used.
  • the aromatic hydrocarbon may have a vinyl skeleton.
  • aromatic hydrocarbons having a vinyl group include 4,4'-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi) and 9,10-bis [4- (2,2-).
  • Diphenylvinyl) phenyl] anthracene abbreviation: DPVPA
  • poly (N-vinylcarbazole) (abbreviation: PVK), poly (4-vinyltriphenylamine) (abbreviation: PVTPA), poly [N- (4- ⁇ N'-[4- (4-diphenylamino)) Phenyl] phenyl-N'-phenylamino ⁇ phenyl) methacrylicamide] (abbreviation: PTPDMA), poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) benzidine] (abbreviation: A polymer compound such as Poly-TPD) can also be used.
  • PVK poly (N-vinylcarbazole)
  • PVTPA poly (4-vinyltriphenylamine)
  • PTPDMA poly [N- (4- ⁇ N'-[4- (4-diphenylamino) Phenyl] phenyl-N'-phenylamino ⁇ phenyl) methacrylic
  • acceptor substance used for the hole injection layer 111 and the hole transport layer 112 7,7,8,8-(abbreviation: F 4 -TCNQ), chloranil, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN) and other electron acceptors (halogen groups and cyano)
  • HAT-CN 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • HAT-CN 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • HAT-CN 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • HAT-CN 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • HAT-CN 2,3,6,7,10
  • vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, and renium oxide are preferable because they have high electron acceptability.
  • molybdenum oxide is particularly preferable because it is stable in the atmosphere, has low hygroscopicity, and is easy to handle.
  • the light emitting layer 113 is a layer containing a light emitting substance.
  • the luminescent substance include a fluorescent luminescent substance and a phosphorescent luminescent substance.
  • the organic metal complex shown in the first embodiment is used as the luminescent substance. It is preferably used for the light emitting layer 113.
  • the light emitting layer 113 preferably contains a substance having a triplet excitation energy larger than that of the organometallic complex (guest material) as a host material.
  • the light emitting layer 113 is a combination of two kinds of organic substances capable of forming an excited complex (also referred to as an excyplex) at the time of recombination of carriers (electrons and holes) in the light emitting layer 113 in addition to the light emitting substance.
  • the composition may contain a compound (which may be any of the above host materials).
  • it is particularly preferable to combine a compound that easily receives electrons (a material having an electron transport property) and a compound that easily receives holes (a material having a hole transport property). ..
  • the mixing ratio of the material having electron transporting property and the material having hole transporting property is used.
  • Examples of compounds (materials having electron transporting properties) that are preferable to be used in forming the above-mentioned excitation complex and that easily receive electrons include ⁇ -electron-deficient heteroaromatic compounds such as nitrogen-containing heteroaromatic compounds and metal complexes. Can be used. Specifically, bis (10-hydroxybenzo [h] quinolinato) berylium (II) (abbreviation: BeBq 2 ), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (III) (abbreviation).
  • heterocyclic compounds having a pyridine skeleton such as -9-yl) phenyl] pyridine (abbreviation: 35DCzPPy) and 1,3,5-tri [3- (3-pyrimidyl) phenyl] benzene (abbreviation: TmPyPB).
  • the heterocyclic compound having a diazine skeleton and the triazine skeleton and the heterocyclic compound having a pyridine skeleton are preferable because they have good reliability.
  • a heterocyclic compound having a diazine (pyrimidine or pyrazine) skeleton and a triazine skeleton has high electron transport properties and contributes to reduction of driving voltage.
  • a compound (material having hole transporting property) preferable for being used for forming the above-mentioned excitation complex a ⁇ -electron excess type heteroaromatic (for example, a carbazole derivative or an indole derivative) or an aromatic is used. Amine or the like can be preferably used.
  • the light emitting layer 113 By forming the light emitting layer 113 by including the above-mentioned organometallic complex (guest material) and the host material, phosphorescent light emission with high luminous efficiency can be obtained from the light emitting layer 113.
  • the light emitting layer 113 is not limited to the single layer structure shown in FIG. 1A in the light emitting device, and may have a laminated structure of two or more layers as shown in FIG. 1B.
  • the configuration is such that the respective light emission can be obtained from each of the stacked layers.
  • the configuration is such that fluorescence emission can be obtained from the first light emitting layer 113 (a1), and phosphorescence is obtained from the second light emitting layer 113 (a2) laminated on the first light emitting layer 113 (a1).
  • the configuration may be such that light emission can be obtained.
  • the stacking order may be reversed.
  • the layer where phosphorescence emission can be obtained it is preferable to have a configuration in which light emission can be obtained by energy transfer from the excited complex to the dopant.
  • the emission color the emission color obtained from one layer and the emission color obtained from the other layer may be the same or different, but if they are different, for example, one of them may be used.
  • the structure may be such that blue light emission can be obtained from the layer, and orange light emission or yellow light emission can be obtained from the other layer.
  • each layer may be configured to include a plurality of types of dopants.
  • a luminescent material that converts singlet excitation energy into luminescence in addition to the organic metal complex shown in the first embodiment, a luminescent material that converts singlet excitation energy into luminescence, a luminescent material that converts triplet excitation energy into luminescence, and the like. Can be used alone or in combination. In this case, for example, the following may be mentioned.
  • Examples of the luminescent substance that converts the singlet excitation energy into luminescence include a substance that emits fluorescence (fluorescent compound).
  • Examples of the fluorescent substance include N, N'-bis [4- (9H-carbazole-9-yl) phenyl] -N, N'-diphenylstylben-4,4'-diamine (abbreviation: YGA2S), 4-.
  • Examples of the luminescent substance that converts triplet excited energy into light emission include a substance that emits phosphorescence (phosphorescent compound) and a TADF material that exhibits thermal activated delayed fluorescence (TADF) (thermally activated delayed fluorescent compound).
  • the delayed fluorescence in the TADF material refers to light emission having a spectrum similar to that of normal fluorescence but having an extremely long lifetime. Its life is 1 ⁇ 10-6 seconds or longer, preferably 1 ⁇ 10 -3 seconds or longer.
  • Phosphorescent substances include bis ⁇ 2- [3', 5'-bis (trifluoromethyl) phenyl] pyridinato-N, C 2' ⁇ iridium (III) picolinate (abbreviation: [Ir (CF 3 py) 2 ).
  • the TADF material examples include fullerene and its derivatives, acridine derivatives such as proflavin, and eosin.
  • metal-containing porphyrins containing magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), palladium (Pd) and the like can be mentioned.
  • the metal-containing porphyrin examples include protoporphyrin-tin fluoride complex (abbreviation: SnF 2 (Proto IX)), mesoporphyrin-tin fluoride complex (abbreviation: SnF 2 (Meso IX)), and hematoporphyrin-fluoride.
  • Tin complex (abbreviation: SnF 2 (Hemato IX)), coproporphyrin tetramethyl ester-tin fluoride complex (abbreviation: SnF 2 (Copro III-4Me)), octaethylporphyrin-tin fluoride complex (abbreviation: SnF 2 ) OEP)), etioporphyrin-tin fluoride complex (abbreviation: SnF 2 (EtioI)), octaethylporphyrin-platinum chloride complex (abbreviation: PtCl 2 OEP) and the like.
  • a substance in which a ⁇ -electron-rich heteroaromatic ring and a ⁇ -electron-deficient heteroaromatic ring are directly bonded has a stronger donor property of the ⁇ -electron-rich heteroaromatic ring and a stronger acceptor property of the ⁇ -electron-deficient heteroaromatic ring.
  • S1 and T1 are particularly preferable because the energy difference is small.
  • quantum dots having unique optical characteristics can also be used for the light emitting layer 113.
  • QD refers to a nanoscale semiconductor crystal, and specifically has a diameter of about several nm to several tens of nm.
  • the optical characteristics and the electronic characteristics can be changed by changing the size of the crystal, it is easy to adjust the emission color and the like.
  • the peak width of the emission spectrum of the quantum dot is narrow, it is possible to obtain emission with good color purity.
  • the materials constituting the quantum dots include group 14 elements, group 15 elements, group 16 elements, compounds composed of a plurality of group 14 elements, elements belonging to groups 4 to 14 and elements 16 of the element period table.
  • cadmium selenium, cadmium sulfide, cadmium tellurized zinc selenium, zinc oxide, zinc sulfide, zinc telluride, mercury sulfide, mercury sulphide, mercury telluride, indium arsenide, indium phosphate, gallium arsenide.
  • alloy-type quantum dots whose composition is represented by an arbitrary ratio may be used.
  • alloy-type quantum dots of cadmium, selenium, and sulfur can change the emission wavelength by changing the content ratio of the elements, and are therefore one of the effective means for obtaining blue emission.
  • the structure of the quantum dot there are a core type, a core-shell type, a core-multishell type and the like, and any of them may be used.
  • core-shell type or core-multi-shell type quantum dots in which a shell is formed by covering the core use another inorganic material with a wider bandgap than the inorganic material used for the core. By forming it, the influence of defects and dangling bonds existing on the surface of the nanocrystal can be reduced, and the quantum efficiency of light emission can be greatly improved, which is preferable.
  • the light emitting layer 113 can be formed by a coating method, an inkjet method, a printing method, or the like. Since the QD is not only bright and vivid in color, but also capable of emitting light having a wide range of wavelengths, has high efficiency, and has a long life, the element characteristics can be improved by using it for the light emitting layer 113.
  • the electron transport layer 114 is a layer containing a substance having a high electron transport property (also referred to as an electron transport compound).
  • the electron transport layer 114 includes tris (8-quinolinolat) aluminum (abbreviation: Alq 3 ), tris (4-methyl-8-quinolinolat) aluminum (abbreviation: Almq 3 ), BeBq 2 , BAlq, and bis [2- (2). -Hydroxyphenyl) benzoxazolate] zinc (abbreviation: Zn (BOX) 2 ), bis [2- (2-hydroxyphenyl) benzothiazolato] zinc (abbreviation: Zn (BTZ) 2 ) and other metal complexes can be used. can.
  • poly (2,5-pyridinediyl) (abbreviation: PPy), poly [(9,9-dihexylfluorene-2,7-diyl) -co- (pyridine-3,5-diyl)] (abbreviation: PF).
  • PPy poly [(9,9-dihexylfluorene-2,7-diyl) -co- (pyridine-3,5-diyl)]
  • PF-Py poly [(9,9-dioctylfluorene-2,7-diyl) -co- (2,2'-bipyridine-6,6'-diyl)] (abbreviation: PF-BPy), as well as phosphine
  • a polymer compound having an oxide skeleton or the like can also be used.
  • the substances described here are mainly substances having electron mobilities of 1 ⁇ 10 -6 cm 2 / Vs or more.
  • the electron transport layer 114 is not limited to a single layer, but may have a structure in which two or more layers made of the above substances are laminated.
  • the electron injection layer 115 is a layer containing a substance having a high electron injection property.
  • the electron injection layer 115 includes an alkali metal such as lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF 2 ), lithium oxide (LiOx), an alkaline earth metal, or a metal thereof. Compounds can be used. In addition, rare earth metal compounds such as erbium fluoride (ErF 3) can be used. Further, an electride may be used for the electron injection layer 115. Examples of the electride include a substance in which a high concentration of electrons is added to a mixed oxide of calcium and aluminum. It should be noted that the substance constituting the electron transport layer 114 described above can also be used.
  • a composite material formed by mixing an organic compound and an electron donor (donor) may be used for the electron injection layer 115.
  • Such a composite material is excellent in electron injecting property and electron transporting property because electrons are generated in an organic compound by an electron donor.
  • the organic compound is preferably a material excellent in transporting generated electrons, and specifically, for example, a substance (metal complex, heteroaromatic compound, etc.) constituting the electron transport layer 114 described above is used.
  • the electron donor may be any substance that exhibits electron donating property to the organic compound. Specific examples thereof include alkali metals, alkaline earth metals and rare earth metals, and examples thereof include lithium, cesium, magnesium, calcium, erbium and ytterbium.
  • alkali metal oxides and alkaline earth metal oxides are preferable, and lithium oxides, calcium oxides, barium oxides and the like can be mentioned. It is also possible to use a Lewis base such as magnesium oxide. Further, an organic compound such as tetrathiafulvalene (abbreviation: TTF) can also be used.
  • TTF tetrathiafulvalene
  • hole injection layer 111, hole transport layer 112, light emitting layer 113, electron transport layer 114, and electron injection layer 115 are each described by a vapor deposition method (including a vacuum vapor deposition method) and a printing method (for example, letterpress printing). It can be formed by a method, an intaglio printing method, a gravure printing method, a lithographic printing method, a stencil printing method, etc.), an inkjet method, a coating method, or the like alone or in combination.
  • an inorganic compound such as a quantum dot or a polymer compound is used. (Oligomer, dendrimer, polymer, etc.) may be used.
  • a current flows due to a potential difference given between the first electrode 101 and the second electrode 103, and holes and electrons recombine in the EL layer 102 to emit light. Then, this light emission is taken out to the outside through either or both of the first electrode 101 and the second electrode 103. Therefore, either one or both of the first electrode 101 and the second electrode 103 is a translucent electrode.
  • the light emitting device described above can obtain phosphorescent light emission based on the organometallic complex, it is possible to realize a highly efficient light emitting device as compared with a light emitting device using only a fluorescent compound.
  • the light emitting device has an EL layer capable of using the organometallic complex manufactured by the production method according to the production method according to the present invention, and is a light emitting device having a structure having a plurality of EL layers (hereinafter referred to as “light emitting device”).
  • a tandem type light emitting device will be described.
  • a plurality of EL layers are interposed between a pair of electrodes (first electrode 201 and second electrode 204) via a charge generation layer 205. It is a tandem type light emitting device having an EL layer 202 (1) and a second EL layer 202 (2)).
  • the first electrode 201 is an electrode that functions as an anode
  • the second electrode 204 is an electrode that functions as a cathode.
  • the first electrode 201 and the second electrode 204 can have the same configuration as that of the second embodiment.
  • the plurality of EL layers may both have the same configuration as the EL layer shown in the second embodiment. , Either one may have the same configuration. That is, the first EL layer 202 (1) and the second EL layer 202 (2) may have the same configuration or different configurations, and when they have the same configuration, the second embodiment is applied. can do.
  • the charge generation layer 205 provided between the plurality of EL layers has a first electrode 201 and a second electrode.
  • first electrode 201 When a voltage is applied to 204, it has a function of injecting electrons into one EL layer and injecting holes into the other EL layer.
  • first electrode 201 when a voltage is applied to the first electrode 201 so that the potential is higher than that of the second electrode 204, electrons are generated from the charge generation layer 205 to the first EL layer 202 (1). It is injected and holes are injected into the second EL layer 202 (2).
  • the charge generation layer 205 is transparent to visible light from the viewpoint of light extraction efficiency (specifically, the visible light transmittance of the charge generation layer 205 is 40% or more). preferable. Further, the charge generation layer 205 functions even if the conductivity is lower than that of the first electrode 201 and the second electrode 204.
  • the charge generation layer 205 has a structure in which an electron acceptor is added to an organic compound having a high hole transport property, but an electron donor is added to the organic compound having a high electron transport property. May be. Further, both of these configurations may be laminated.
  • the organic compound having high hole transporting property includes the hole injection layer 111 and the hole transporting layer 112 in the second embodiment.
  • a substance shown as a substance having a high hole transport property can be used.
  • aromatic amine compounds such as NPB, TPD, TDATA, MTDATA, and BSPB can be used.
  • the substances described here are mainly substances having a hole mobility of 1 ⁇ 10 -6 cm 2 / Vs or more.
  • a substance other than the above may be used as long as it is an organic compound having a higher transportability of the stop hole than the electron.
  • the electron acceptor 7,7,8,8-(abbreviation: F 4 -TCNQ), chloranil, and the like can be given.
  • the oxides of metals belonging to Group 4 to Group 8 in the Periodic Table of the Elements can be mentioned. Specifically, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, and renium oxide are preferable because they have high electron acceptability. Among them, molybdenum oxide is particularly preferable because it is stable in the atmosphere, has low hygroscopicity, and is easy to handle.
  • the organic compound having high electron transport property is the substance having high electron transport property used for the electron transport layer 114 in the second embodiment.
  • the substance shown as can be used.
  • a metal complex having a quinoline skeleton or a benzoquinoline skeleton such as Alq, Almq 3 , BeBq 2, and BAlq can be used.
  • a metal complex having an oxazole-based ligand such as Zn (BOX) 2 or Zn (BTZ) 2 or a thiazole-based ligand can also be used.
  • PBD, OXD-7, TAZ, BPhen, BCP and the like can also be used.
  • the substances described here are mainly substances having electron mobilities of 1 ⁇ 10 -6 cm 2 / Vs or more.
  • a substance other than the above may be used as long as it is an organic compound having a higher electron transport property than holes.
  • an alkali metal, an alkaline earth metal, a rare earth metal, a metal belonging to the second and thirteenth groups in the Periodic Table of the Elements, an oxide thereof, and a carbonate can be used.
  • an organic compound such as tetrathianaphthalene may be used as an electron donor.
  • the method for forming the charge generation layer 205 includes a vapor deposition method (including a vacuum vapor deposition method), a printing method (for example, a letterpress printing method, an intaglio printing method, a gravure printing method, a lithographic printing method, a stencil printing method, etc.), and an inkjet. It can be formed by a method, a coating method, or the like alone or in combination.
  • n layers (where n is 3 or more) are EL layers (202 (1) to 202 (n)).
  • EL layers 202 (1) to 202 (n)
  • ) Can be similarly applied to a light emitting device in which.
  • charge generation layers (205 (1) to 205 (n-1)) are formed between the EL layers and the EL layers, respectively.
  • the emission color of each EL layer different, it is possible to obtain emission of a desired color for the entire light emitting device.
  • a light emitting device that emits white light as a whole by making the light emitting color of the first EL layer and the light emitting color of the second EL layer have a complementary color relationship.
  • the complementary color refers to the relationship between colors that become achromatic when mixed. That is, white light can be obtained by mixing light of complementary colors with each other.
  • Specific examples thereof include a combination in which blue emission is obtained from the first EL layer and yellow emission or orange emission is obtained from the second EL layer. In this case, both blue emission and yellow emission (or orange emission) do not have to be the same fluorescent emission or phosphorescence emission, and the combination in which blue emission is fluorescence emission and yellow emission (or orange emission) is phosphorescence emission. Or vice versa.
  • the light emitting color of the first EL layer is red
  • the light emitting color of the second EL layer is green
  • the third EL layer is blue
  • white light emission can be obtained for the light emitting device as a whole.
  • Step 1 Synthesis of 5- (5-cyano-2-methylphenyl) -2,3-bis (3,5-dimethylphenyl) pyrazine (abbreviation: Hdmdmpr-m5CP)>
  • 5-cyano-2-methylphenylboronic acid 0.79 g
  • tripotassium phosphate 3.17 g
  • 33 mL of toluene and 3.3 mL of water were placed in a three-necked flask, and the inside was replaced with nitrogen.
  • the synthesis scheme of step 1 is shown in (a-1) below.
  • Step 2 Di- ⁇ -chloro-tetrakis ⁇ 4,6-dimethyl-2- [5- (5-cyano-2-methylphenyl) -3- (3,5-dimethylphenyl) -2-pyrazinyl- ⁇ N ] Phenyl- ⁇ C ⁇ Diiridium (III) (abbreviation: [Ir (dmdppr-m5CP) 2 Cl] 2 ) synthesis> Then, 2-ethoxyethanol 15mL of water 5mL, Hdmdppr-m5CP (abbreviation) obtained in the above Step 1 1.59 g, iridium hydrate (IrCl 3 ⁇ H 2 O) chloride (manufactured by Furuya Metal Co., Ltd.) 0.57 g was placed in a eggplant flask equipped with a reflux tube, and the inside of the flask was replaced with argon.
  • Ir (dmdppr-m5CP) 2 Cl] 2 2-ethoxyethanol 15mL
  • step 2 The synthesis scheme of step 2 is shown in (a-2) below.
  • Step 3 Bis ⁇ 4,6-dimethyl-2- [5- (5-cyano-2-methylphenyl) -3- (3,5-dimethylphenyl) -2-pyrazinyl- ⁇ N] phenyl- ⁇ C ⁇ ( Synthesis of 2,2,6,6-tetramethyl-3,5-heptandionat- ⁇ 2 O, O') iridium (III) (abbreviation: [Ir (dmdppr-m5CP) 2 (dpm)]> Next, reflux the dinuclear complex obtained in step 2 above, [Ir (dmdppr-m5CP) 2 Cl] 2 1.00 g, dipivaloylmethane (abbreviation: Hdpm) 0.38 g, and sodium carbonate 0.51 g.
  • step 3 The synthesis scheme of step 3 is shown in (a-3) below.
  • the aprotic solvent hinders the generation of protons more than the protonic solvent, for example, the proton reacts with the cyano group having a high electron density contained in the organic metal complex as an electrophile. Side reactions such as elimination of the cyano group can be suppressed. Therefore, it is preferable to use an aprotic solvent as the reaction solvent in the above reaction.
  • aprotic solvents those having a particularly high boiling point, preferably having a boiling point of 80 ° C.
  • the above aprotic solvent more preferably an aprotic solvent having a boiling point of 150 ° C. or higher is preferable.
  • an aprotonic solvent and base having a boiling point of 80 ° C. or higher such as amide compounds, ethers, and nitriles.

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