Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/82—Carbazoles; Hydrogenated carbazoles
  • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
  • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
  • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
  • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/649—Aromatic compounds comprising a hetero atom
  • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
  • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/658—Organoboranes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/05—Isotopically modified compounds, e.g. labelled
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2101/00—Properties of the organic materials covered by group H10K85/00
  • H10K2101/20—Delayed fluorescence emission
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2101/00—Properties of the organic materials covered by group H10K85/00
  • H10K2101/27—Combination of fluorescent and phosphorescent emission
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2101/00—Properties of the organic materials covered by group H10K85/00
  • H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values

Definitions

• the present invention relates to an organic electroluminescence device with high luminous efficiency.
• Patent Literature 1 proposes a three-component organic electroluminescence device in which a light-emitting layer is composed of a host material, a delayed fluorescent material, and a fluorescent material.
• the excited triplet energy transferred from the host material to the delayed fluorescent material and the excited triplet energy generated in the delayed fluorescent material undergo reverse intersystem crossing from triplet to singlet in the delayed fluorescent material. is converted into excited singlet energy by , which migrates to the fluorescent material and is emitted as fluorescence. It is said that, as a result, excited triplet energy generated in the light-emitting layer is effectively utilized for light emission of the fluorescent material, resulting in high luminous efficiency.
• the emission wavelength of fluorescent materials depends on the HOMO-LUMO energy gap and Stokes shift, and various fluorescent materials with different energy values have been developed. Therefore, in the three-component light-emitting layer, depending on the fluorescent material used, the LUMO energy of the fluorescent material may be higher than the LUMO energy of the delayed fluorescent material, or it may be lower (deeper) than that. There is also Under these circumstances, the present inventors combined various delayed fluorescent materials and fluorescent materials with a host material to form a light-emitting layer. It was found that when the concentration of the fluorescent material was increased, a phenomenon was observed in which the luminous efficiency decreased, and the luminous efficiency could not be sufficiently improved.
• the present inventors have developed an organic electroluminescence device containing a host material, a delayed fluorescent material, and a fluorescent material in a light emitting layer, in which the LUMO energy of the fluorescent material is higher than the LUMO energy of the delayed fluorescent material, even if it is lower Intensive studies have been carried out for the purpose of providing an organic electroluminescence device that can obtain high luminous efficiency.
• the present inventors found that even when the LUMO energy of the fluorescent material is lower than the LUMO energy of the delayed fluorescent material, the orientation value S of the organic compound molecules used as the fluorescent material is ⁇ 0. .3 or less, the luminous efficiency can be improved even if the concentration of the fluorescent material is increased.
• the present invention has been proposed based on these findings, and specifically has the following configurations.
• An organic electroluminescence device having an anode, a cathode, and at least one organic layer including a light-emitting layer between the anode and the cathode,
• the light-emitting layer contains a first organic compound, a second organic compound and a third organic compound, and satisfies the following (a) and the following formula (b), the second organic compound is a delayed fluorescence material,
• the organic electroluminescence device wherein the largest component of light emission from the device is fluorescence from the third organic compound.
• E LUMO (2) is the LUMO energy of the second organic compound
• E LUMO (3) is the LUMO energy of the third organic compound
• S represents the orientation value of the third organic compound in the light-emitting layer.
• the third organic compound is a compound having a structure in which a hetero 6-membered ring containing a boron atom and a nitrogen atom is condensed with a pyrrole ring and two benzene rings sharing a nitrogen atom, [1] to [ 3].
• the organic electroluminescence device according to any one of [1] to [4], wherein the third organic compound is a compound represented by the following general formula (16).
• general formula (16) [In the general formula (16), one of X 1 and X 2 is a nitrogen atom, and the other is a boron atom.
• R 1 to R 26 , A 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R10 , R10 and R11 , R11 and R12 , R13 and R14 , R14 and R15 , R15 and R16 , R16 and R17 , R17 and R18 , R18 and R 19 , R 19 and R 20 , R 20 and R 21 , R 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 24 and R 25 , R 25 and R 26 are bonded together to form a cyclic It may form a structure.
• X 1 is a nitrogen atom
• R 7 and R 8 and R 21 and R 22 are bonded through the nitrogen atom to form a 6-membered ring
• R 17 and R 18 are bonded together to form a single bond at least one of R 1 to R 6 is a substituted or unsubstituted aryl group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R5 and R6 are bonded to each other to form an aromatic ring or heteroaromatic ring.
• [6] The organic electroluminescence device according to any one of [1] to [5], wherein the concentration of the second organic compound in the light-emitting layer is 25% by weight or more.
• E LUMO (1) is the LUMO energy of the first organic compound
• E LUMO (2) is the LUMO energy of the second organic compound
• E LUMO (3) is the LUMO energy of the third organic compound S is , represents the orientation value of the third organic compound in the light-emitting layer.
• the LUMO energy of the second organic compound is Even when the LUMO energy of the third organic compound is lower than that, the concentration of the third organic compound can be increased to improve the luminous efficiency.
• substituted means an atom or group of atoms other than a hydrogen atom and a deuterium atom.
• the expressions "substituted or unsubstituted” and “optionally substituted” mean that a hydrogen atom may be substituted with a deuterium atom or a substituent.
• the term “transparent” in the present invention means that the visible light transmittance is 50% or more, preferably 80% or more, more preferably 90% or more, and still more preferably 99% or more. Visible light transmittance can be measured with an ultraviolet/visible spectrophotometer.
• the organic electroluminescence device of the present invention is an organic electroluminescence device having an anode, a cathode, and at least one organic layer including a light-emitting layer between the anode and the cathode.
• the organic layer may be composed only of the light-emitting layer, or may include organic layers other than the light-emitting layer.
• an organic layer may or may not be interposed between the anode and the light-emitting layer and between the light-emitting layer and the cathode.
• the anode and the light-emitting layer may be laminated so as to be in direct contact with each other, or may be laminated so as not to be in direct contact with each other.
• the light emitting layer and the cathode may be laminated so as to be in direct contact with each other, or may be laminated so as not to be in direct contact with each other.
• the light-emitting layer is located between the anode and the cathode, and is preferably arranged without protruding into the region between the anode and the cathode.
• the organic electroluminescence device of the present invention may have a substrate supporting at least one organic layer including an anode, a cathode, and a light-emitting layer.
• the substrate may be arranged on the side of the anode opposite to the light emitting layer, or may be arranged on the side of the cathode opposite to the light emitting layer.
• the organic electroluminescence device of the present invention may be a top emission type device in which most of the light is emitted from the side opposite to the substrate, or a bottom emission type device in which most of the light is emitted from the substrate side.
• “most light” means light that is 60% or more of the amount of light emitted from the device.
• the organic electroluminescence device of the present invention contains a first organic compound, a second organic compound and a third organic compound in the light emitting layer.
• the second organic compound is a delayed fluorescence material.
• the third organic compound is a compound that emits fluorescence.
• the maximum component of light emission from the device is fluorescence from the third organic compound.
• the second organic compound and the third organic compound contained in the light-emitting layer satisfy the following formulas (a) and (b).
• the first organic compound, the second organic compound, and the third organic compound contained in the light-emitting layer satisfy formula (a1) and formula (b) below.
• E LUMO (1) in formula (a) and formula (a1) represents the LUMO energy of the first organic compound
• E LUMO (2) represents the LUMO energy of the second organic compound
• E LUMO (3) represents It represents the LUMO energy of the third organic compound.
• LUMO is an abbreviation for Lowest Unoccupied Molecular Orbital, and can be obtained by atmospheric photoelectron spectroscopy (AC-3 manufactured by Riken Keiki Co., Ltd.). Since the present invention satisfies the relationship of formula (a), the LUMO energy of the second organic compound contained in the light-emitting layer is higher than the LUMO energy of the third organic compound.
• the first organic compound has the highest LUMO energy among the first organic compound, the second organic compound, and the third organic compound contained in the light-emitting layer, and the second organic compound has the highest LUMO energy. is the next highest and the third organic compound is the lowest.
• LUMO energy difference [E LUMO (1) - E LUMO (2)] is, for example, in the range of 0.1 eV or more, or in the range of 0.5 eV or more, or in the range of 0.8 eV or more, 1.0 eV or more, 2.0 eV or less, 1.5 eV or less, 1.3 eV or less, or 1.1 eV or less.
• the LUMO energy difference [E LUMO (2) - E LUMO (3)] is, for example, in the range of 0.01 eV or more, or in the range of 0.05 eV or more, or in the range of 0.1 eV or more, 0.15 eV or more, 0.2 eV or more, 0.7 eV or less, 0.5 eV or less, or 0.4 eV or less. can be within the range, or within the range of 0.3 eV or less.
• a compound having a LUMO energy in the range of ⁇ 2.0 to ⁇ 5.0 eV or a compound having a LUMO energy in the range of ⁇ 2.5 to ⁇ 4.0 eV is employed as the first organic compound. can do.
• a compound having a LUMO energy in the range of ⁇ 2.0 to ⁇ 5.0 eV or a compound having a LUMO energy in the range of ⁇ 2.5 to ⁇ 4.0 eV is employed as the second organic compound. can do.
• a compound having a LUMO energy in the range of ⁇ 2.0 to ⁇ 5.0 eV or a compound in the range of ⁇ 2.5 to ⁇ 4.0 eV is employed as the third organic compound. You can
• the relationship of the HOMO energies of the first organic compound, the second organic compound and the third organic compound is not particularly limited.
• the HOMO energy of the second organic compound may be less than or greater than the HOMO energy of the first organic compound, or may be the same as the HOMO energy of the first organic compound.
• the HOMO energy of the third organic compound may be smaller or larger than the HOMO energy of the second organic compound, or may be the same as the HOMO energy of the second organic compound.
• HOMO is an abbreviation for Highest Occupied Molecular Orbital, and can be determined by atmospheric photoelectron spectroscopy (AC-3 manufactured by Riken Keiki Co., Ltd.).
• a compound having a HOMO energy in the range of ⁇ 4.0 to ⁇ 6.5 eV or a compound in the range of ⁇ 5.5 to ⁇ 6.2 eV is used as the first organic compound. can do.
• a compound having a HOMO energy within the range of ⁇ 4.0 to ⁇ 6.5 eV or a compound having a HOMO energy within the range of ⁇ 5.5 to ⁇ 6.2 eV is employed as the second organic compound.
• a compound having a HOMO energy in the range of ⁇ 4.0 to ⁇ 6.5 eV or a compound in the range of ⁇ 5.0 to ⁇ 6.0 eV is employed as the third organic compound. You can
• S in formula (b) represents the orientation value of the third organic compound in the light-emitting layer. Since the present invention satisfies the formula (b), the orientation value of the third organic compound in the light-emitting layer is -0.3 or less.
• the orientation value is also called an S value, and is an index indicating the degree of orientation of the third organic compound in the light-emitting layer. A larger negative value (a smaller value) means a higher orientation.
• the orientation value (S value) is from Scientific Reports 2017, 7, 8405. In the organic electroluminescence device of the present invention, since the orientation value of the third organic compound is ⁇ 0.3 or less, a high external quantum yield is realized while satisfying the LUMO energy relationship of formula (a). can do.
• the LUMO energy of the third organic compound that emits fluorescence is set lower than the LUMO energy of the second organic compound, which is the delayed fluorescence material.
• the third organic compound having an orientation value of ⁇ 0.3 or less has high stability, and the use of this as a light-emitting material has the effect of improving the life of the device.
• the orientation value of the third organic compound in the light-emitting layer is preferably ⁇ 0.38 or less, more preferably ⁇ 0.40 or less, further preferably ⁇ 0.41 or less, and ⁇ 0.42. It is even more preferred that:
• the first organic compound, the second organic compound, and the third organic compound contained in the light-emitting layer preferably satisfy the following formula (c).
• E S1 (1) in formula (c) represents the lowest excited singlet energy of the first organic compound
• E S1 (2) represents the lowest excited singlet energy of the second organic compound
• E S1 (3) represents the second 3 represents the lowest excited singlet energy of organic compounds.
• eV is adopted as a unit.
• the lowest excited singlet energy can be obtained by preparing a thin film or a toluene solution (concentration 10 ⁇ 5 mol/L) of the compound to be measured and measuring the fluorescence spectrum at room temperature (300 K) (for details, see the second organic See the measurement method of the lowest excited singlet energy in the description column of the compound).
• E S1 (1) - E S1 (2) can be, for example, in the range of 0.20 eV or more, or in the range of 0.40 eV or more, or in the range of 0.60 eV or more, and It can be in the range of 1.50 eV or less, in the range of 1.20 eV or less, or in the range of 0.80 eV or less.
• E S1 (2) - E S1 (3) can be, for example, in the range of 0.05 eV or more, or in the range of 0.10 eV or more, or in the range of 0.15 eV or more, and It can be in the range of 0.50 eV or less, in the range of 0.30 eV or less, or in the range of 0.20 eV or less.
• E S1 (1) - E S1 (3) can be, for example, in the range of 0.25 eV or more, or in the range of 0.45 eV or more, or in the range of 0.65 eV or more, and It can be in the range of 2.00 eV or less, in the range of 1.70 eV or less, or in the range of 1.30 eV or less.
• the largest component of light emission from the device is fluorescence from the third organic compound.
• "Emission from a device" in the present invention means light emitted from the device when the device is driven at 20.degree.
• the emission from the organic electroluminescence device of the present invention can be emitted from phosphorescence from the third organic compound, phosphorescence from the first organic compound or the second organic compound, as long as the maximum component of light emission from the device is fluorescence from the third organic compound. Emissions may be included, but it is preferred that these emissions be insignificant compared to the fluorescence from the third organic compound.
• 70% or more of the light emitted from the device may be fluorescence from the third organic compound, 90% or more may be fluorescence from the third organic compound, and 99% or more may be fluorescence from the third organic compound. It may be fluorescence from a compound.
• the concentration of the third organic compound in the light-emitting layer of the organic electroluminescence device of the present invention is preferably higher than 0.3% by weight.
• the concentration of the third organic compound in the light-emitting layer is in the range of 0.35% by weight or more, 0.5% by weight or more, 1% by weight or more, or 2% by weight or more. be able to.
• the concentration of the third organic compound in the light-emitting layer can be in the range of 10% by weight or less, 5% by weight or less, or 3% by weight or less.
• Conc(1), Conc(2), and Conc(3) are the concentrations of the first organic compound, the second organic compound, and the third organic compound in the light emitting layer of the organic electroluminescence device of the present invention, respectively, the following It is preferable to satisfy the relationship of formula (d).
• Conc (1) is preferably 30% by weight or more, can be in the range of 50% by weight or more, can be in the range of 60% by weight or more, and can be in the range of 99% by weight or less. , 85% by weight or less, or 70% by weight or less.
• Conc (2) is preferably 5% by weight or more, and can be in the range of 15% by weight or more, 25% by weight or more, or 30% by weight or more, and , 45% by weight or less, 40% by weight or less, or 35% by weight or less. In a preferred embodiment of the invention, Conc(2) is 25-45% by weight.
• Conc(1)/Conc(3) can be in the range of 10 or more, 50 or more, or 90 or more, and can be in the range of 10000 or less, or 1000 or less. , or 200 or less.
• Conc(2)/Conc(3) can be in the range of 10 or more, in the range of 50 or more, or in the range of 90 or more, and in the range of 10000 or less, or 1000 or less. , or 200 or less.
• the light-emitting layer of the organic electroluminescence device of the present invention preferably does not contain metal elements other than boron.
• a light-emitting layer that does not contain a metal element containing boron can also be used.
• the light emitting layer can be composed only of compounds consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, oxygen atoms, sulfur atoms, fluorine atoms and boron atoms.
• the light emitting layer can be composed only of compounds consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, oxygen atoms, sulfur atoms, fluorine atoms and boron atoms.
• the light emitting layer can be composed only of compounds consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, oxygen atoms and sulfur atoms.
• the light emitting layer can be composed only of compounds consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms and oxygen atoms.
• the first organic compound used in the light-emitting layer of the organic electroluminescence device of the present invention is selected from compounds having higher LUMO energy than the second organic compound and the third organic compound.
• the first organic compound is selected from compounds having a LUMO energy higher than that of the second organic compound and the third organic compound and having a lowest excited singlet energy higher than that of the second organic compound and the third organic compound.
• the first organic compound preferably functions as a host material that transports carriers.
• the first organic compound preferably has a function of confining the energy of the third organic compound in the compound.
• the third organic compound can efficiently convert the energy generated by recombination of holes and electrons in the molecule and the energy received from the first organic compound and the second organic compound into light emission.
• the first organic compound is preferably an organic compound that has a hole-transporting ability and an electron-transporting ability, prevents emission from having a longer wavelength, and has a high glass transition temperature.
• the first organic compound is selected from compounds that do not emit delayed fluorescence. Emission from the first organic compound is preferably less than 1% of the light emission from the organic electroluminescent device of the present invention, more preferably less than 0.1%, for example less than 0.01%, detection limit It may be below.
• the first organic compound does not contain metal atoms.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, oxygen atoms and sulfur atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms and oxygen atoms can be selected.
• a compound consisting of carbon atoms, hydrogen atoms and nitrogen atoms can be selected as the first organic compound.
• Preferred compounds that can be used as the first organic compound are listed below.
• the second organic compound used in the light-emitting layer of the organic electroluminescence device of the present invention is a delayed fluorescence material having a lower LUMO energy than the first organic compound and a higher LUMO energy than the third organic compound.
• the second organic compound has a lower LUMO energy than the first organic compound, a higher LUMO energy than the third organic compound, and a lower minimum than the first organic compound and a higher minimum than the third organic compound.
• a delayed fluorescence material having excited singlet energy is preferred.
• the “delayed fluorescence material” in the present invention means that in an excited state, a reverse intersystem crossing occurs from an excited triplet state to an excited singlet state, and fluorescence (delayed fluorescence) when returning from the excited singlet state to the ground state is an organic compound that emits
• a delayed fluorescence material is defined as a material that emits fluorescence with an emission lifetime of 100 ns (nanoseconds) or more when measured by a fluorescence lifetime measurement system (such as a streak camera system manufactured by Hamamatsu Photonics).
• the second organic compound is a material capable of emitting delayed fluorescence, it is not essential to emit delayed fluorescence derived from the second organic compound when used in the organic electroluminescence device of the present invention.
• the emission from the second organic compound is preferably less than 10% of the emission from the organic electroluminescent device of the present invention, for example, less than 1%, less than 0.1%, less than 0.01%, and below the detection limit. There may be.
• the second organic compound receives energy from the first organic compound in the excited singlet state and transitions to the excited singlet state.
• the second organic compound may receive energy from the first organic compound in the excited triplet state and transition to the excited triplet state. Since the difference ( ⁇ E ST ) between the excited singlet energy and the excited triplet energy of the second organic compound is small, the second organic compound in the excited triplet state undergoes reverse intersystem crossing to the second organic compound in the excited singlet state. Cheap.
• the excited singlet state second organic compound generated by these pathways gives energy to the third organic compound, causing the third organic compound to transition to an excited singlet state.
• the difference ⁇ E ST between the lowest excited singlet energy and the lowest excited triplet energy at 77 K is preferably 0.3 eV or less, more preferably 0.25 eV or less, and 0.2 eV or less. is more preferably 0.15 eV or less, more preferably 0.1 eV or less, even more preferably 0.07 eV or less, and still more preferably 0.05 eV or less It is preferably 0.03 eV or less, more preferably 0.01 eV or less, and particularly preferably 0.01 eV or less.
• thermally activated delayed fluorescence material absorbs the heat emitted by the device and relatively easily undergoes reverse intersystem crossing from the excited triplet state to the excited singlet state, and efficiently contributes the excited triplet energy to light emission. can be done.
• the lowest excited singlet energy (E S1 ) and the lowest excited triplet energy (E T1 ) of the compound in the present invention are values determined by the following procedure.
• ⁇ E ST is a value obtained by calculating E S1 -E T1 .
• (2) Lowest excited singlet energy (E S1 ) A thin film or a toluene solution (concentration 10 ⁇ 5 mol/L) of the compound to be measured is prepared and used as a sample. The fluorescence spectrum of this sample is measured at room temperature (300K). In the fluorescence spectrum, the vertical axis is light emission and the horizontal axis is wavelength.
• the maximum point with a peak intensity of 10% or less of the maximum peak intensity of the spectrum is not included in the maximum value on the shortest wavelength side described above, and is closest to the maximum value on the short wavelength side.
• the tangent line drawn at the point where the value is taken is taken as the tangent line to the rise on the short wavelength side of the phosphorescence spectrum.
• the second organic compound preferably does not contain metal atoms.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, oxygen atoms and sulfur atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms and oxygen atoms can be selected as the second organic compound.
• a compound consisting of carbon atoms, hydrogen atoms and nitrogen atoms can be selected as the second organic compound.
• a typical second organic compound is a compound having a structure in which one to two cyano groups and at least one donor group are bonded to a benzene ring.
• a preferred example of the donor group is a substituted or unsubstituted carbazol-9-yl group.
• a specific example of the group having a structure in which a substituted or unsubstituted benzofuran ring is fused to a benzene ring constituting a carbazol-9-yl group is substituted or unsubstituted 5H-benzofuro[3,2-c]carbazole-5. -yl group.
• X 1 to X 5 represent N or CR.
• R represents a hydrogen atom, a deuterium atom or a substituent.
• X 1 to X 5 represent C—R
• those C—R may be the same or different.
• at least one of X 1 to X 5 is CD (wherein D represents a donor group).
• Z represents an acceptor group.
• a compound represented by the following general formula (2) is particularly preferable among the compounds represented by the general formula (1).
• X 1 to X 5 represent N or CR.
• R represents a hydrogen atom, a deuterium atom or a substituent.
• X 1 to X 5 represent C—R
• those C—R may be the same or different.
• at least one of X 1 to X 5 is CD (wherein D represents a donor group).
• none of X 1 to X 5 are C—CN. That is, it is a compound having a structure in which one to two cyano groups and at least one donor group are bonded to a benzene ring.
• only X 2 represents C-CN and X 1 , X 3 -X 5 are not C-CN.
• X 3 represents C-CN and X 1 , X 2 , X 4 , X 5 are not C-CN. That is, it is a compound having a structure in which at least one donor group is bonded to the benzene ring of terephthalonitrile.
• the acceptor group represented by Z in the general formula (1) is a group having the property of donating electrons to the ring to which Z is bonded, and for example, selected from groups having a positive Hammett's ⁇ p value. can be done.
• the donor group represented by D in the general formulas (1) and (2) is a group having the property of attracting electrons to the ring to which D is bonded, for example, a group having a negative Hammett's ⁇ p value. can be selected from In the following, the acceptor group may be referred to as A.
• "Hammet's ⁇ p value" is defined by L.P. P.
• the equilibrium constant of the benzene derivative substituted with ⁇ represents the reaction constant determined by the type and conditions of the reaction.
• the acceptor group include a cyano group and an acceptor group preferable as A in general formulas (12) to (14) described later.
• the donor group reference can be made to a donor group preferable as D in general formulas (12) to (14) described later.
• X 1 to X 5 represent N or CR, at least one of which is CD.
• the number of N in X 1 to X 5 is 0 to 4, for example, X 1 and X 3 and X 5 , X 1 and X 3 , X 1 and X 4 , X 2 and X 3 , X 1 and X 5 , X 2 and X 4 , X 1 only, X 2 only, and X 3 only are N.
• the number of CDs is 1 to 5, preferably 2 to 5.
• X 1 and X 2 and X 3 and X 4 and X 5 , X 1 and X 2 and X 4 and X 5 , X 1 and X 2 and X 3 and X 4 , X 1 and X 3 and X 4 and X 5 , X 1 and X 3 and X 5 , X 1 and X 2 and X 5 , X 1 and X 2 and X 4 , X 1 and X 3 and X 4 , X 1 and X 3 and X 4 , X 1 and X 3 , X 1 and X 4 , X 2 and X 3 , X 1 and X 5 , X 2 and X 4 , X 1 only, X 2 only, and X 3 only are CD.
• At least one of X 1 to X 5 may be CA.
• a here represents an acceptor group.
• the number of CAs is preferably 0 to 2, more preferably 0 or 1.
• a of CA preferably includes a cyano group and a heterocyclic aromatic group having an unsaturated nitrogen atom.
• X 1 to X 5 may each independently be CD or CA.
• the two R's may be bonded together to form a cyclic structure.
• the cyclic structure formed by bonding to each other may be an aromatic ring or an alicyclic ring, or may contain a heteroatom, and the cyclic structure may be a condensed ring of two or more rings. .
• heteroatoms referred to here are preferably those selected from the group consisting of nitrogen atoms, oxygen atoms and sulfur atoms.
• cyclic structures formed include benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, imidazoline ring, oxazole ring, isoxazole ring, thiazole ring, iso thiazole ring, cyclohexadiene ring, cyclohexene ring, cyclopentaene ring, cycloheptatriene ring, cycloheptadiene ring, cycloheptaene ring, furan ring, thiophene ring, naphthyridine ring, quinoxaline ring, quinoline ring and the like. .
• the donor group D in general formulas (1) and (2) is preferably, for example, a group represented by general formula (3) below.
• General formula (3)
• R 11 and R 12 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.
• R 11 and R 12 may combine with each other to form a cyclic structure.
• L represents a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
• a substituent that can be introduced into the arylene group or heteroarylene group of L may be a group represented by general formula (1) or general formula (2), or general formulas (3) to (6) described later.
• alkyl group may be linear, branched, or cyclic. Moreover, two or more of the linear portion, the cyclic portion and the branched portion may be mixed.
• the number of carbon atoms in the alkyl group can be, for example, 1 or more, 2 or more, or 4 or more.
• the number of carbon atoms can be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less.
• alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, 2-ethylhexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decanyl group, isodecanyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group.
• alkyl group as a substituent may be further substituted with an aryl group.
• An "alkenyl group” may be linear, branched, or cyclic. Moreover, two or more of the linear portion, the cyclic portion and the branched portion may be mixed.
• the number of carbon atoms in the alkenyl group can be, for example, 2 or more and 4 or more. Also, the number of carbon atoms can be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less.
• alkenyl groups include ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, n-pentenyl, isopentenyl, n-hexenyl, isohexenyl, and 2-ethylhexenyl groups. can be mentioned.
• the alkenyl group as a substituent may be further substituted with a substituent.
• the “aryl group” and “heteroaryl group” may be monocyclic or condensed rings in which two or more rings are condensed. In the case of condensed rings, the number of condensed rings is preferably 2 to 6, and can be selected from 2 to 4, for example.
• rings include benzene ring, pyridine ring, pyrimidine ring, triazine ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, quinoline ring, pyrazine ring, quinoxaline ring, and naphthyridine ring.
• aryl or heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 2-pyridyl, 3-pyridyl, 4 - pyridyl group.
• Arylene group and “heteroaryl group” can be read by changing the valence number from 1 to 2 in the description of the aryl group and heteroaryl group.
• a substituent means a monovalent group capable of substituting a hydrogen atom, and does not include condensed groups.
• the explanation and preferred range of the substituent the explanation and preferred range of the substituent of general formula (7) described later can be referred to.
• the compound represented by the general formula (3) is preferably a compound represented by any one of the following general formulas (4) to (6).
• R 51 to R 60 , R 61 to R 68 and R 71 to R 78 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• R 51 to R 60 , R 61 to R 68 and R 71 to R 78 is independently a group represented by any one of the general formulas (4) to (6).
• the number of substituents in general formulas (4) to (6) is not particularly limited. It is also preferred if all are unsubstituted (ie hydrogen or deuterium atoms).
• substituents in each of the general formulas (4) to (6) may be the same or different.
• the substituent is preferably any one of R 52 to R 59 in general formula (4), and general formula (5) Any one of R 62 to R 67 is preferred in the case of general formula (6), and any one of R 72 to R 77 is preferred in the case of general formula (6).
• X is a divalent oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted carbon atom, a substituted or unsubstituted silicon atom, or a carbonyl having a linked chain length of 1 atom. or a divalent substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted o-arylene group, or a substituted or unsubstituted o-hetero represents an arylene group. Specific examples and preferred ranges of the substituents can be referred to the description of the substituents in the general formulas (1) and (2) above.
• L 12 to L 14 each represent a single bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
• L 12 to L 14 are preferably single bonds or substituted or unsubstituted arylene groups.
• the substituents of the arylene group and heteroarylene group referred to herein may be groups represented by general formulas (1) to (6).
• the groups represented by formulas (1) to (6) may be introduced into L 11 to L 14 up to the maximum number of substituents that can be introduced. Moreover, when a plurality of groups represented by formulas (1) to (6) are introduced, the substituents thereof may be the same or different.
• * represents the bonding position to the carbon atom (C) constituting the ring skeleton of the ring in general formula (1) or general formula (2).
• R 51 and R 52 , R 52 and R 53 , R 53 and R 54 , R 54 and R 55 , R 55 and R 56 , R 56 and R 57 , R 57 and R58 , R58 and R59 , R59 and R60 , R61 and R62 , R62 and R63 , R63 and R64 , R65 and R66 , R66 and R67 , R67 and R68 , R 71 and R 72 , R 72 and R 73 , R 73 and R 74 , R 75 and R 76 , R 76 and R 77 , R 77 and R 78 may be bonded to each other to form a cyclic structure. good.
• the description and preferred examples of the cyclic structure the description and preferred examples of the cyclic structure for X 1 to X 5 in general formulas (1) and (2) above can be referred to.
• cyclic structures Preferred among cyclic structures are a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted indene ring, and a substituted or unsubstituted silaindene ring, It is a structure fused to at least one benzene ring of general formulas (4) to (6). More preferred are groups represented by the following general formulas (5a) to (5f) condensed with general formula (5).
• L 11 and L 21 to L 26 each represent a single bond or a divalent linking group.
• the description and preferred ranges of L 11 and L 21 to L 26 can be referred to the description and preferred ranges of L 2 above.
• R 41 to R 110 each independently represent a hydrogen atom or a substituent.
• the cyclic structure formed by bonding to each other may be an aromatic ring or an alicyclic ring, or may contain a heteroatom, and the cyclic structure may be a condensed ring of two or more rings.
• the heteroatoms referred to here are preferably those selected from the group consisting of nitrogen atoms, oxygen atoms and sulfur atoms.
• Examples of cyclic structures formed include benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, imidazoline ring, oxazole ring, isoxazole ring, thiazole ring, iso thiazole ring, cyclohexadiene ring, cyclohexene ring, cyclopentaene ring, cycloheptatriene ring, cycloheptadiene ring, cycloheptaene ring, furan ring, thiophene ring, naphthyridine ring, quinoxaline ring, quinoline ring and the like.
• a ring formed by condensing a large number of rings such as a phenanthrene ring or a triphenylene ring may be formed.
• the number of rings contained in the group represented by formula (6) may be selected from the range of 3-5, or may be selected from the range of 5-7.
• the number of rings contained in the groups represented by general formulas (5a) to (5f) may be selected from within the range of 5 to 7, and may be 5.
• substituents that R 41 to R 110 can take include the groups of the above-described substituent group B, preferably an unsubstituted alkyl group having 1 to 10 carbon atoms or an unsubstituted alkyl group having 1 to 10 carbon atoms.
• R 41 to R 110 are hydrogen atoms or unsubstituted alkyl groups having 1 to 10 carbon atoms.
• R 41 to R 110 are hydrogen atoms or unsubstituted aryl groups having 6 to 10 carbon atoms.
• all of R 41 to R 110 are hydrogen atoms.
• the carbon atoms (ring skeleton-constituting carbon atoms) to which R 41 to R 110 are bonded in general formulas (5a) to (5f) may each independently be substituted with a nitrogen atom.
• C—R 41 to C—R 110 in general formulas (5a) to (5f) may each independently be substituted with N.
• the number of nitrogen atoms substituted is preferably 0 to 4, more preferably 1 to 2, among the groups represented by general formulas (5a) to (5f). In one aspect of the present invention, the number of nitrogen atoms substituted is 0. Also, when two or more are substituted with nitrogen atoms, the number of nitrogen atoms substituted in one ring is preferably one.
• X 1 to X 6 represent an oxygen atom, a sulfur atom or NR. In one aspect of the invention, X 1 -X 6 are oxygen atoms.
• X 1 -X 6 are sulfur atoms. In one aspect of the invention, X 1 -X 6 are NR.
• R represents a hydrogen atom or a substituent, preferably a substituent.
• a substituent selected from the substituent group A can be exemplified. For example, an unsubstituted phenyl group or a phenyl group substituted with one or a combination of two or more groups selected from the group consisting of alkyl groups and aryl groups can be preferably employed.
• * represents a bonding position.
• a compound that is represented by the following general formula (7) and emits delayed fluorescence can be particularly preferably used as the delayed fluorescence material.
• a compound represented by general formula (7) can be employed as the second organic compound.
• R 1 to R 5 represent a cyano group
• at least one of R 1 to R 5 represents a substituted amino group
• the remaining R 1 to R 5 represent hydrogen atoms
• It represents a deuterium atom or a substituent other than a cyano group and a substituted amino group.
• the substituted amino group here is preferably a substituted or unsubstituted diarylamino group, and two aryl groups constituting the substituted or unsubstituted diarylamino group may be linked to each other.
• the linkage may be a single bond (in which case a carbazole ring is formed), -O-, -S-, -N(R 6 )-, -C(R 7 )(R 8 )-, -Si(R 9 )(R 10 )- or the like.
• R 6 to R 10 each represent a hydrogen atom, a deuterium atom or a substituent
• R 7 and R 8 and R 9 and R 10 may be linked together to form a cyclic structure.
• Substituted amino groups can be any of R 1 to R 5 , for example R 1 and R 2 , R 1 and R 3 , R 1 and R 4 , R 1 and R 5 , R 2 and R 3 , R 2 and R 4 , R 1 and R 2 and R 3 , R 1 and R 2 and R 4 , R 1 and R 2 and R 5 , R 1 and R 3 and R 4 , R 1 and R 3 and R 5 , R 2 and R 3 and R 4 , R 1 and R 2 and R 3 and R 4 , R 1 and R 2 and R 3 and R 4 , R 1 and R 2 and R 3 and R 4 , R 1 and R 2 and R 3 and R 5 , R 1 and R 2 and R 4 and R 5 , R 1 and R 2 and R 3 , R 4 and R 5 can be substituted amino groups, and the like.
• Cyano groups may also be any of R 1 to R 5 , for example R 1 , R 2 , R 3 , R 1 and R 2 , R 1 and R 3 , R 1 and R 4 , R 1 and R 5 , R 2 and R 3 , R 2 and R 4 , R 1 and R 2 and R 3 , R 1 and R 2 and R 4 , R 1 and R 2 and R 5 , R 1 and R 3 and R 4 , R 1 and R 3 and R 5 , R 2 and R 3 and R 4 can be cyano groups.
• R 1 to R 5 which are neither a cyano group nor a substituted amino group represent a hydrogen atom, a deuterium atom or a substituent.
• substituents here include hydroxyl group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (eg, 1 to 40 carbon atoms), alkoxy group (eg, 1 to 40 carbon atoms).
• halogen atom eg, fluorine atom, chlorine atom, bromine atom, iodine atom
• alkyl group eg, 1 to 40 carbon atoms
• alkoxy group eg, 1 to 40 carbon atoms
• an alkylthio group eg, 1 to 40 carbon atoms
• an aryl group eg, 6 to 30 carbon atoms
• an aryloxy group eg, 6 to 30 carbon atoms
• an arylthio group eg, 6 to 30 carbon atoms
• a heteroaryl group For example, ring skeleton atoms of 5 to 30), heteroaryloxy groups (for example, ring skeleton atoms of 5 to 30), heteroarylthio groups (for example, ring skeleton atoms of 5 to 30), acyl groups (for example, carbon atoms of 1 to 40), alkenyl groups (eg, 1 to 40 carbon atoms), alkynyl groups (eg, 1 to 40 carbon atoms), alkoxycarbonyl groups (eg, 1 to 40 carbon atoms), aryloxycarbonyl groups (eg, 1 to 40 carbon atoms) , a heteroaryloxycarbonyl group (e.g., 1
• Substituent group A consisting of substituted groups can be mentioned.
• substituent when the aryl group of the diarylamino group is substituted include the substituents of the above substituent group A, and further include a cyano group and a substituted amino group.
• Specific examples of the compound group and compounds encompassed by the general formula (7) are referred to here as part of the present specification, paragraphs 0008 to 0048 of WO2013/154064, and paragraphs 0009 to WO2015/080183. 0030, paragraphs 0006 to 0019 of WO2015/129715, paragraphs 0013 to 0025 of JP-A-2017-119663, and paragraphs 0013-0026 of JP-A-2017-119664.
• any two of Y 1 , Y 2 and Y 3 represent a nitrogen atom and the remaining one represents a methine group, or all of Y 1 , Y 2 and Y 3 represent a nitrogen atom.
• Z 1 and Z 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• R 11 to R 18 each independently represent a hydrogen atom, a deuterium atom or a substituent, and at least one of R 11 to R 18 is a substituted or unsubstituted arylamino group or a substituted or unsubstituted carbazolyl group is preferably
• the benzene ring constituting the arylamino group and the benzene ring constituting the carbazolyl group may each form a single bond or a linking group together with R 11 to R 18 .
• the compound represented by general formula (8) contains at least two carbazole structures in its molecule. Examples of the substituents that Z 1 and Z 2 can take include the substituents of the substituent group A described above.
• R 11 to R 18 , the arylamino group and the carbazolyl group can take include the substituents of the substituent group A, the cyano group, the substituted arylamino group and the substituted alkylamino group. be able to.
• R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 are bonded to each other to form a cyclic structure. good too.
• the compounds represented by the general formula (9) are particularly useful.
• any two of Y 1 , Y 2 and Y 3 represent a nitrogen atom and the remaining one represents a methine group, or all of Y 1 , Y 2 and Y 3 represent a nitrogen atom.
• Z2 represents a hydrogen atom, a deuterium atom or a substituent.
• R 11 to R 18 and R 21 to R 28 each independently represent a hydrogen atom, a deuterium atom or a substituent. At least one of R 11 to R 18 and/or at least one of R 21 to R 28 preferably represents a substituted or unsubstituted arylamino group or a substituted or unsubstituted carbazolyl group.
• the benzene ring constituting the arylamino group and the benzene ring constituting the carbazolyl group may be combined with R 11 to R 18 or R 21 to R 28 to form a single bond or a linking group.
• substituents that Z 2 can take include the substituents of the substituent group A described above.
• specific examples of the substituents that R 11 to R 18 , R 21 to R 28 , the arylamino group and the carbazolyl group can take include the substituents of the above substituent group A, the cyano group, the substituted arylamino group, Substituted alkylamino groups may be mentioned.
• R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 15 and R 16 , R 16 and R 17 , R 17 and R 18 , R 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 25 and R 26 , R 26 and R 27 , R 27 and R 28 may combine with each other to form a cyclic structure.
• Specific examples of the compound group and compounds encompassed by general formula (9) are described in paragraphs 0020 to 0062 of WO2013/081088, which is cited here as part of the present specification, and Appl. Phys. Let, 98, 083302 (2011) can be referred to.
• R 91 to R 96 each independently represent a hydrogen atom, a deuterium atom, a donor group, or an acceptor group, at least one of which is the donor group, and at least two One is the acceptor group.
• Substitution positions of at least two acceptor groups are not particularly limited, but two acceptor groups in a meta-position relationship with each other are preferably included.
• R 91 is a donor group
• a structure in which at least R 92 and R 94 are acceptor groups and a structure in which at least R 92 and R 96 are acceptor groups can be preferably exemplified.
• Acceptor groups present in the molecule may all be the same or different from each other, but for example, it is possible to select a structure in which all are the same.
• the number of acceptor groups is preferably 2-3, and for example 2 can be selected.
• two or more donor groups may be present, and the donor groups in that case may all be the same or different from each other.
• the number of donor groups is preferably 1 to 3, and may be, for example, only 1 or 2.
• the description and preferred ranges of the donor group and the acceptor group the description and preferred ranges of D and Z in formula (1) can be referred to.
• the donor group is preferably represented by general formula (3)
• the acceptor group is preferably represented by a cyano group or general formula (11) below.
• Y 4 to Y 6 represent a nitrogen atom or a methine group, at least one of which represents a nitrogen atom, preferably all of which represent a nitrogen atom.
• Each of R 101 to R 110 independently represents a hydrogen atom, a deuterium atom, or a substituent, and at least one is preferably an alkyl group.
• L 15 represents a single bond or a linking group, and the description and preferred range of L in general formula (3) can be referred to.
• L15 in general formula ( 11) is a single bond. * represents the bonding position to the carbon atom (C) constituting the ring skeleton of the ring in general formula (10).
• a compound represented by general formula (12) can be employed as the second organic compound.
• Compounds represented by general formula (12) include compounds represented by general formula (12a).
• a compound represented by general formula (15) can be employed as the second organic compound.
• D represents a donor group
• A represents an acceptor group
• R represents a hydrogen atom, a deuterium atom or a substituent.
• Two D's in the general formula (15) may be the same or different.
• substituents for R include an alkyl group and an aryl group optionally substituted with one or a combination of two or more groups selected from the group consisting of an alkyl group and an aryl group. Specific examples of preferred donor groups for D in formulas (12) to (15) are shown below.
• * represents a bonding position and "D" represents a deuterium atom.
• hydrogen atoms may be substituted, for example, with alkyl groups.
• a substituted or unsubstituted benzene ring may be further condensed.
• R in formulas (12) to (15) are shown below.
• * represents a binding position and "D" represents deuterium.
• a compound represented by the following general formula (15a) is particularly preferable among the compounds represented by the general formula (15).
• R 201 to R 221 each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, an aryl group, or a group in which an alkyl group and an aryl group are bonded.
• R201 and R202 , R202 and R203 , R203 and R204 , R205 and R206 , R206 and R207 , R207 and R208 , R214 and R215 , R215 and R216 , R216 and R 217 , R 218 and R 219 , R 219 and R 220 , R 220 and R 221 are bonded to each other to form a benzofuro structure or a benzothieno structure.
• R 201 and R 202 , R 202 and R 203 , R 203 and R 204 , R 205 and R 206 , R 206 and R 207 , R 207 and R 208 and R 214 and R 215 , R 215 and R 216 , R 216 and R 217 , R 218 and R 219 , R 219 and R 220 , R 220 and R 221 are bonded together to form a benzofuro structure or It forms a benzothieno structure.
• R 203 and R 204 are bonded together to form a benzofuro structure or a benzothieno structure, and even more preferably R 203 and R 204 and R 216 and R 217 are bonded together to form a benzofuro structure or a benzothieno structure.
• R 203 and R 204 , R 216 and R 217 are bonded to each other to form a benzofuro structure or benzothieno structure
• R 206 and R 219 are substituted or unsubstituted aryl groups (preferably substituted or unsubstituted a substituted phenyl group, more preferably an unsubstituted phenyl group).
• Some or all of the hydrogen atoms in general formula (15a) may be replaced with deuterium atoms.
• some or all of the hydrogen atoms of the two phenyl groups bonded to the triazinyl group may be replaced with deuterium atoms.
• some or all of the hydrogen atoms bonded to the two carbazolyl groups may be replaced with deuterium atoms.
• R 209 to R 213 may be deuterium atoms.
• t-Bu represents a tertiary butyl group.
• the second organic compound it is possible to use a suitable combination of known delayed fluorescence materials other than those described above. Moreover, even unknown delayed fluorescence materials can be used.
• compounds represented by the general formula (1) described in paragraphs 0013 to 0042 of Japanese Patent Application No. 2021-188860 cited here as part of the present specification, particularly described in paragraphs 0043 to 0048 A compound can be preferably used.
• JP 2013-253121, WO2013/133359, WO2014/034535, WO2014/115743, WO2014/122895, WO2014/126200, WO2014/136758, WO2014/133121 Publications, WO2014/136860, WO2014/196585, WO2014/189122, WO2014/168101, WO2015/008580, WO2014/203840, WO2015/002213, WO2010/01620 WO2015/019725, WO2015/072470, WO2015/108049, WO2015/080182, WO2015/072537, WO2015/080183, JP 2015-129240, WO2015/129714, WO2015/129715, WO2015/133501, WO2015/136880, WO2015/137244, WO2015/137202, WO2015/137136, WO2015/146541, WO2015/159541
• a luminescent material that emits delayed fluorescence can also be employed.
• the third organic compound used in the light-emitting layer of the organic electroluminescence device of the present invention is a compound that emits fluorescence and has a lower LUMO energy than the first organic compound and the second organic compound.
• the third organic compound is a compound that emits fluorescence, has a lower LUMO energy than the first organic compound and the second organic compound, and is the lowest excited singlet smaller than the first organic compound and the second organic compound.
• a compound having energy is preferred.
• the orientation value of the third organic compound in the light-emitting layer is ⁇ 0.3 or less. Then, the organic electroluminescence device of the present invention emits fluorescence derived from the third organic compound.
• Emission from the third organic compound usually includes delayed fluorescence.
• the largest component of light emission from the device is fluorescence from the third organic compound. That is, among the light emitted from the organic electroluminescence device of the present invention, the amount of fluorescence emitted from the third organic compound is the largest.
• the third organic compound includes the first organic compound in an excited singlet state, the second organic compound in an excited singlet state, and the excited singlet state through reverse intersystem crossing from the excited triplet state. It receives energy from the second organic compound and transitions to an excited singlet state.
• the third organic compound has energy from the second organic compound in the excited singlet state and the second organic compound in the excited singlet state through reverse intersystem crossing from the excited triplet state. and transits to the excited singlet state. The resulting excited singlet state of the third organic compound then emits fluorescence when returning to the ground state.
• any fluorescent material fluorescent compound that satisfies predetermined conditions can be used without particular limitation.
• the term “fluorescent material” refers to a material for which fluorescence with an emission lifetime of less than 100 ns (nanoseconds) is observed when the emission lifetime is measured using a fluorescence lifetime measurement system (such as a streak camera system manufactured by Hamamatsu Photonics).
• the emission from the third organic compound may contain delayed fluorescence or phosphorescence, but the largest component of the emission from the third organic compound is fluorescence.
• the organic electroluminescent device does not emit phosphorescence, or emits less than 1% of the fluorescence.
• Two or more of the third organic compounds may be used as long as they satisfy the conditions of the present invention. For example, by using together two or more third organic compounds having different emission colors, it is possible to emit light of a desired color. Moreover, monochromatic light may be emitted from the third organic compound by using one type of the third organic compound.
• the maximum emission wavelength of the compound that can be used as the third organic compound is not particularly limited.
• a luminescent material having a maximum emission wavelength in the visible region (380 to 780 nm), a luminescent material having a maximum emission wavelength in the infrared region (780 nm to 1 mm), or a luminescent material having a maximum emission wavelength in the ultraviolet region (for example, 280 to 380 nm)
• a compound or the like can be appropriately selected and used.
• fluorescent materials having emission maxima in the visible region For example, a luminescent material with a maximum emission wavelength in the range of 380 to 780 nm is selected and used, or a luminescent material with a maximum emission wavelength in the range of 570 to 650 nm is selected and used.
• a luminescent material having a maximum emission wavelength in the range of 650 to 700 nm may be selected and used, or a luminescent material having a maximum emission wavelength in the range of 700 to 780 nm may be selected and used.
• the compounds are selected and combined such that there is overlap between the emission wavelength range of the second organic compound and the absorption wavelength range of the third organic compound.
• the third organic compound does not contain metal atoms other than boron atoms.
• the third organic compound may be a compound containing both boron and fluorine atoms. Moreover, it may be a compound containing a boron atom but not containing a fluorine atom. It may also contain no metal atoms at all.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, sulfur atoms, fluorine atoms and boron atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, fluorine atoms and boron atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, sulfur atoms and boron atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms and boron atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms and sulfur atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms and oxygen atoms can be selected.
• a compound consisting of carbon atoms and hydrogen atoms can be selected as the third organic compound.
• Examples of the third organic compound include compounds having a multiple resonance effect of boron atoms and nitrogen atoms, and compounds containing condensed aromatic ring structures such as anthracene, pyrene, and perylene.
• Examples of the third organic compound include compounds having a condensed ring structure containing a boron atom and a nitrogen atom exhibiting a multiple resonance effect and having four or more constituent rings.
• a compound having a structure in which a hetero 6-membered ring containing a boron atom and a nitrogen atom is condensed with a pyrrole ring and two benzene rings sharing a nitrogen atom can also be exemplified.
• a compound represented by the following general formula (16) is used as the third organic compound.
• one of X 1 and X 2 is a nitrogen atom and the other is a boron atom.
• X 1 is a nitrogen atom and X 2 is a boron atom.
• R 17 and R 18 combine with each other to form a single bond to form a pyrrole ring.
• X 1 is a boron atom and X 2 is a nitrogen atom.
• R 21 and R 22 combine with each other to form a single bond to form a pyrrole ring.
• R 1 to R 26 , A 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R10 , R10 and R11 , R11 and R12 , R13 and R14 , R14 and R15 , R15 and R16 , R16 and R17 , R17 and R18 , R18 and R 19 , R 19 and R 20 , R 20 and R 21 , R 21 and R 22 , R 22 and R 23 , R 23 and R 24 , R 24 and R 25 , R 25 and R 26 are bonded together to form a cyclic It may form a structure.
• the cyclic structure formed by combining R 7 and R 8 contains a boron atom and 4 carbon atoms as ring skeleton-constituting atoms.
• the cyclic structure formed by combining R 17 and R 18 contains a boron atom and 4 carbon atoms as ring skeleton constituent atoms when X 1 is a boron atom.
• X 1 is a nitrogen atom
• the cyclic structure is limited to pyrrole rings.
• the cyclic structure formed by combining R 21 and R 22 contains a boron atom and 4 carbon atoms as ring skeleton constituent atoms when X 2 is a boron atom.
• the cyclic structure is limited to pyrrole rings.
• R 7 and R 8 , R 17 and R 18 , R 21 and R 22 are bonded together to form a cyclic structure containing a boron atom, the cyclic structure is preferably a 5- to 7-membered ring.
• a 6-membered ring is more preferred, and a 6-membered ring is even more preferred.
• R 7 and R 8 , R 17 and R 18 , R 21 and R 22 are bonded to each other, they are bonded to form a single bond, —O—, —S—, —N(R 27 )—, —C( R 28 )(R 29 )—, —Si(R 30 )(R 31 )—, —B(R 32 )—, —CO—, —CS—, are preferably formed, and —O—, —S It is more preferred to form - or -N(R 27 )-, and more preferred to form -N(R 27 )-.
• R 27 to R 32 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• R 27 is particularly preferably a substituted or unsubstituted aryl group.
• R 27 to R 32 in the ring formed by combining R 17 and R 18 may combine with at least one of R 16 and R 19 to further form a cyclic structure
• R 21 and R R 27 to R 32 in the ring formed by combining 22 with each other may further combine with at least one of R 20 and R 23 to form a cyclic structure.
• only one pair of R 7 and R 8 , R 17 and R 18 , R 21 and R 22 are bound together.
• only two pairs of R 7 and R 8 , R 17 and R 18 , R 21 and R 22 are attached to each other.
• all of R 7 and R 8 , R 17 and R 18 , R 21 and R 22 are bonded together.
• R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , R 11 and R 12 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 17 , R 18 and R 19 , R 19 and R 20 , R 20 and R 21 , R 22 and R 23 , R 23 and R 24 , R 24 and R 25 , and R 25 and R 26 may be bonded to each other to form a cyclic structure, which may be an aromatic ring or an aliphatic ring, It may also contain a heteroatom, and may be condensed with one or more other rings.
• heteroatoms referred to here are preferably those selected from the group consisting of nitrogen atoms, oxygen atoms and sulfur atoms.
• cyclic structures formed include benzene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, imidazoline ring, furan ring, thiophene ring, oxazole ring, and isoxazole ring.
• the cyclic structure is a substituted or unsubstituted benzene ring (the ring may be further condensed), for example, a benzene ring optionally substituted with an alkyl group or an aryl group. .
• the cyclic structure is a substituted or unsubstituted heteroaromatic ring, preferably a furan ring of benzofuran or a thiophene ring of benzothiophene.
• any one of 1 to 4 can be selected, and 1 can be selected, 2 can be selected, 3 or 4 can be selected.
• a pair selected from R 1 and R 2 , R 2 and R 3 , R 3 and R 4 are bonded together to form a cyclic structure.
• R 5 and R 6 are linked together to form a cyclic structure.
• a pair selected from R 9 and R 10 , R 10 and R 11 , and R 11 and R 12 are bonded together to form a cyclic structure.
• both R 1 and R 2 and R 13 and R 14 are bonded together to form a cyclic structure.
• a pair selected from R 1 and R 2 , R 2 and R 3 , R 3 and R 4 are bonded to each other to form a cyclic structure, and R 5 and R 6 are bonded to each other to form a ring structure.
• both R 5 and R 6 and R 19 and R 20 are bonded together to form a cyclic structure.
• R 1 to R 26 that are not bonded to adjacent R n are hydrogen atoms, deuterium atoms or substituents.
• substituents a group selected from any of Substituent Groups A to E described later can be employed.
• Preferred substituents that R 1 to R 26 can take are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, for example, the substituent is a substituted or unsubstituted aryl groups and, for example, substituents may be substituted or unsubstituted alkyl groups.
• the substituents of the alkyl group, aryl group, and heteroaryl group referred to herein can also adopt a group selected from any one of the substituent groups A to E, but preferably an alkyl group, an aryl group, and a heteroaryl group. It is one or more groups selected from the group consisting of, more preferably a group of substituent group E, which may be unsubstituted.
• at least one of R 1 to R 6 is a substituent, preferably a group of substituents E.
• at least one of R 1 to R 6 is a substituent, preferably a group of substituents E.
• At least one of R 5 and R 6 is a substituent, preferably a group of substituent group E.
• at least one of R 3 and R 6 is a substituent, more preferably both are substituents, preferably a group of substituents E.
• when X 1 is a nitrogen atom at least one of R 15 and R 20 is a substituent, more preferably both are substituents, preferably a group of substituent group E be. At this time, R16 and R17 are bonded to each other to form a single bond.
• R19 and R24 are substituents, more preferably both are substituents, preferably a group of substituent group E be.
• R 21 and R 22 are bonded together to form a single bond.
• at least one of R 8 and R 12 is a substituent, preferably both are substituents.
• R 8 , R 10 and R 12 are substituents.
• Unsubstituted alkyl groups are preferred as substituents for R 8 to R 12 .
• X 1 is a boron atom
• at least one of R 13 and R 17 is a substituent, preferably both are substituents.
• R 13 , R 15 and R 17 are substituents when X 1 is a boron atom.
• the substituents of R 13 to R 17 are preferably unsubstituted alkyl groups.
• X2 is a boron atom
• at least one of R22 and R26 is a substituent, preferably both are substituents.
• R 22 , R 24 and R 26 are substituents when X 2 is a boron atom.
• the substituents of R 22 to R 26 are preferably unsubstituted alkyl groups.
• a 1 and A 2 are hydrogen atoms, deuterium atoms or substituents.
• substituents a group selected from any of Substituent Groups A to E described later can be employed.
• a preferred substituent that A 1 and A 2 can take is an acceptor group.
• the acceptor group is a group having a positive Hammett ⁇ p value.
• Hammet's ⁇ p value is defined by L.P. P. Proposed by Hammett, it quantifies the effect of substituents on the reaction rate or equilibrium of para-substituted benzene derivatives.
• k 0 is the rate constant of the benzene derivative without a substituent
• k is the rate constant of the benzene derivative substituted with a substituent
• K 0 is the equilibrium constant of the benzene derivative without the substituent
• K is the substituent
• the equilibrium constant of the benzene derivative substituted with ⁇ represents the reaction constant determined by the type and conditions of the reaction.
• the acceptor group that A 1 and A 2 can take is more preferably a group having a Hammett's ⁇ p value of greater than 0.2.
• Groups having a Hammett's ⁇ p value of greater than 0.2 include a cyano group, an aryl group substituted with at least a cyano group, a group containing a fluorine atom, and a substituted or unsubstituted heteroaryl group containing a nitrogen atom as a ring skeleton-constituting atom.
• the aryl group substituted with at least a cyano group here may be substituted with a substituent other than a cyano group (for example, an alkyl group or an aryl group), but it is an aryl group substituted only with a cyano group.
• the aryl group substituted with at least a cyano group is preferably a phenyl group substituted with at least a cyano group.
• the number of substituents of the cyano group is preferably 1 or 2, and may be 1 or 2, for example.
• the group containing a fluorine atom includes a fluorine atom, a fluorinated alkyl group, and an aryl group substituted with at least a fluorine atom or a fluorinated alkyl group.
• the fluorinated alkyl group is preferably a perfluoroalkyl group and preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
• a heteroaryl group containing a nitrogen atom as a ring skeleton-constituting atom may be a monocyclic ring or a condensed ring in which two or more rings are condensed.
• the number of rings after condensed is preferably 2 to 6, and can be selected from 2 to 4, or can be 2, for example.
• Specific examples of the ring constituting the heteroaryl group include pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, naphthyridine ring other than quinazoline ring and quinoxaline ring. .
• the ring constituting the heteroaryl group may be substituted with a deuterium atom or a substituent, and the substituent is, for example, one or two groups selected from the group consisting of alkyl groups, aryl groups and heteroaryl groups
• a group composed of one or more can be mentioned.
• a cyano group is particularly preferred as an acceptor group that A 1 and A 2 can take.
• a 1 and A 2 are each independently a hydrogen atom or a deuterium atom.
• at least one of A 1 and A 2 is an acceptor group.
• at least one of A 1 and A 2 is an acceptor group.
• both A 1 and A 2 are acceptor groups.
• both A 1 and A 2 are acceptor groups. In one aspect of the invention, A 1 and A 2 are cyano groups. In one aspect of the invention, A 1 and A 2 are halogen atoms, for example bromine atoms.
• Methyl groups are omitted in this specification. Therefore, for example, A15 indicates a group containing two 4-methylphenyl groups.
• D represents a deuterium atom. * represents a binding position.
• X 1 is a nitrogen atom
• R 7 and R 8 are bonded via a nitrogen atom to form a 6-membered ring
• R 21 and R 22 are bonded via a nitrogen atom to form a 6-membered ring.
• R 17 and R 18 are joined together to form a single bond
• at least one of R 1 to R 6 is a substituted or unsubstituted aryl group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 5 and R 6 are bonded to each other to form an aromatic ring (optionally condensed substituted or unsubstituted benzene ring) or heteroaromatic It forms a ring (preferably a furan ring of optionally condensed substituted or unsubstituted benzofuran, or a thiophene ring of optionally condensed substituted or unsubstituted benzothiophene).
• Each hydrogen atom in skeletons (16a) and (16b) may be substituted with a deuterium atom or a substituent. In addition, it may be substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• R 1 to R 26 , A 1 and A 2 in general formula (16) a compound in which the phenyl groups bonded to the boron atoms in the skeletons (16a) and (16b) are all substituted with a mesityl group, a 2,6-diisopropylphenyl group or a 2,4,6-triisopropylphenyl group; can be exemplified.
• each hydrogen atom in skeletons (16a) and (16b) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• Ar 1 to Ar 4 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• R 41 and R 42 each independently represent a substituted or unsubstituted alkyl group.
• m1 and m2 each independently represent an integer of 0 to 5;
• n1 and n3 each independently represent an integer of 0 to 4;
• n2 and n4 each independently represent an integer of 0 to 3;
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• each of n1-n4 independently represents an integer of 0-2.
• n1 to n4 is 1 or more, preferably at least one of n1 and n2 is 1 or more, and at least one of n3 and n4 is 1 or more.
• n1 and n3 are each independently 1 or 2, and n2 and n4 are 0.
• n2 and n4 are each independently 1 or 2
• n1 and n3 are 0.
• n1-n4 are each independently 1 or 2.
• n1 and n3 are equal and n2 and n4 are equal.
• n1 and n3 are 1 and n2 and n4 are 0. In one aspect of the invention, n1 and n3 are 0 and n2 and n4 are 1. In one aspect of the present invention, n1 to n4 are all 1.
• the bonding positions of Ar 1 to Ar 4 may be at least one of the 3- and 6-positions of the carbazole ring, at least one of the 2- and 7-positions, or at least one of the 1- and 8-positions. It may be one or at least one of the 4th and 5th positions.
• the bonding positions of Ar 1 to Ar 4 may be both 3 and 6 positions, both 2 and 7 positions, or both 1 and 8 positions of the carbazole ring. and may be both 4th and 5th.
• positions 3 and 6 can be preferably selected, or both positions 3 and 6 can be more preferably selected.
• Ar 1 to Ar 4 are all the same group.
• Ar 1 to Ar 4 are each independently a substituted or unsubstituted aryl group, more preferably a substituted or unsubstituted phenyl group or naphthyl group, still more preferably a substituted or unsubstituted is the phenyl group of Examples of the substituent include a group selected from any one of Substituent Groups A to E described below, but an unsubstituted phenyl group is also preferred.
• Ar 1 to Ar 4 include a phenyl group, an o-biphenyl group, an m-biphenyl group, a p-biphenyl group and a terphenyl group.
• m1 and m2 are each independently 0.
• m1 and m2 are each independently an integer from 1 to 5.
• m1 and m2 are equal.
• R 41 and R 42 are alkyl groups having 1 to 6 carbon atoms and can be selected, for example, from alkyl groups having 1 to 3 carbon atoms, or can be selected as methyl groups. .
• substitution positions of the alkyl group are 2-position only, 3-position only, 4-position only, 3-position and 5-position, 2-position and 4-position, 2-position and 6-position with the carbon atom bonded to the boron atom as 1-position.
• 2-position, 4-position and 6-position can be exemplified, preferably at least 2-position, more preferably at least 2-position and 6-position.
• a 1 and A 2 reference can be made to the corresponding description of general formula (16).
• Ar 5 to Ar 8 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• R43 and R44 each independently represent a substituted or unsubstituted alkyl group.
• m3 and m4 each independently represent an integer of 0 to 5;
• n6 and n8 each independently represent an integer of 0 to 3;
• n5 and n7 each independently represent an integer of 0 to 4;
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• the compound of the present invention has, for example, the following skeleton (17a) when X 1 is a nitrogen atom, and X When 2 is a nitrogen atom, it has, for example, the following skeleton (17b).
• Ph is a phenyl group.
• Each hydrogen atom in skeletons (17a) and (17b) may be substituted with a deuterium atom or a substituent. In addition, it may be substituted with a linking group together with adjacent hydrogen atoms to form a cyclic structure.
• a deuterium atom or a substituent may be substituted with a linking group together with adjacent hydrogen atoms to form a cyclic structure.
• R 1 to R 26 A 1 and A 2 in general formula (16).
• At least one hydrogen atom of the benzene ring constituting the carbazole partial structure contained in skeleton (17a) is substituted with a substituted or unsubstituted aryl group.
• each hydrogen atom in skeletons (17a) and (17b) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• Ar 9 to Ar 14 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• n9, n11, n12 and n14 each independently represent an integer of 0 to 4; n10 and n13 each independently represent an integer of 0 to 2; However, at least one of n9, n10, n12, and n13 is 1 or more.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• each of n9-n14 independently represents an integer of 0-2. In one aspect of the present invention, at least one of n9 to n14 is 1 or more.
• n9 and n12 can be 1 or more, and n10 and n13 can be 1 or more. In a preferred embodiment of the present invention, at least one of n9, n10, n12 and n13 is 1 or more. In one aspect of the present invention, n9 and n12 are each independently 1 or 2, and n10, n11, n13 and n14 are 0. In one aspect of the present invention, n10 and n13 are each independently 1 or 2, and n9, n11, n12 and n14 are 0. In one aspect of the present invention, n9 and n12 are each independently 1 or 2, n10 and n13 are each independently 1 or 2, and n11 and n14 are 0.
• n9-n14 are all 1.
• the binding positions of Ar 9 to Ar 14 can be the 3,6 positions of the carbazole ring or other positions.
• Ar 9 to Ar 14 are all the same group.
• Ar 15 to Ar 20 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• n15, n17, n18 and n20 each independently represent an integer of 0 to 4; n16 and n19 each independently represent an integer of 0 to 2; A 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• Ar 15 to Ar 20 , n15 to n20, A 1 and A 2 the descriptions of Ar 9 to Ar 14 , n9 to n14, A 1 and A 2 in general formula (17a) can be referred to in order. .
• the compound of the present invention has, for example, the following skeleton (18a) when X 1 is a nitrogen atom, and X 2 is a nitrogen atom, it has, for example, the following skeleton (18b).
• Each hydrogen atom in skeletons (18a) and (18b) may be substituted with a deuterium atom or a substituent. In addition, it may be substituted with a linking group together with adjacent hydrogen atoms to form a cyclic structure.
• R 1 to R 26 , A 1 and A 2 in general formula (16) each hydrogen atom in skeletons (18a) and (18b) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• Ar 21 to Ar 26 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• n21, n23, n24 and n26 each independently represent an integer of 0 to 4;
• n22 and n25 each independently represent an integer of 0 to 2;
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• Ar 9 to Ar 14 , n9 to n14, A 1 and A 2 in general formula (17a) can be referred to.
• Ar 27 to Ar 32 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• n27, n29, n30 and n32 each independently represent an integer of 0 to 4; n28 and n31 each independently represent an integer of 0 to 2;
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• a compound is selected in which two benzene rings constituting the carbazole partial structure present in general formula (16) are condensed with another ring.
• a compound in which a benfuran ring is condensed, a compound in which a benzothiophene ring is condensed, and a compound in which a benzene ring is condensed can be particularly preferably selected. Compounds in which these rings are condensed will be described below with specific examples.
• Preferred examples include compounds in which a benzofuran ring or a benzothiophene ring is condensed with a benzene ring to which a boron atom is not directly bonded, of the two benzene rings constituting the carbazole partial structure present in general formula (16).
• Examples of such compounds include compounds having the following skeleton (19a) and compounds having the following skeleton (19b).
• Y 1 to Y 4 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• the two hydrogen atoms here indicate a state in which two benzene rings bonded to the boron atom are not connected to each other.
• Y 1 and Y 2 are preferably the same, and Y 3 and Y 4 are preferably the same, but they may be different.
• Y 1 -Y 4 are single bonds.
• Y 1 -Y 4 are N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• Z 1 to Z 4 each independently represent an oxygen atom or a sulfur atom.
• Z 1 and Z 2 are preferably the same, and Z 3 and Z 4 are preferably the same, but they may be different.
• Z 1 -Z 4 are oxygen atoms.
• the furan ring of benzofuran is fused to the benzene ring constituting the carbazole partial structure in (19a) and (19b).
• the orientation of the condensed furan ring is not restricted.
• Z 1 -Z 4 are sulfur atoms.
• the thiophene ring of benzothiophene is fused to the benzene ring that constitutes the carbazole moiety in (19a) and (19b).
• the orientation of the fused thiophene rings is not restricted.
• Each hydrogen atom in skeletons (19a) and (19b) may be substituted with a deuterium atom or a substituent. In addition, it may be substituted with a linking group together with adjacent hydrogen atoms to form a cyclic structure.
• a deuterium atom or a substituent may be substituted with a linking group together with adjacent hydrogen atoms to form a cyclic structure.
• R 1 to R 26 A 1 and A 2 in general formula (16).
• each hydrogen atom in skeletons (19a) and (19b) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• Ar 51 and Ar 52 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• R51 and R52 each independently represent a substituted or unsubstituted alkyl group.
• m51 and m52 each independently represent an integer of 0 to 4;
• n51 and n52 each independently represent an integer of 0 to 2;
• Y 1 to Y 4 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• Z 1 to Z 4 each independently represent an oxygen atom or a sulfur atom.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• n51 and n52 are the same number.
• n51 and n52 may be 0, and n51 and n52 may be 1.
• m51 and m52 are the same number.
• m51 and m52 are integers from 0-3.
• m51 and m52 may be 0, m51 and m52 may be 1, m51 and m52 may be 2, and m51 and m52 may be 3.
• Preferred groups for Ar 51 , Ar 52 , R 51 , R 52 , A 1 and A 2 are the corresponding descriptions for Ar 1 to Ar 4 , R 41 to R 42 , A 1 and A 2 in general formula (16a) can be referred to.
• Ar 53 and Ar 54 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• R53 and R54 each independently represent a substituted or unsubstituted alkyl group.
• m53 and m54 each independently represent an integer of 0 to 4;
• n53 and n54 each independently represent an integer of 0 to 2;
• Y 3 and Y 4 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• Z3 and Z4 each independently represent an oxygen atom or a sulfur atom.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• Ar 53 , Ar 54 , R 53 , R 54 , m53, m54, n53, n54, A 1 and A 2 refer to Ar 51 , Ar 52 , R 51 , R 52 , m51, The descriptions of m52, n51, n52, A 1 and A 2 can be referred to.
• the compound represented by the general formula (19b) is not limited to the following specific examples.
• compounds in which all Xs in the molecule are oxygen atoms and compounds in which all Xs in the molecule are sulfur atoms are disclosed, respectively.
• a compound in which a part of X in the molecule is an oxygen atom and the rest is a sulfur atom can also be employed.
• a compound in which a benzofuran ring or a benzothiophene ring is condensed with a benzene ring to which a boron atom is directly bonded, of the two benzene rings constituting the carbazole partial structure present in general formula (16) can be preferably mentioned.
• Examples of such compounds include compounds having the following skeleton (20a) and compounds having the following skeleton (20b).
• Y 5 to Y 8 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• Z 5 to Z 8 each independently represent an oxygen atom or a sulfur atom.
• each hydrogen atom in skeletons (20a) and (20b) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• Ar 55 and Ar 56 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• R55 and R56 each independently represent a substituted or unsubstituted alkyl group.
• m55 and m56 each independently represents an integer of 0 to 4;
• n55 and n56 each independently represent an integer of 0 to 4;
• Y 5 and Y 6 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• Z5 and Z6 each independently represent an oxygen atom or a sulfur atom.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• n55 and n56 are integers from 0-2.
• n55 and n56 may be 0 and n55 and n56 may be 1.
• m51 and m52 are the same number.
• the description of m51 and m52 in general formula (19a) can be referred to.
• corresponding descriptions of Ar 1 , Ar 3 , R 41 , R 42 , A 1 and A 2 in general formula (16a) can be referred to.
• Ar 57 and Ar 58 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• R57 and R58 each independently represent a substituted or unsubstituted alkyl group.
• m57 and m58 each independently represents an integer of 0 to 4;
• n57 and n58 each independently represent an integer of 0 to 4;
• Y7 and Y8 each independently represent two hydrogen atoms, a single bond or N( R27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• Z7 and Z8 each independently represent an oxygen atom or a sulfur atom.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• Ar 57 , Ar 58 , R 57 , R 58 , m57, m58, n57, n58, A 1 and A 2 refer to Ar 55 , Ar 56 , R 55 , R 56 , m55, The descriptions of m56, n55, n56, A 1 and A 2 can be referred to.
• the compound represented by the general formula (20b) is not limited to the following specific examples.
• compounds in which all Xs in the molecule are oxygen atoms and compounds in which all Xs in the molecule are sulfur atoms are disclosed, respectively.
• a compound in which a part of X in the molecule is an oxygen atom and the rest is a sulfur atom can also be employed.
• a compound in which a benzofuran ring or a benzothiophene ring is condensed with both of the two benzene rings constituting the carbazole partial structure present in general formula (16) can be preferably mentioned.
• Examples of such compounds include compounds having the following skeleton (21a) and compounds having the following skeleton (21b).
• Y 9 to Y 12 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• Z 9 to Z 16 each independently represent an oxygen atom or a sulfur atom.
• Z 9 to Z 16 are preferably the same, but may be different.
• Z 9 -Z 16 are oxygen atoms.
• Z 9 -Z 16 are sulfur atoms.
• each hydrogen atom in skeletons (21a) and (21b) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• R 59 and R 60 each independently represent a substituted or unsubstituted alkyl group.
• m59 and m60 each independently represents an integer of 0 to 4;
• Y9 and Y10 each independently represent two hydrogen atoms, a single bond or N( R27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• Z 9 to Z 12 each independently represent an oxygen atom or a sulfur atom.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• R 61 and R 62 each independently represent a substituted or unsubstituted alkyl group.
• m61 and m60 each independently represents an integer of 0 to 4;
• Y 11 and Y 12 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• Z 13 to Z 16 each independently represent an oxygen atom or a sulfur atom.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• the compound represented by the general formula (21b) is not limited to the following specific examples.
• compounds in which all Xs in the molecule are oxygen atoms and compounds in which all Xs in the molecule are sulfur atoms are disclosed, respectively.
• a compound in which a part of X in the molecule is an oxygen atom and the rest is a sulfur atom can also be used.
• a compound in which a benzene ring is condensed with a benzene ring to which a boron atom is not directly bonded can be preferably mentioned.
• examples of such compounds include compounds having the following skeleton (22a) and compounds having the following skeleton (22b).
• Y 21 to Y 24 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• Y 21 to Y 24 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• the descriptions of Y 1 to Y 4 in skeletons (19a) and (19b) can be referred to.
• each hydrogen atom in skeletons (22a) and (22b) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• Ar 71 to Ar 74 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• n71 and n73 each independently represents an integer of 0 to 2;
• n72 and n74 each independently represents an integer of 0 to 4;
• Y 21 and Y 22 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• n71-n74 are integers from 0-2.
• n71 and n73 are the same number, and n72 and n74 are the same number.
• n71 to n74 may be the same number.
• n71-n74 may be zero. All of n71 to n74 may be 1.
• n71 and n73 may be 0, and n72 and n74 may be 1, for example.
• Ar 71 to Ar 74 , A 1 and A 2 the corresponding descriptions of Ar 1 to Ar 4 , A 1 and A 2 in general formula (16a) can be referred to.
• Ar 75 to Ar 78 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• n75 and n77 each independently represent an integer of 0 to 2;
• n76 and n78 each independently represents an integer of 0 to 4;
• Y 23 and Y 24 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• n75 to n78 the descriptions of n71 to n74 in general formula (22a) can be referred to.
• the corresponding descriptions of Ar 1 to Ar 4 in general formula (16a) can be referred to.
• a compound in which a benzene ring is condensed with a benzene ring to which a boron atom is directly bonded can be preferably mentioned.
• examples of such compounds include compounds having the following skeleton (23a) and compounds having the following skeleton (23b).
• Y 25 to Y 28 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• Y 25 -Y 28 For details of Y 25 -Y 28 , reference can be made to the corresponding descriptions of skeletons (19a) and (19b).
• each hydrogen atom in skeletons (23a) and (23b) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• Ar 79 and Ar 80 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• R71 and R72 each independently represent a substituted or unsubstituted alkyl group.
• m71 and m72 each independently represents an integer of 0 to 4;
• n79 and n80 each independently represent an integer of 0 to 4;
• Y 25 and Y 26 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• n79 and n80 are integers from 0-2. In one aspect of the present invention, n79 and n80 are the same number, for example both may be 0 or both may be 1. In one aspect of the invention, m71 and m72 are integers from 0-2. In one aspect of the invention, m71 and m72 are the same number, for example both may be 0 or both may be 1. For preferred groups of Ar 79 , Ar 80 , R 71 , R 72 , A 1 and A 2 , corresponding descriptions of Ar 1 , Ar 3 , R 41 , R 42 , A 1 and A 2 in general formula (16a) can be referred to.
• Ar 81 and Ar 82 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• R73 and R74 each independently represent a substituted or unsubstituted alkyl group.
• m73 and m74 each independently represents an integer of 0 to 4;
• n81 and n82 each independently represents an integer of 0 to 4;
• Y 27 and Y 28 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• a compound in which benzene rings are condensed to both of the two benzene rings constituting the carbazole partial structure present in general formula (16) can be preferably mentioned.
• Examples of such compounds include compounds having the following skeleton (24a) and compounds having the following skeleton (24b).
• Y 29 to Y 32 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• Y 29 -Y 32 For details of Y 29 -Y 32 , reference can be made to the corresponding descriptions of skeletons (19a) and (19b).
• each hydrogen atom in skeletons (24a) and (24b) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• R 75 and R 76 each independently represent a substituted or unsubstituted alkyl group.
• m75 and m76 each independently represents an integer of 0 to 4;
• Y 29 and Y 30 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• R 75 , R 76 , m75, m76, A 1 and A 2 the descriptions of R 71 , R 72 , m71, m72, A 1 and A 2 in general formula (23a) can be referred to.
• R 77 and R 78 each independently represent a substituted or unsubstituted alkyl group.
• m77 and m78 each independently represent an integer of 0 to 4;
• Y 31 and Y 32 each independently represent two hydrogen atoms, a single bond or N(R 27 ).
• R27 represents a hydrogen atom, a deuterium atom or a substituent.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• R 77 , R 78 , m77, m78, A 1 and A 2 the description of R 71 , R 72 , m71, m72, A 1 and A 2 in general formula (23a) can be referred to.
• Each hydrogen atom in skeleton (25) may be replaced by a deuterium atom or a substituent. In addition, it may be substituted with a linking group together with adjacent hydrogen atoms to form a cyclic structure.
• a deuterium atom or a substituent may be substituted with a linking group together with adjacent hydrogen atoms to form a cyclic structure.
• R 1 to R 26 A 1 and A 2 in general formula (16).
• At least one hydrogen atom of the benzene ring constituting the carbazole moiety contained in skeleton (25) is substituted with a substituted or unsubstituted aryl group.
• each hydrogen atom in skeleton (25) is not substituted with a linking group together with an adjacent hydrogen atom to form a cyclic structure.
• Ar 91 to Ar 94 each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• n91 and n93 each independently represent an integer of 0-4, and n92 and n94 each independently represent an integer of 0-3.
• ⁇ ring, ⁇ ring, ⁇ ring, and ⁇ ring may be substituted, and at least one ring is substituted with a substituted or unsubstituted aryl group, or optionally substituted benzene ring is condensed or the furan ring of substituted or unsubstituted benzofuran or the thiophene ring of substituted or unsubstituted thiophene are condensed.
• a 1 and A 2 each independently represent a hydrogen atom, a deuterium atom or a substituent.
• n91-n94 are integers from 0-2.
• n91 and n93 are the same number, and n92 and n94 are the same number. All of n91 to n94 may be the same number, for example, all may be 0 or all may be 1.
• Ar 91 to Ar 94 the corresponding descriptions of Ar 1 to Ar 4 in general formula (16a) can be referred to.
• the ⁇ and ⁇ rings have the same substituents or have the same condensed structure, and the ⁇ and ⁇ rings have the same substituents or have the same condensed structure. have.
• both the ⁇ ring and the ⁇ ring are substituted with a substituted or unsubstituted aryl group, an optionally substituted benzene ring is condensed, or a substituted or unsubstituted furan ring of benzofuran Alternatively, the thiophene rings of substituted or unsubstituted thiophene are condensed.
• both the ⁇ ring and the ⁇ ring are substituted with a substituted or unsubstituted aryl group, an optionally substituted benzene ring is condensed, or a substituted or unsubstituted furan ring of benzofuran Alternatively, the thiophene rings of substituted or unsubstituted thiophene are condensed.
• all of the ⁇ ring, ⁇ ring, ⁇ ring, and ⁇ ring are substituted with a substituted or unsubstituted aryl group, or condensed with an optionally substituted benzene ring, or substituted
• the furan ring of unsubstituted benzofuran or the thiophene ring of substituted or unsubstituted thiophene is condensed.
• a 1 and A 2 reference can be made to the corresponding description of general formula (16).
• the skeletons (16a) to (25) are skeletons to which other rings are not condensed. In one aspect of the present invention, the skeletons (16a) to (25) are skeletons to which other rings may be condensed.
• R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 8 and R9 , R9 and R10 , R10 and R11 , R11 and R12 , R13 and R14 , R14 and R15 , R15 and R16 , R16 and R17 , R18 and R19 , R 19 and R 20 , R 20 and R 21 , R 22 and R 23 , R 23 and R 24 , R 24 and R 25 , R 25 and R 26 are linked to each other to form a ring structure. be able to.
• a 1 and A 2 in general formula (16) are acceptor groups.
• examples thereof include compounds having acceptor groups at positions A 1 and A 2 and having any of skeletons (16a) to (25).
• the description and specific examples of the acceptor group the description and specific examples of the acceptor groups of A 1 and A 2 in formula (16) above can be referred to.
• Specific examples of compounds in which A 1 and A 2 are acceptor groups are given below.
• the compounds in which A 1 and A 2 are acceptor groups that can be used in the present invention are not limited to the following specific examples.
• the following specific examples have a structure in which both A 1 and A 2 are "A", and the structure of each compound is specified by individually specifying "A".
• a compound having a rotationally symmetric structure is selected as the compound represented by general formula (16).
• a compound having an axisymmetric structure is selected as the compound represented by General Formula (16).
• a compound having an asymmetric structure is selected as the compound represented by general formula (16).
• Specific examples of compounds having an asymmetric skeleton are given below.
• the compound having an asymmetric skeleton and the compound having an asymmetric structure that can be used in the present invention are not limited to the following specific examples.
• compounds in which all Xs in the molecule are oxygen atoms and compounds in which all Xs in the molecule are sulfur atoms are disclosed, respectively.
• a compound in which a part of X in the molecule is an oxygen atom and the rest is a sulfur atom can also be used.
• a compound having at least one of a tert-butyl group and a phenyl group introduced into the skeleton (26a) or (26b) below is selected as the third organic compound.
• the molecular weight of the compound represented by the general formula (16) is, for example, 1500 or less when the organic layer containing the compound represented by the general formula (16) is intended to be formed by a vapor deposition method and used. It is preferably 1,200 or less, more preferably 1,000 or less, and even more preferably 900 or less.
• the lower limit of molecular weight is the molecular weight of the smallest compound in the compound group represented by general formula (16). Preferably it is 624 or more.
• the compound represented by general formula (16) may be formed into a film by a coating method regardless of its molecular weight. If a coating method is used, it is possible to form a film even with a compound having a relatively large molecular weight.
• the compound represented by general formula (16) has the advantage of being easily dissolved in an organic solvent. Therefore, the compound represented by the general formula (16) can be easily applied to the coating method, and can be easily purified to increase its purity.
• a compound containing a plurality of structures represented by general formula (16) in its molecule as a light-emitting material.
• a polymerizable group is preliminarily present in the structure represented by the general formula (16), and a polymer obtained by polymerizing the polymerizable group is used as the light-emitting material.
• a monomer containing a polymerizable functional group in any of the structures represented by the general formula (16) and polymerizing it alone or copolymerizing it with other monomers, repeating It is conceivable to obtain a polymer having units and use the polymer as a light-emitting material. Alternatively, it is conceivable to obtain a dimer or trimer by coupling the compounds represented by the general formula (16) and use them as a light-emitting material.
• Examples of the polymer having a repeating unit containing the structure represented by general formula (16) include polymers containing the structure represented by the following general formula.
• Q represents a group containing a structure represented by general formula (16), and L 1 and L 2 represent linking groups.
• the number of carbon atoms in the linking group is preferably 0-20, more preferably 1-15, still more preferably 2-10.
• the linking group preferably has a structure represented by -X 11 -L 11 -.
• X 11 represents an oxygen atom or a sulfur atom, preferably an oxygen atom.
• L 11 represents a linking group, preferably a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted A phenylene group is more preferred.
• R 101 , R 102 , R 103 and R 104 each independently represent a substituent. Preferred are substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 6 carbon atoms, and halogen atoms, more preferably unsubstituted alkyl groups having 1 to 3 carbon atoms.
• linking groups represented by L 1 and L 2 can be bonded to any position of the structure representing Q and represented by general formula (16). Two or more linking groups may be linked to one Q to form a crosslinked structure or network structure.
• a polymer having a repeating unit containing these formulas is obtained by introducing a hydroxy group at any position of the structure represented by the general formula (16), and using it as a linker, reacting the following compound to obtain a polymerizable group.
• the polymer containing the structure represented by the general formula (16) in the molecule may be a polymer consisting only of repeating units having the structure represented by the general formula (16), or may have other structures. It may be a polymer containing a repeating unit having Moreover, the repeating unit having the structure represented by the general formula (16) contained in the polymer may be of a single type or of two or more types. Examples of repeating units having no structure represented by general formula (16) include those derived from monomers used in ordinary copolymerization. Examples thereof include repeating units derived from monomers having ethylenically unsaturated bonds such as ethylene and styrene.
• the compound represented by general formula (16) preferably does not contain a metal atom.
• a boron atom is not contained in the metal atom here.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, sulfur atoms and boron atoms can be selected. can be done.
• a compound consisting of atoms selected from the group consisting of carbon, hydrogen, deuterium, nitrogen, oxygen and boron atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon, hydrogen, deuterium, nitrogen, sulfur and boron atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms and boron atoms can be selected.
• a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, oxygen atoms, sulfur atoms and boron atoms can be selected.
• the "alkyl group” may be linear, branched, or cyclic. Moreover, two or more of the linear portion, the cyclic portion and the branched portion may be mixed.
• the number of carbon atoms in the alkyl group can be, for example, 1 or more, 2 or more, or 4 or more. Also, the number of carbon atoms can be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less.
• alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, 2-ethylhexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decanyl group, isodecanyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group.
• alkyl group as a substituent may be further substituted with an aryl group.
• An "alkenyl group” may be linear, branched, or cyclic. Moreover, two or more of the linear portion, the cyclic portion and the branched portion may be mixed.
• the number of carbon atoms in the alkenyl group can be, for example, 2 or more and 4 or more. Also, the number of carbon atoms can be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less.
• alkenyl groups include ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, n-pentenyl, isopentenyl, n-hexenyl, isohexenyl, and 2-ethylhexenyl groups. can be mentioned.
• the alkenyl group as a substituent may be further substituted with a substituent.
• the “aryl group” and “heteroaryl group” may be monocyclic or condensed rings in which two or more rings are condensed. In the case of condensed rings, the number of condensed rings is preferably 2 to 6, and can be selected from 2 to 4, for example.
• rings include benzene ring, pyridine ring, pyrimidine ring, triazine ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, quinoline ring, pyrazine ring, quinoxaline ring, and naphthyridine ring, which are condensed. It may be a circular ring.
• aryl or heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 2-pyridyl, 3-pyridyl, 4 - pyridyl group.
• the number of atoms constituting the ring skeleton of the aryl group is preferably 6 to 40, more preferably 6 to 20, selected within the range of 6 to 14, or selected within the range of 6 to 10.
• the number of atoms constituting the ring skeleton of the heteroaryl group is preferably 4 to 40, more preferably 5 to 20, selected within the range of 5 to 14, or selected within the range of 5 to 10. You may "Arylene group” and "heteroaryl group” can be read by changing the valence number from 1 to 2 in the description of the aryl group and heteroaryl group.
• substituted group A refers to a hydroxyl group, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (e.g., 1 to 40 carbon atoms), an alkoxy group (e.g., 1 to 40), alkylthio groups (eg, 1 to 40 carbon atoms), aryl groups (eg, 6 to 30 carbon atoms), aryloxy groups (eg, 6 to 30 carbon atoms), arylthio groups (eg, 6 to 30 carbon atoms), Heteroaryl group (eg, 5 to 30 ring atoms), heteroaryloxy group (eg, 5 to 30 ring atoms), heteroarylthio group (eg, 5 to 30 ring atoms), acyl group ( For example, 1 to 40 carbon atoms), alkenyl groups (eg, 1 to 40 carbon atoms), alkenyl groups (eg, 1 to 40
• substituted group B means an alkyl group (eg, 1 to 40 carbon atoms), an alkoxy group (eg, 1 to 40 carbon atoms), an aryl group (eg, 6 to 30 carbon atoms), an aryloxy group (eg for example, 6 to 30 carbon atoms), heteroaryl groups (eg, 5 to 30 ring atoms), heteroaryloxy groups (eg, 5 to 30 ring atoms), diarylaminoamino groups (eg, 0 to 30 carbon atoms).
• substituted group C refers to an alkyl group (eg, 1 to 20 carbon atoms), an aryl group (eg, 6 to 22 carbon atoms), a heteroaryl group (eg, 5 to 20 ring skeleton atoms), It means one group or a combination of two or more groups selected from the group consisting of diarylamino groups (eg, 12 to 20 carbon atoms).
• substituted group D refers to an alkyl group (eg, 1 to 20 carbon atoms), an aryl group (eg, 6 to 22 carbon atoms) and a heteroaryl group (eg, 5 to 20 ring skeleton atoms). It means one group selected from the group consisting of or a combination of two or more groups.
• substituted group E refers to one group selected from the group consisting of an alkyl group (eg, 1 to 20 carbon atoms) and an aryl group (eg, 6 to 22 carbon atoms), or a combination of two or more means a group.
• substituent when described as “substituent” or “substituted or unsubstituted” may be selected from, for example, substituent group A, or selected from substituent group B may be selected from Substituent Group C, may be selected from Substituent Group D, or may be selected from Substituent Group E.
• Ar 1 to Ar 3 are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen atom in these rings may be substituted, or the rings are condensed.
• a hydrogen atom is substituted, it is preferably substituted with one or a combination of two or more groups selected from the group consisting of deuterium atoms, aryl groups, heteroaryl groups and alkyl groups.
• a benzene ring or a heteroaromatic ring for example, a furan ring, a thiophene ring, a pyrrole ring, etc.
• R a and R a ' each independently represent a substituent, preferably one or a combination of two or more selected from the group consisting of a deuterium atom, an aryl group, a heteroaryl group and an alkyl group.
• Ra and Ar 1 , Ar 1 and Ar 2 , Ar 2 and Ra′, Ra ′ and Ar 3 , and Ar 3 and Ra may combine with each other to form a cyclic structure.
• the compound represented by general formula (27) preferably contains at least one carbazole structure.
• one benzene ring constituting the carbazole structure may be a ring represented by Ar 1
• one benzene ring constituting the carbazole structure may be a ring represented by Ar 2
• the carbazole structure may be a ring represented by Ar 3 .
• a carbazolyl group may be bonded to one or more of Ar 1 to Ar 3 .
• a substituted or unsubstituted carbazol-9-yl group may be attached to the ring represented by Ar 3 .
• a condensed aromatic ring structure such as anthracene, pyrene, or perylene may be bonded to Ar 1 to Ar 3 .
• the rings represented by Ar 1 to Ar 3 may be one ring constituting a condensed aromatic ring structure.
• at least one of R a and R a ′ may be a group having a condensed aromatic ring structure.
• a plurality of skeletons represented by general formula (27) may be present in the compound.
• it may have a structure in which skeletons represented by general formula (27) are bonded to each other via a single bond or a linking group.
• the skeleton represented by the general formula (27) may be added with a structure exhibiting a multiple resonance effect in which benzene rings are connected to each other by a boron atom, a nitrogen atom, an oxygen atom, or a sulfur atom.
• a compound containing a BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) structure is used as the third organic compound.
• a compound represented by the following general formula (28) is used.
• R 1 to R 7 are each independently a hydrogen atom, a deuterium atom or a substituent. At least one of R 1 to R 7 is preferably a group represented by general formula (29) below.
• general formula (29) In general formula (29), R 11 to R 15 each independently represent a hydrogen atom, a deuterium atom or a substituent, and * represents a bonding position.
• the group represented by general formula (29) may be one, two, or three of R 1 to R 7 in general formula (28). Also, it may be at least four, for example four or five. In a preferred embodiment of the present invention, one of R 1 to R 7 is a group represented by general formula (29).
• R 1 , R 3 , R 5 and R 7 are groups represented by general formula (29). In a preferred embodiment of the present invention, only R 1 , R 3 , R 4 , R 5 and R 7 are groups represented by general formula (29). In a preferred embodiment of the present invention, R 1 , R 3 , R 4 , R 5 and R 7 are groups represented by general formula (29), R 2 and R 4 are hydrogen atoms, deuterium atoms, A substituted alkyl group (eg, 1 to 10 carbon atoms) or an unsubstituted aryl group (eg, 6 to 14 carbon atoms). In one aspect of the present invention, all of R 1 to R 7 are groups represented by general formula (29).
• R 1 and R 7 are the same. In one preferred aspect of the invention, R 3 and R 5 are the same. In one preferred aspect of the invention, R 2 and R 6 are the same. In a preferred embodiment of the present invention, R 1 and R 7 are the same, R 3 and R 5 are the same, and R 1 and R 3 are different from each other. In one preferred aspect of the invention, R 1 , R 3 , R 5 and R 7 are identical. In one preferred embodiment of the invention, R 1 , R 4 and R 7 are the same and different from R 3 and R 5 . In a preferred embodiment of the invention, R3 , R4 and R5 are the same and different from R1 and R7 . In one preferred aspect of the invention, R 1 , R 3 , R 5 and R 7 are all different from R 4 .
• the groups of the substituent group A can be selected.
• Substituents that R 11 to R 15 can take include substituted or unsubstituted alkyl groups (eg, 1 to 40 carbon atoms), substituted or unsubstituted alkoxy groups (eg, 1 to 40 carbon atoms), and substituted or unsubstituted aryl groups. group (eg, 6 to 30 carbon atoms), substituted or unsubstituted aryloxy group (eg, 6 to 30 carbon atoms), substituted or unsubstituted amino group (eg, 0 to 20 carbon atoms).
• Substituent group C groups it is preferably one group or a combination of two or more groups (these groups are hereinafter referred to as "substituent group C groups").
• Substituent group C unsubstituted alkyl groups having 1 to 20 carbon atoms, unsubstituted alkoxy groups having 1 to 20 carbon atoms, unsubstituted aryl groups having 6 to 14 carbon atoms, and aryl groups having 6 to 14 carbon atoms. It is preferable to select an oxy group or an unsubstituted diarylamino group having 5 to 20 ring skeleton atoms (hereinafter, these groups are referred to as "substituent group D groups").
• the substituted amino group here is preferably a disubstituted amino group, and the two substituents for the amino group are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted A substituted alkyl group is preferred, and a substituted or unsubstituted aryl group (diarylamino group) is particularly preferred.
• a group of the above substituent group A, a group of the above substituent group B, or a group of the above substituent group C can be selected.
• the two aryl groups of the diarylamino group may be bonded to each other via a single bond or a linking group, and the linking group referred to here can be referred to the description of the linking group for R 33 and R 34 .
• a specific example of the diarylamino group is, for example, a substituted or unsubstituted carbazol-9-yl group.
• substituted or unsubstituted carbazol-9-yl groups include groups in which L 11 in the above general formula (6) is a single bond.
• R 13 in general formula (29) is a substituent, and R 11 , R 12 , R 14 and R 15 are hydrogen atoms.
• R 11 in general formula (29) is a substituent
• R 12 , R 13 , R 14 and R 15 are hydrogen atoms.
• R 11 and R 13 in general formula (29) are substituents
• R 12 , R 14 and R 15 are hydrogen atoms.
• R 1 to R 7 of general formula (28) may include a group in which all of R 11 to R 15 of general formula (29) are hydrogen atoms (ie, phenyl group).
• R2 , R4 , R6 may be phenyl groups.
• R 8 and R 9 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group (eg, 1 to 40 carbon atoms), an alkoxy group (eg, 1 to 40 carbon atoms), an aryloxy It is preferably one or a combination of two or more groups selected from the group consisting of a group (for example, 6 to 30 carbon atoms) and a cyano group.
• R8 and R9 are the same .
• R 8 and R 9 are halogen atoms, particularly preferably fluorine atoms.
• the total number of substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryloxy groups, and substituted or unsubstituted amino groups present in R 1 to R 9 of general formula (28) is The number is preferably three or more, and for example, three compounds or four compounds can be employed. More preferably, the total number of substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryloxy groups, and substituted or unsubstituted amino groups present in R 1 to R 7 in general formula (28) is 3 or more. is preferable, and for example, a compound with three or a compound with four can be used.
• an alkoxy group, an aryloxy group, or an amino group may not be present in R8 and R9. More preferably, substituted or unsubstituted alkoxy group , substituted or unsubstituted aryloxy group, substituted or unsubstituted amino
• the total number of groups is preferably 3 or more, and for example, a compound with 3 or a compound with 4 can be used.
• R 2 , R 6 , R 8 and R 9 may be free of an alkoxy group, an aryloxy group and an amino group. In a preferred embodiment of the invention, there are 3 or more substituted or unsubstituted alkoxy groups.
• each of R 1 , R 4 and R 7 is a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy. In a preferred embodiment of the present invention, each of R 1 , R 4 and R 7 has a substituted or unsubstituted alkoxy group.
• the total number of substituents having a Hammett's ⁇ p value of less than ⁇ 0.2 in R 1 to R 9 of the general formula (28) is 3 or more.
• Hammett's ⁇ p value is less than -0.2 substituents, for example, methoxy group (-0.27), ethoxy group (-0.24), n-propoxy group (-0.25), isopropoxy group (- 0.45) and the n-butoxy group (-0.32).
• fluorine atom (0.06), methyl group (-0.17), ethyl group (-0.15), tert-butyl group (-0.20), n-hexyl group (-0.15), cyclohexyl Groups such as ( ⁇ 0.15) are not substituents with a Hammett ⁇ p value of less than ⁇ 0.2.
• a compound in which the number of substituents having a Hammett's ⁇ p value of less than ⁇ 0.2 in R 1 to R 9 of the general formula (28) is three, or four can be employed.
• the number of substituents having a Hammett's ⁇ p value of less than ⁇ 0.2 in R 1 to R 7 of the general formula (28) is preferably 3 or more, for example, a compound having 3 can be employed, or a compound that is four. At this time, a substituent having a Hammett's ⁇ p value of less than ⁇ 0.2 may not be present in R 8 and R 9 . More preferably, the number of substituents having a Hammett's ⁇ p value of less than ⁇ 0.2 in R 1 , R 3 , R 4 , R 5 and R 7 of the general formula (28) is 3 or more. Preferably, for example, three compounds can be employed, or four compounds can be employed.
• each of R 1 , R 4 and R 7 has a Hammett's ⁇ p value of less than ⁇ 0.2.
• t-Bu represents a tertiary butyl group.
• Derivatives of the above-exemplified compounds include compounds in which at least one hydrogen atom is substituted with a deuterium atom, an alkyl group, an aryl group, a heteroaryl group, or a diarylamino group.
• the light-emitting layer of the organic electroluminescence device of the present invention contains a first organic compound, a second organic compound and a third organic compound that satisfy the conditions (a) and (b).
• compound T132 is used as the second organic compound
• a compound selected from the group consisting of compounds F101 to F128 is used as the third organic compound.
• the light-emitting layer may have a structure that does not contain any compound that transfers charge or energy, or a metal element other than boron, in addition to the first organic compound, the second organic compound, and the third organic compound.
• the light-emitting layer can also be composed only of a compound consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, boron atoms, oxygen atoms and sulfur atoms.
• the light-emitting layer can consist only of compounds consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, boron atoms and oxygen atoms.
• the light-emitting layer can consist only of compounds consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, boron atoms and sulfur atoms.
• the light-emitting layer can consist only of compounds consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms and boron atoms.
• the light-emitting layer can consist only of compounds consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms and sulfur atoms.
• the light-emitting layer can consist only of compounds consisting of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms and nitrogen atoms.
• the light-emitting layer comprises a first organic compound composed of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms and oxygen atoms, and carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms and sulfur.
• a second organic compound composed of atoms selected from the group consisting of atoms and atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, boron atoms, oxygen atoms and sulfur atoms may contain a third organic compound.
• the light-emitting layer comprises a first organic compound composed of atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms and oxygen atoms, and a group consisting of carbon atoms, hydrogen atoms, deuterium atoms and nitrogen atoms. and a third organic compound composed of atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms and boron atoms.
• the light-emitting layer may be formed by co-depositing the first organic compound, the second organic compound and the third organic compound, or a solution in which the first organic compound, the second organic compound and the third organic compound are dissolved.
• the light-emitting layer may be formed by a coating method using .
• the light-emitting layer is formed by co-evaporation, two or more of the first organic compound, the second organic compound and the third organic compound are mixed in advance and placed in a crucible or the like to form a vapor deposition source, and the vapor deposition source is used.
• a light-emitting layer may be formed by co-evaporation.
• the first organic compound and the second organic compound are mixed in advance to form one vapor deposition source, and the vapor deposition source and the third organic compound vapor deposition source are used to co-evaporate to form the light-emitting layer.
• the organic electroluminescent device of the present invention is held by a substrate, which is not particularly limited and commonly used in organic electroluminescent devices such as glass, transparent plastic, quartz and silicon. Any material formed by
• the anode of the organic electroluminescent device is made from metals, alloys, conductive compounds, or combinations thereof.
• the metal, alloy or conductive compound has a high work function (4 eV or greater).
• the metal is Au.
• the conductive transparent material is selected from CuI, indium tin oxide ( ITO), SnO2 and ZnO. Some embodiments use amorphous materials that can form transparent conductive films, such as IDIXO (In 2 O 3 —ZnO).
• the anode is a thin film. In some embodiments, the thin film is made by evaporation or sputtering.
• the film is patterned by photolithographic methods. In some embodiments, if the pattern does not need to be highly precise (eg, about 100 ⁇ m or greater), the pattern may be formed using a mask with a shape suitable for vapor deposition or sputtering onto the electrode material. In some embodiments, wet film forming methods such as printing and coating methods are used when coating materials such as organic conductive compounds can be applied.
• the anode has a transmittance of greater than 10% when emitted light passes through the anode, and the anode has a sheet resistance of several hundred ohms per unit area or less. In some embodiments, the thickness of the anode is 10-1,000 nm. In some embodiments, the thickness of the anode is 10-200 nm. In some embodiments, the thickness of the anode varies depending on the materials used.
• the cathode is made of electrode materials such as metals with a low work function (4 eV or less) (referred to as electron-injecting metals), alloys, conductive compounds, or combinations thereof.
• the electrode material is sodium, sodium-potassium alloys, magnesium, lithium, magnesium-copper mixtures, magnesium-silver mixtures, magnesium-aluminum mixtures, magnesium-indium mixtures, aluminum - aluminum oxide (Al2 O 3 ) mixtures, indium, lithium-aluminum mixtures and rare earth elements.
• a mixture of an electron-injecting metal and a second metal that is a stable metal with a higher work function than the electron-injecting metal is used.
• the mixture is selected from magnesium-silver mixtures, magnesium-aluminum mixtures, magnesium-indium mixtures, aluminum-aluminum oxide (Al 2 O 3 ) mixtures, lithium-aluminum mixtures and aluminum. In some embodiments, the mixture improves electron injection properties and resistance to oxidation.
• the cathode is manufactured by depositing or sputtering the electrode material as a thin film. In some embodiments, the cathode has a sheet resistance of no more than several hundred ohms per unit area. In some embodiments, the thickness of said cathode is between 10 nm and 5 ⁇ m. In some embodiments, the thickness of the cathode is 50-200 nm.
• either one of the anode and cathode of the organic electroluminescent device is transparent or translucent to allow transmission of emitted light.
• transparent or translucent electroluminescent elements enhance light radiance.
• the cathode is formed of a conductive transparent material as described above for the anode, thereby forming a transparent or translucent cathode.
• the device includes an anode and a cathode, both transparent or translucent.
• the injection layer is the layer between the electrode and the organic layer. In some embodiments, the injection layer reduces drive voltage and enhances light radiance. In some embodiments, the injection layer comprises a hole injection layer and an electron injection layer. The injection layer can be placed between the anode and the light-emitting layer or hole-transporting layer and between the cathode and the light-emitting layer or electron-transporting layer. In some embodiments, an injection layer is present. In some embodiments, there is no injection layer. Preferred examples of compounds that can be used as the hole injection material are given below.
• a barrier layer is a layer that can prevent charges (electrons or holes) and/or excitons present in the light-emitting layer from diffusing out of the light-emitting layer.
• an electron blocking layer is between the light-emitting layer and the hole-transporting layer to block electrons from passing through the light-emitting layer to the hole-transporting layer.
• a hole blocking layer is between the emissive layer and the electron transport layer and blocks holes from passing through the emissive layer to the electron transport layer.
• the barrier layer prevents excitons from diffusing out of the emissive layer.
• the electron blocking layer and the hole blocking layer constitute an exciton blocking layer.
• the terms "electron blocking layer” or "exciton blocking layer” include layers that have the functionality of both an electron blocking layer and an exciton blocking layer.
• Hole blocking layer functions as an electron transport layer. In some embodiments, the hole blocking layer blocks holes from reaching the electron transport layer during electron transport. In some embodiments, the hole blocking layer increases the probability of recombination of electrons and holes in the emissive layer.
• the materials used for the hole blocking layer can be the same materials as described above for the electron transport layer. Preferred examples of compounds that can be used in the hole blocking layer are given below.
• Electron barrier layer The electron blocking layer transports holes. In some embodiments, the electron blocking layer prevents electrons from reaching the hole transport layer during hole transport. In some embodiments, the electron blocking layer increases the probability of recombination of electrons and holes in the emissive layer.
• the materials used for the electron blocking layer may be the same materials as described above for the hole transport layer. Specific examples of preferred compounds that can be used as the electron barrier material are given below.
• Exciton barrier layer The exciton blocking layer prevents diffusion of excitons generated through recombination of holes and electrons in the light emitting layer to the charge transport layer. In some embodiments, the exciton blocking layer allows effective confinement of excitons in the emissive layer. In some embodiments, the light emission efficiency of the device is improved. In some embodiments, an exciton blocking layer is adjacent to the emissive layer on either the anode side or the cathode side, and on both sides thereof. In some embodiments, when an exciton blocking layer is present on the anode side, it may be present between and adjacent to the hole-transporting layer and the light-emitting layer.
• an exciton blocking layer when an exciton blocking layer is present on the cathode side, it may be between and adjacent to the emissive layer and the cathode. In some embodiments, a hole-injection layer, electron-blocking layer, or similar layer is present between the anode and an exciton-blocking layer adjacent to the light-emitting layer on the anode side. In some embodiments, a hole injection layer, electron blocking layer, hole blocking layer or similar layer is present between the cathode and an exciton blocking layer adjacent to the emissive layer on the cathode side. In some embodiments, the exciton blocking layer comprises an excited singlet energy and an excited triplet energy, at least one of which is higher than the excited singlet energy and triplet energy, respectively, of the emissive material.
• the hole-transporting layer comprises a hole-transporting material.
• the hole transport layer is a single layer.
• the hole transport layer has multiple layers.
• the hole transport material has one property of a hole injection or transport property and an electron barrier property.
• the hole transport material is an organic material.
• the hole transport material is an inorganic material. Examples of known hole transport materials that can be used in the present invention include, but are not limited to, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolones.
• the hole transport material is selected from porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds. In some embodiments, the hole transport material is an aromatic tertiary amine compound. Specific examples of preferred compounds that can be used as the hole-transporting material are given below.
• the electron transport layer includes an electron transport material.
• the electron transport layer is a single layer.
• the electron transport layer has multiple layers.
• the electron-transporting material need only function to transport electrons injected from the cathode to the emissive layer.
• the electron transport material also functions as a hole blocking material.
• electron-transporting layers examples include, but are not limited to, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidene methane derivatives, anthraquinodimethanes, anthrone derivatives, oxazide Azole derivatives, azole derivatives, azine derivatives or combinations thereof, or polymers thereof.
• the electron transport material is a thiadiazole derivative or a quinoxaline derivative.
• the electron transport material is a polymeric material. Specific examples of preferred compounds that can be used as the electron-transporting material are given below.
• examples of preferred compounds as materials that can be added to each organic layer are given.
• it may be added as a stabilizing material.
• Preferred materials that can be used in organic electroluminescence elements are specifically exemplified, but materials that can be used in the present invention are not limitedly interpreted by the following exemplified compounds. Moreover, even compounds exemplified as materials having specific functions can be used as materials having other functions.
• the emissive layer is incorporated into the device.
• devices include, but are not limited to, OLED bulbs, OLED lamps, television displays, computer monitors, mobile phones and tablets.
• an electronic device includes an OLED having at least one organic layer including an anode, a cathode, and a light-emitting layer between the anode and the cathode.
• compositions described herein can be incorporated into various photosensitive or photoactivated devices, such as OLEDs or optoelectronic devices.
• the composition may be useful in facilitating charge or energy transfer within a device and/or as a hole transport material.
• OLEDs organic light emitting diodes
• OICs organic integrated circuits
• O-FETs organic field effect transistors
• O-TFTs organic thin film transistors
• O-LETs organic light emitting transistors
• O-SC organic solar cells.
• O-SC organic optical detectors
• O-FQD organic field-quench devices
• LOC luminescent fuel cells
• O-lasers organic laser diodes
• an electronic device includes an OLED including at least one organic layer including an anode, a cathode, and a light-emitting layer between the anode and the cathode.
• the device includes OLEDs of different colors.
• the device includes an array including combinations of OLEDs.
• said combination of OLEDs is a combination of three colors (eg RGB).
• the combination of OLEDs is a combination of colors other than red, green, and blue (eg, orange and yellow-green).
• said combination of OLEDs is a combination of two, four or more colors.
• the device a circuit board having a first side with a mounting surface and a second opposite side and defining at least one opening; at least one OLED on the mounting surface, wherein the at least one OLED is configured to emit light, wherein the at least one OLED includes at least one organic layer including an anode, a cathode, and a light-emitting layer between the anode and the cathode; at least one OLED comprising a housing for a circuit board; at least one connector disposed at an end of said housing, said housing and said connector defining a package suitable for attachment to a lighting fixture.
• the OLED light comprises multiple OLEDs mounted on a circuit board such that light is emitted in multiple directions. In some embodiments, some light emitted in the first direction is polarized and emitted in the second direction. In some embodiments, a reflector is used to polarize light emitted in the first direction.
• the emissive layers of the invention can be used in screens or displays.
• the compounds of the present invention are deposited onto a substrate using processes such as, but not limited to, vacuum evaporation, deposition, evaporation or chemical vapor deposition (CVD).
• the substrate is a photoplate structure useful in two-sided etching to provide unique aspect ratio pixels.
• Said screens also called masks
• the corresponding artwork pattern design allows placement of very steep narrow tie-bars between pixels in the vertical direction as well as large and wide beveled openings in the horizontal direction.
• the internal patterning of the pixels makes it possible to construct three-dimensional pixel openings with various aspect ratios in the horizontal and vertical directions. Further, the use of imaged "stripes" or halftone circles in pixel areas protects etching in specific areas until these specific patterns are undercut and removed from the substrate. All pixel areas are then treated with a similar etch rate, but their depth varies with the halftone pattern. Varying the size and spacing of the halftone patterns allows for etching with varying degrees of protection within the pixel, allowing for the localized deep etching necessary to form steep vertical bevels. . A preferred material for the evaporation mask is Invar.
• Invar is a metal alloy that is cold rolled into long thin sheets in steel mills. Invar cannot be electrodeposited onto a spin mandrel as a nickel mask.
• a suitable and low-cost method for forming the open areas in the deposition mask is by wet chemical etching.
• the screen or display pattern is a matrix of pixels on a substrate.
• screen or display patterns are fabricated using lithography (eg, photolithography and e-beam lithography).
• the screen or display pattern is processed using wet chemical etching.
• the screen or display pattern is fabricated using plasma etching.
• An OLED display is generally manufactured by forming a large mother panel and then cutting the mother panel into cell panels.
• each cell panel on a mother panel is formed by forming a thin film transistor (TFT) having an active layer and source/drain electrodes on a base substrate, coating the TFT with a planarizing film, pixel electrodes, and a light emitting layer. , a counter electrode and an encapsulation layer, are sequentially formed and cut from the mother panel.
• TFT thin film transistor
• An OLED display is generally manufactured by forming a large mother panel and then cutting the mother panel into cell panels.
• each cell panel on a mother panel is formed by forming a thin film transistor (TFT) having an active layer and source/drain electrodes on a base substrate, coating the TFT with a planarizing film, pixel electrodes, and a light emitting layer. , a counter electrode and an encapsulation layer, are sequentially formed and cut from the mother panel.
• TFT thin film transistor
• an organic light emitting diode (OLED) display comprising: forming a barrier layer on the base substrate of the mother panel; forming a plurality of display units on the barrier layer in cell panel units; forming an encapsulation layer over each of the display units of the cell panel; and applying an organic film to the interfaces between the cell panels.
• the barrier layer is an inorganic film, eg, made of SiNx, and the edges of the barrier layer are covered with an organic film, made of polyimide or acrylic.
• the organic film helps the mother panel to be softly cut into cell panels.
• a thin film transistor (TFT) layer has an emissive layer, a gate electrode, and source/drain electrodes.
• Each of the plurality of display units may have a thin film transistor (TFT) layer, a planarization film formed on the TFT layer, and a light emitting unit formed on the planarization film, and The applied organic film is made of the same material as that of the planarizing film, and is formed at the same time as the planarizing film is formed.
• the light-emitting unit is coupled with the TFT layer by a passivation layer, a planarizing film therebetween, and an encapsulation layer that covers and protects the light-emitting unit.
• the organic film is not connected to the display unit or encapsulation layer.
• each of the organic film and the planarizing film may include one of polyimide and acrylic.
• the barrier layer may be an inorganic film.
• the base substrate may be formed of polyimide.
• the method further includes attaching a carrier substrate made of a glass material to another surface of a base substrate made of polyimide before forming a barrier layer on the other surface of the base substrate; separating the carrier substrate from the base substrate prior to cutting along the interface.
• the OLED display is a flexible display.
• the passivation layer is an organic film placed on the TFT layer to cover the TFT layer.
• the planarizing film is an organic film formed over a passivation layer.
• the planarizing film is formed of polyimide or acrylic, as is the organic film formed on the edge of the barrier layer. In some embodiments, the planarizing film and the organic film are formed simultaneously during the manufacture of an OLED display. In some embodiments, the organic film may be formed on the edge of the barrier layer such that a portion of the organic film is in direct contact with the base substrate and a remaining portion of the organic film is , in contact with the barrier layer while surrounding the edges of the barrier layer.
• the emissive layer comprises a pixel electrode, a counter electrode, and an organic emissive layer disposed between the pixel electrode and the counter electrode.
• the pixel electrodes are connected to source/drain electrodes of the TFT layer.
• a suitable voltage is formed between the pixel electrode and the counter electrode, causing the organic light-emitting layer to emit light, thereby displaying an image. is formed.
• An image forming unit having a TFT layer and a light emitting unit is hereinafter referred to as a display unit.
• the encapsulation layer that covers the display unit and prevents the penetration of external moisture may be formed into a thin encapsulation structure in which organic films and inorganic films are alternately laminated.
• the encapsulation layer has a thin film-like encapsulation structure in which multiple thin films are stacked.
• the organic film applied to the interface portion is spaced apart from each of the plurality of display units.
• the organic film is formed such that a portion of the organic film is in direct contact with the base substrate and a remaining portion of the organic film is in contact with the barrier layer while surrounding the edges of the barrier layer. be done.
• the OLED display is flexible and uses a flexible base substrate made of polyimide.
• the base substrate is formed on a carrier substrate made of glass material, and then the carrier substrate is separated.
• a barrier layer is formed on the surface of the base substrate opposite the carrier substrate.
• the barrier layer is patterned according to the size of each cell panel. For example, a base substrate is formed on all surfaces of a mother panel, while barrier layers are formed according to the size of each cell panel, thereby forming grooves at the interfaces between the barrier layers of the cell panels. Each cell panel can be cut along the groove.
• the manufacturing method further comprises cutting along the interface, wherein a groove is formed in the barrier layer, at least a portion of the organic film is formed with the groove, and the groove is Does not penetrate the base substrate.
• a TFT layer of each cell panel is formed, and a passivation layer, which is an inorganic film, and a planarization film, which is an organic film, are placed on and cover the TFT layer.
• the planarizing film eg made of polyimide or acrylic
• the interface grooves are covered with an organic film, eg made of polyimide or acrylic. This prevents cracking by having the organic film absorb the impact that occurs when each cell panel is cut along the groove at the interface.
• the grooves at the interfaces between the barrier layers are coated with an organic film to absorb shocks that might otherwise be transmitted to the barrier layers, so that each cell panel is softly cut and the barrier layers It may prevent cracks from forming.
• the organic film covering the groove of the interface and the planarizing film are spaced apart from each other. For example, when the organic film and the planarizing film are connected to each other as a single layer, external moisture may enter the display unit through the planarizing film and the portion where the organic film remains. The organic film and planarizing film are spaced from each other such that the organic film is spaced from the display unit.
• the display unit is formed by forming a light emitting unit and an encapsulating layer is placed over the display unit to cover the display unit.
• the carrier substrate carrying the base substrate is separated from the base substrate.
• the carrier substrate separates from the base substrate due to the difference in coefficient of thermal expansion between the carrier substrate and the base substrate.
• the mother panel is cut into cell panels.
• the mother panel is cut along the interfaces between the cell panels using a cutter.
• the interface groove along which the mother panel is cut is coated with an organic film so that the organic film absorbs impact during cutting.
• the barrier layer can be prevented from cracking during cutting.
• the method reduces the reject rate of the product and stabilizes its quality.
• Another embodiment includes a barrier layer formed on a base substrate, a display unit formed on the barrier layer, an encapsulation layer formed on the display unit, and an organic layer applied to the edges of the barrier layer.
• An OLED display comprising a film.
• the HOMO energies E HOMO and LUMO energies E LUMO of the above compounds are shown in Table 1 below.
• the lowest excited singlet energy ES1 and the lowest excited triplet energy ET1 measured for some compounds are also shown.
• Examples 1 to 10, Comparative Examples 5 to 7, 9, 10, 12 Each thin film was laminated at a degree of vacuum of 1 ⁇ 10 ⁇ 6 Pa by a vacuum evaporation method on a 2 mm-thick glass substrate on which an anode made of indium tin oxide (ITO) with a thickness of 50 nm was formed.
• ITO indium tin oxide
• HATCN was deposited on ITO to a thickness of 5 nm to form a hole injection layer
• NPD was deposited thereon to a thickness of 60 nm to form a hole transport layer.
• EB1 was deposited to a thickness of 5 nm to form an electron blocking layer.
• the first organic compound, the second organic compound, and the third organic compound were co-deposited from different vapor deposition sources so as to have the composition shown in Table 2 or Table 3, thereby forming a light-emitting layer with a thickness of 40 nm.
• HB1 was deposited to a thickness of 10 nm to form a hole blocking layer, followed by deposition of ET1 to a thickness of 30 nm to form an electron transport layer.
• Liq was vapor-deposited to a thickness of 2 nm to form an electron injection layer, and then aluminum (Al) was vapor-deposited to a thickness of 100 nm to form a cathode.
• An organic electroluminescence device was thus produced. It was confirmed that all the devices produced here satisfied the formula (a), and the maximum component of light emission was the fluorescence from the third organic compound.
• the light-emitting layer having the composition shown in Table 2 was formed by co-evaporation of the first organic compound and the second organic compound without using the evaporation source of the third organic compound.
• An organic electroluminescence device was produced in the same manner as in 1.
• Table 2 shows the composition of the light-emitting layer, the measurement results of the external quantum efficiency EQE and the emission maximum wavelength for each of the devices fabricated in Examples 1-6 and Comparative Examples 1-10.
• the composition ratio of the third organic compound in Examples 1 to 4 and Comparative Examples 5 to 7, 9, and 10 is the ratio (% by weight) of the total weight of the first organic compound and the second organic compound.
• the composition ratio of other organic compounds is expressed as a ratio (% by weight) to the total weight of the organic compounds constituting the light-emitting layer.
• "-" indicates that the third organic compound was not added.
• Table 3 shows the composition of the light-emitting layer of each element produced in Examples 7 to 10 and evaluation results of durability.
• "LT95%” in Table 3 is measured by measuring the time (T95%) until the luminance reaches 95% of the initial luminance by continuously driving each device at a current density of 12.6 mA/cm is a relative value calculated by dividing the value of by T95% of the element manufactured in Example 7. A larger value of LT95% means better durability.
• the devices of Examples 7 to 10 differed in the concentration of the second organic compound in the light emitting layer, and had the same emission maximum wavelength of 529 nm and an external quantum efficiency of about 22%. Moreover, Table 3 shows that the durability of the device tends to be improved by increasing the concentration of the second organic compound.
• the LUMO energy of the second organic compound is Even if the LUMO energy of the first organic compound is lower than that of the second organic compound, the external quantum efficiency can be improved by increasing the concentration of the second organic compound. As a result, the range of selection of the LUMO energy of the third organic compound can be expanded, so that the degree of freedom in designing the material of the organic electroluminescence device can be increased. Therefore, the present invention has high industrial applicability.

Landscapes

• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Organic Chemistry (AREA)
• Optics & Photonics (AREA)
• Electroluminescent Light Sources (AREA)

Priority Applications (5)

Applications Claiming Priority (8)

Publications (1)

Family

ID=84545566

Family Applications (1)

Country Status (5)

Cited By (1)

Citations (34)

Family Cites Families (5)

• 2022
  • 2022-03-30 WO PCT/JP2022/015888 patent/WO2022270113A1/ja not_active Ceased
  • 2022-03-30 KR KR1020237044678A patent/KR20240025546A/ko active Pending
  • 2022-03-30 JP JP2023529615A patent/JP7802383B2/ja active Active
  • 2022-03-30 US US18/573,055 patent/US20240324263A1/en active Pending
  • 2022-03-30 EP EP22828032.7A patent/EP4361158A4/en active Pending

Patent Citations (35)

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events