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WO2015137244A1 - Matériau d'émission de lumière, élément électroluminescent organique et composé associé - Google Patents

Matériau d'émission de lumière, élément électroluminescent organique et composé associé Download PDF

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WO2015137244A1
WO2015137244A1 PCT/JP2015/056622 JP2015056622W WO2015137244A1 WO 2015137244 A1 WO2015137244 A1 WO 2015137244A1 JP 2015056622 W JP2015056622 W JP 2015056622W WO 2015137244 A1 WO2015137244 A1 WO 2015137244A1
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group
general formula
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light emitting
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佐藤　忠久
ジエ リ
安達　千波矢
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Kyushu University NUC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains three hetero rings
    • C07D513/14—Ortho-condensed systems
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • 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
    • 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
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • C09K2211/1081—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with sulfur
    • 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
    • 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

Definitions

  • the present invention relates to a compound useful as a light emitting material and an organic light emitting device using the compound.
  • organic light emitting devices such as organic electroluminescence devices (organic EL devices)
  • organic electroluminescence devices organic electroluminescence devices
  • various efforts have been made to increase the light emission efficiency by newly developing and combining electron transport materials, hole transport materials, light emitting materials, and the like constituting the organic electroluminescence element.
  • the results of studies on synthesis methods and optical properties of compounds having a bisthiadiazoloquinoxaline skeleton have been reported. There are also reports mentioning that they can be used as materials for electroluminescent devices.
  • Non-Patent Document 1 describes a method for synthesizing a compound having a bisthiadiazoloquinoxaline skeleton. However, Non-Patent Document 1 does not describe at all that a compound having a bisthiadiazoloquinoxaline skeleton is useful as a light-emitting material of an organic electroluminescence device.
  • Non-Patent Document 2 describes the results of studying spectroscopic characteristics and electrochemical characteristics of a compound having a bisthiadiazoloquinoxaline skeleton, and this compound is useful as a carrier transfer material for organic electroluminescence devices. It also mentions that there is. However, Non-Patent Document 2 does not describe at all the usefulness of a compound having a bisthiadiazoloquinoxaline skeleton as a luminescent material.
  • the compounds specifically exemplified in the same document have an alkyl group or a substituted phenyl group in a structure in which a phenyl group is substituted on the pyrazine ring of the bisthiadiazoloquinoxaline skeleton or a structure in which the phenyl group is condensed.
  • a substituent other than an alkyl group or a substituted phenyl group on a phenyl group substituted with a bisthiadiazoloquinoxaline skeleton or a condensed ring of a phenyl group There is no description of compounds that are substituted and substituted with a substituent other than an alkyl group or a substituted phenyl group on a phenyl group substituted with a bisthiadiazoloquinoxaline skeleton or a condensed ring of a phenyl group.
  • Non-Patent Document 1 describes a method for synthesizing a compound having a bisthiadiazoloquinoxaline skeleton, but it describes that the compound can be used as a material for an organic electroluminescence device.
  • Non-Patent Document 2 describes that a compound having a bisthiadiazoloquinoxaline skeleton is useful as a carrier transfer material for an organic electroluminescence device.
  • no investigation has been made as to whether or not the compound described in Non-Patent Document 2 can function as a light-emitting material.
  • Non-Patent Document 2 Since the light-emitting material is different in required properties and functions from the carrier transfer material, the usefulness of the compound described in Non-Patent Document 2 as the light-emitting material is unknown. Further, Non-Patent Document 2 does not describe a compound in which a diarylaminoaryl group is substituted on the pyrazine ring of a bisthiadiazoloquinoxaline skeleton, and its usefulness as a light-emitting material cannot be predicted.
  • the present inventors have further investigated the usefulness of a compound having a bisthiadiazoloquinoxaline skeleton as a light-emitting material, and conducted research aiming to find a compound having excellent light-emitting properties. Piled up. And the general formula of the compound useful as a luminescent material was derived, and the earnest examination was advanced for the purpose of generalizing the structure of the organic light emitting element with high luminous efficiency.
  • the present inventors have confirmed that a compound in which a specific substituent is substituted on a pyrazine ring of a bisthiadiazoloquinoxaline skeleton has excellent properties as a light emitting material.
  • a group of compounds is useful as a delayed fluorescent material, and it has been clarified that an organic light-emitting device having high emission efficiency can be provided at low cost.
  • a light emitting material comprising a compound represented by the following general formula (1).
  • R 1 and R 2 each independently represents a substituted or unsubstituted aryl group, and at least one of R 1 and R 2 is an aryl group substituted with an N, N-diarylamino group. is there.
  • * represents the bonding site to the pyrazine ring in General Formula (1).
  • Ar 1 to Ar 3 each independently represents a substituted or unsubstituted carbocyclic aromatic group having 4 to 10 carbon atoms or a substituted or unsubstituted heterocyclic aromatic group having 4 to 10 carbon atoms.
  • Ar 1 in the general formula (2) is an unsubstituted phenylene group, an unsubstituted naphthylene group, or an unsubstituted biphenylene group.
  • Ar 1 in the general formula (2) is an unsubstituted phenylene group.
  • R 3 and R 4 each independently represent a hydrogen atom or a substituent, and at least one of R 3 and R 4 is a group represented by the following General Formula (4).
  • * represents the bonding site to the benzene ring in General Formula (3).
  • X represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom.
  • the compound of the present invention is useful as a light emitting material.
  • the compounds of the present invention include those that emit delayed fluorescence.
  • An organic light emitting device using the compound of the present invention as a light emitting material can realize high luminous efficiency.
  • 2 is an emission absorption spectrum of a toluene solution of exemplary compound (1) of Example 1. It is an emission absorption spectrum of the thin film type organic photoluminescence element of Exemplified Compound (1) of Example 1 and CBP. It is a transient attenuation
  • 2 is a transient decay curve of a toluene solution of Example Compound (2) in Example 2. It is a transient attenuation
  • 2 is an emission spectrum of an organic electroluminescent element of the exemplary compound (2) of Example 3.
  • 6 is a graph showing voltage-current density-luminance characteristics of an organic electroluminescence device of Example Compound (2) of Example 3. 6 is a graph showing the current density-external quantum efficiency characteristics of an organic electroluminescent element of Example Compound (2) of Example 3.
  • 4 is a graph showing the current density-power efficiency characteristics of an organic electroluminescent element of Example Compound (2) of Example 3.
  • 6 is a graph showing current density-current efficiency characteristics of an organic electroluminescent element of Example Compound (2) of Example 3.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the isotope species of the hydrogen atom present in the molecule of the compound used in the present invention is not particularly limited. For example, all the hydrogen atoms in the molecule may be 1 H, or a part or all of them are 2 H. (Deuterium D) may be used.
  • the luminescent material of the present invention is characterized by comprising a compound represented by the following general formula (1).
  • R 1 and R 2 each independently represents a substituted or unsubstituted aryl group, and at least one of R 1 and R 2 is an aryl group substituted with an N, N-diarylamino group .
  • N, N-aryl group diarylamino group is substituted may be one of R 1 and R 2, may be both of R 1 and R 2, R 1 and R 2 Both are preferred.
  • both R 1 and R 2 are aryl groups substituted by N, N-diarylamino groups, these N, N-diarylamino groups may be the same or different from each other, but are the same It is preferable.
  • the aryl group substituted by the N, N-diarylamino group is preferably a group represented by the following general formula (2).
  • Ar 1 to Ar 3 each independently represents a substituted or unsubstituted carbocyclic aromatic group having 4 to 10 carbon atoms or a substituted or unsubstituted heterocyclic aromatic group having 4 to 10 carbon atoms.
  • the aromatic groups represented by Ar 1 to Ar 3 may be the same or different from each other, but Ar 2 and Ar 3 are preferably the same as each other. Further, when a plurality of groups represented by the general formula (2) are present in the compound represented by the general formula (1), the plurality of Ar 1 to Ar 3 may be the same as or different from each other.
  • Ar 1 is preferably an unsubstituted carbocyclic aromatic group, more preferably an unsubstituted phenylene group, an unsubstituted naphthylene group, or an unsubstituted biphenylene group.
  • the phenylene group is more preferable.
  • Ar 2 and Ar 3 are preferably each independently a substituted or unsubstituted carbocyclic aromatic group, more preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. More preferably, it is a substituted phenyl group.
  • Ar 2 and Ar 3 may be bonded by a single bond or may be linked via a linking group.
  • linking group examples include a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom.
  • the ethylene group and the vinylene group are substituted with a plurality of substituents, two adjacent substituents may be bonded to each other to form a cyclic structure.
  • R 1 and R 2 are aryl group substituted with an N, N-diarylamino group
  • the substituted or unsubstituted aryl group that the other can take is a substituted or unsubstituted carbocyclic aromatic group Or a substituted or unsubstituted heterocyclic aromatic group, preferably a substituted or unsubstituted carbocyclic aromatic group, preferably a substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl It is more preferably a group or a substituted or unsubstituted biphenyl group, and further preferably a substituted or unsubstituted phenyl group.
  • Preferable examples of the compound represented by the general formula (1) include a compound represented by the following general formula (3).
  • R 3 and R 4 each independently represent a hydrogen atom or a substituent, and at least one of R 3 and R 4 is a group represented by the following general formula (4).
  • Groups represented by the following general formula (4) may be one of R 3 and R 4, may it be both R 3 and R 4, both of R 3 and R 4 It is preferable that When both R 3 and R 4 are groups represented by the following general formula (4), the two groups represented by the following general formula (4) may be the same or different from each other. Are preferably the same.
  • * represents a binding site to the benzene ring in the general formula (3).
  • X represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom, and a methylene group substituted with a methyl group Or it is preferably an oxygen atom, and more preferably an oxygen atom.
  • Substituents that can be substituted for R 1 and R 2 , substituents that R 3 and R 4 can take, substituents that can be substituted for Ar 1 to Ar 3, and substituents that can be substituted for X include, for example, hydroxy groups, halogen atoms Cyano group, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, alkyl-substituted amino group having 1 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms Aryl group having 6 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, carbon number 1 to 10 alkylsulfonyl groups, 1 to 10 carbon haloalkyl groups, amide groups, 2 to
  • substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, carbon A substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, and a dialkyl-substituted amino group having 1 to 20 carbon atoms.
  • substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, carbon A substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, and a dialkyl-substituted amino group having 1 to 20 carbon
  • substituents are a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted group having 6 to 15 carbon atoms.
  • it is an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
  • X is an ethylene group or vinylene group substituted with a plurality of substituents
  • two adjacent substituents of the ethylene group or vinylene group may be bonded to each other to form a cyclic structure.
  • the cyclic structure may be an aromatic ring or an alicyclic ring, may contain a hetero atom, and the cyclic structure may be a condensed ring of two or more rings.
  • the hetero atom here is preferably selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
  • Examples of cyclic structures formed include benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, imidazoline ring, oxazole ring, isoxazole ring, thiazole And a ring, an isothiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentaene ring, a cycloheptatriene ring, a cycloheptadiene ring, and a cycloheptaene ring.
  • the molecular weight of the compound represented by the general formula (1) is, for example, 1500 or less when the organic layer containing the compound represented by the general formula (1) is intended to be formed by vapor deposition. Preferably, it is preferably 1200 or less, and more preferably 1000 or less. The lower limit of the molecular weight is the molecular weight of the minimum compound represented by the general formula (1).
  • the compound represented by the general formula (1) may be formed by a coating method regardless of the molecular weight. If a coating method is used, a film can be formed even with a compound having a relatively large molecular weight.
  • a compound containing a plurality of structures represented by the general formula (1) in the molecule as a light emitting material.
  • a polymer obtained by previously polymerizing a polymerizable group in the structure represented by the general formula (1) and polymerizing the polymerizable group as a light emitting material.
  • a monomer containing a polymerizable functional group in either R 1 or R 2 of the general formula (1) and polymerizing this alone or copolymerizing with other monomers, It is conceivable to obtain a polymer having a repeating unit and use the polymer as a light emitting material.
  • dimers and trimers are obtained by reacting compounds having a structure represented by the general formula (1) and used as a luminescent material.
  • a polymer having a repeating unit including a structure represented by the general formula (1) As an example of a polymer having a repeating unit including a structure represented by the general formula (1), a polymer including a structure represented by the following general formula (5) or (6) can be given.
  • Q represents a group including the structure represented by the general formula (1)
  • L 1 and L 2 represent a linking group.
  • the linking group preferably has 0 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 2 to 10 carbon atoms. And preferably has a structure represented by - linking group -X 11 -L 11.
  • X 11 represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
  • L 11 represents a linking group, preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted group A phenylene group is more preferable.
  • R 101 , R 102 , R 103 and R 104 each independently represent a substituent.
  • it is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms.
  • An unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, and a chlorine atom and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms and an unsubstituted alkoxy group having 1 to 3 carbon atoms.
  • the linking group represented by L 1 and L 2 is any one of R 1 and R 2 in the structure of general formula (1) constituting Q, any one of Ar 1 to Ar 3 in general formula (2), It can be bonded to any of R 3 and R 4 in the structure of the formula (3), or X in the structure of the general formula (4).
  • Two or more linking groups may be linked to one Q to form a crosslinked structure or a network structure.
  • repeating unit examples include structures represented by the following formulas (7) to (10).
  • a hydroxy group is introduced into either R 1 or R 2 in the structure of the general formula (1), and this is used as a linker as described below. It can be synthesized by reacting a compound to introduce a polymerizable group and polymerizing the polymerizable group.
  • the polymer containing the structure represented by the general formula (1) in the molecule may be a polymer composed only of repeating units having the structure represented by the general formula (1), or other structures may be used. It may be a polymer containing repeating units.
  • the repeating unit having a structure represented by the general formula (1) contained in the polymer may be a single type or two or more types. Examples of the repeating unit not having the structure represented by the general formula (1) include those derived from monomers used in ordinary copolymerization. Examples thereof include a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene and styrene.
  • R 3 and R 4 each independently represent a hydrogen atom or a substituent, and at least one of R 3 and R 4 is a group represented by the following general formula (4).
  • * represents a bonding site to the benzene ring in the general formula (3).
  • X represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted imino group, an oxygen atom or a sulfur atom.
  • R 3 , R 4 in the general formula (3) and X in the general formula (4) and preferred ranges thereof the general formula (3) illustrated as a preferred example of the compound represented by the general formula (1) above. Reference may be made to the description of the compounds represented.
  • a compound in which R 3 in the general formula (3) is a group represented by the general formula (4) and R 4 is a hydrogen atom is a compound A (4,5-Diamino-bisbenzo [1,2,5 ] thiadiazole) and the compound obtained by the following reaction I can be synthesized by the following reaction II using the starting material as a starting material.
  • Z represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom are preferable.
  • Ar represents a phenyl group.
  • the above reaction is an application of a known reaction, and known reaction conditions can be appropriately selected and used.
  • Compound A as a starting material can be synthesized by the method described in A. P. Komin, M. Carmack, J. Heterocyclic Chem. 1975, 12, 829-833. The details of the above reaction can be referred to the synthesis examples described below.
  • the compound represented by the general formula (3) can also be synthesized by combining other known synthesis reactions.
  • the compound represented by the general formula (1) of the present invention is useful as a light emitting material of an organic light emitting device. For this reason, the compound represented by General formula (1) of this invention can be effectively used as a luminescent material for the light emitting layer of an organic light emitting element.
  • the compound represented by the general formula (1) includes a delayed fluorescent material (delayed phosphor) that emits delayed fluorescence. That is, the present invention relates to a delayed phosphor having a structure represented by the general formula (1), an invention using a compound represented by the general formula (1) as a delayed phosphor, and a general formula (1).
  • An invention of a method for emitting delayed fluorescence using the represented compound is also provided.
  • An organic light emitting device using such a compound as a light emitting material emits delayed fluorescence and has a feature of high luminous efficiency. The principle will be described below by taking an organic electroluminescence element as an example.
  • the organic electroluminescence element carriers are injected into the light emitting material from both positive and negative electrodes to generate an excited light emitting material and emit light.
  • 25% of the generated excitons are excited to the excited singlet state, and the remaining 75% are excited to the excited triplet state. Therefore, the use efficiency of energy is higher when phosphorescence, which is light emission from an excited triplet state, is used.
  • the excited triplet state has a long lifetime, energy saturation occurs due to saturation of the excited state and interaction with excitons in the excited triplet state, and in general, the quantum yield of phosphorescence is often not high.
  • delayed fluorescent materials after energy transition to an excited triplet state due to intersystem crossing, etc., are then crossed back to an excited singlet state due to triplet-triplet annihilation or absorption of thermal energy, and emit fluorescence.
  • a thermally activated delayed fluorescent material by absorption of thermal energy is particularly useful.
  • excitons in the excited singlet state emit fluorescence as usual.
  • excitons in the excited triplet state absorb heat generated by the device and cross between the excited singlets to emit fluorescence.
  • the light is emitted from the excited singlet, the light is emitted at the same wavelength as the fluorescence, but the light lifetime (luminescence lifetime) generated by the reverse intersystem crossing from the excited triplet state to the excited singlet state is normal. Since the fluorescence becomes longer than the fluorescence and phosphorescence, it is observed as fluorescence delayed from these. This can be defined as delayed fluorescence. If such a heat-activated exciton transfer mechanism is used, the ratio of the compound in an excited singlet state, which normally generated only 25%, is increased to 25% or more by absorbing thermal energy after carrier injection. It can be raised.
  • the heat of the device will sufficiently cause intersystem crossing from the excited triplet state to the excited singlet state and emit delayed fluorescence. Efficiency can be improved dramatically.
  • the compound represented by the general formula (1) of the present invention as a light-emitting material of a light-emitting layer, excellent organic light-emitting devices such as an organic photoluminescence device (organic PL device) and an organic electroluminescence device (organic EL device) Can be provided.
  • the compound represented by the general formula (1) of the present invention may have a function of assisting light emission of another light emitting material included in the light emitting layer as a so-called assist dopant. That is, the compound represented by the general formula (1) of the present invention contained in the light emitting layer includes the lowest excitation singlet energy level of the host material contained in the light emitting layer and the lowest excitation of other light emitting materials contained in the light emitting layer.
  • the organic photoluminescence element has a structure in which at least a light emitting layer is formed on a substrate.
  • the organic electroluminescence element has a structure in which an organic layer is formed at least between an anode, a cathode, and an anode and a cathode.
  • the organic layer includes at least a light emitting layer, and may consist of only the light emitting layer, or may have one or more organic layers in addition to the light emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer.
  • the hole transport layer may be a hole injection / transport layer having a hole injection function
  • the electron transport layer may be an electron injection / transport layer having an electron injection function.
  • FIG. 1 A specific example of the structure of an organic electroluminescence element is shown in FIG.
  • 1 is a substrate
  • 2 is an anode
  • 3 is a hole injection layer
  • 4 is a hole transport layer
  • 5 is a light emitting layer
  • 6 is an electron transport layer
  • 7 is a cathode.
  • each member and each layer of an organic electroluminescent element are demonstrated.
  • substrate and a light emitting layer corresponds also to the board
  • the organic electroluminescence device of the present invention is preferably supported on a substrate.
  • the substrate is not particularly limited and may be any substrate conventionally used for organic electroluminescence elements.
  • a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.
  • an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) that can form a transparent conductive film may be used.
  • a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 ⁇ m or more) ), A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
  • wet film-forming methods such as a printing system and a coating system, can also be used.
  • the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • cathode a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture
  • Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum and the like.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission luminance is advantageously improved.
  • a transparent or semi-transparent cathode can be produced. By applying this, an element in which both the anode and the cathode are transparent is used. Can be produced.
  • the light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from each of the anode and the cathode, and the light emitting material may be used alone for the light emitting layer. , Preferably including a luminescent material and a host material. As a luminescent material, the 1 type (s) or 2 or more types chosen from the compound group of this invention represented by General formula (1) can be used. In order for the organic electroluminescence device and the organic photoluminescence device of the present invention to exhibit high luminous efficiency, it is important to confine singlet excitons and triplet excitons generated in the light emitting material in the light emitting material.
  • a host material in addition to the light emitting material in the light emitting layer.
  • the host material an organic compound having at least one of excited singlet energy and excited triplet energy higher than that of the light emitting material of the present invention can be used.
  • singlet excitons and triplet excitons generated in the light emitting material of the present invention can be confined in the molecules of the light emitting material of the present invention, and the light emission efficiency can be sufficiently extracted.
  • high luminous efficiency can be obtained, so that host materials that can achieve high luminous efficiency are particularly limited. And can be used in the present invention.
  • the organic light emitting device or organic electroluminescent device of the present invention light emission is generated from the light emitting material of the present invention contained in the light emitting layer. This emission includes both fluorescence and delayed fluorescence. However, light emission from the host material may be partly or partly emitted.
  • the amount of the compound of the present invention, which is a light emitting material is preferably 0.1% by weight or more, more preferably 1% by weight or more, and 50% or more. It is preferably no greater than wt%, more preferably no greater than 20 wt%, and even more preferably no greater than 10 wt%.
  • the host material in the light-emitting layer is preferably an organic compound that has a hole transporting ability and an electron transporting ability, prevents the emission of longer wavelengths, and has a high glass transition temperature.
  • the injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission, and includes a hole injection layer and an electron injection layer, Further, it may be present between the cathode and the light emitting layer or the electron transport layer.
  • the injection layer can be provided as necessary.
  • the blocking layer is a layer that can prevent diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer.
  • the electron blocking layer can be disposed between the light emitting layer and the hole transport layer and blocks electrons from passing through the light emitting layer toward the hole transport layer.
  • a hole blocking layer can be disposed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer toward the electron transporting layer.
  • the blocking layer can also be used to block excitons from diffusing outside the light emitting layer. That is, each of the electron blocking layer and the hole blocking layer can also function as an exciton blocking layer.
  • the term “electron blocking layer” or “exciton blocking layer” as used herein is used in the sense of including a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.
  • the hole blocking layer has a function of an electron transport layer in a broad sense.
  • the hole blocking layer has a role of blocking holes from reaching the electron transport layer while transporting electrons, thereby improving the recombination probability of electrons and holes in the light emitting layer.
  • the material for the hole blocking layer the material for the electron transport layer described later can be used as necessary.
  • the electron blocking layer has a function of transporting holes in a broad sense.
  • the electron blocking layer has a role to block electrons from reaching the hole transport layer while transporting holes, thereby improving the probability of recombination of electrons and holes in the light emitting layer. .
  • the exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved.
  • the exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously.
  • the layer when the exciton blocking layer is provided on the anode side, the layer can be inserted adjacent to the light emitting layer between the hole transport layer and the light emitting layer, and when inserted on the cathode side, the light emitting layer and the cathode Between the luminescent layer and the light-emitting layer.
  • a hole injection layer, an electron blocking layer, or the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and the excitation adjacent to the cathode and the cathode side of the light emitting layer can be provided.
  • an electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided.
  • the blocking layer is disposed, at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is preferably higher than the excited singlet energy and the excited triplet energy of the light emitting material.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • hole transport materials that can be used include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Examples include amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • An aromatic tertiary amine compound and an styrylamine compound are preferably used, and an aromatic tertiary amine compound is more preferably used.
  • the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
  • the electron transport material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • Examples of the electron transport layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.
  • a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • the compound represented by the general formula (1) may be used not only for the light emitting layer but also for layers other than the light emitting layer.
  • the compound represented by General formula (1) used for a light emitting layer and the compound represented by General formula (1) used for layers other than a light emitting layer may be same or different.
  • the compound represented by the general formula (1) may be used for the injection layer, blocking layer, hole blocking layer, electron blocking layer, exciton blocking layer, hole transporting layer, electron transporting layer, and the like. .
  • the method for forming these layers is not particularly limited, and the layer may be formed by either a dry process or a wet process.
  • the preferable material which can be used for an organic electroluminescent element is illustrated concretely.
  • the material that can be used in the present invention is not limited to the following exemplary compounds. Moreover, even if it is a compound illustrated as a material which has a specific function, it can also be diverted as a material which has another function.
  • R and R 1 to R 7 each independently represents a hydrogen atom or a substituent.
  • n represents an integer of 3 to 5.
  • the organic electroluminescent device produced by the above-described method emits light by applying an electric field between the anode and the cathode of the obtained device. At this time, if the light is emitted by excited singlet energy, light having a wavelength corresponding to the energy level is confirmed as fluorescence emission and delayed fluorescence emission. In addition, in the case of light emission by excited triplet energy, a wavelength corresponding to the energy level is confirmed as phosphorescence. Since normal fluorescence has a shorter fluorescence lifetime than delayed fluorescence, the emission lifetime can be distinguished from fluorescence and delayed fluorescence.
  • the excited triplet energy is unstable and is converted into heat and the like, and the lifetime is short and it is immediately deactivated.
  • the excited triplet energy of a normal organic compound it can be measured by observing light emission under extremely low temperature conditions.
  • the organic electroluminescence element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. According to the present invention, an organic light emitting device with greatly improved light emission efficiency can be obtained by containing the compound represented by the general formula (1) in the light emitting layer.
  • the organic light emitting device such as the organic electroluminescence device of the present invention can be further applied to various uses. For example, it is possible to produce an organic electroluminescence display device using the organic electroluminescence element of the present invention.
  • organic electroluminescence device of the present invention can be applied to organic electroluminescence illumination and backlights that are in great demand.
  • source meter manufactured by Keithley: 2400 series
  • semiconductor parameter analyzer manufactured by Agilent Technologies: E5273A
  • optical power meter measuring device manufactured by Newport: 1930C
  • optical spectrometer Ocean Optics, USB2000
  • spectroradiometer Topcon, SR-3
  • streak camera Haamamatsu Photonics C4334
  • Singlet energy E S1 A sample having a thickness of 100 nm was prepared on a Si substrate by co-evaporating the measurement target compound and mCBP so that the measurement target compound had a concentration of 6% by weight. The fluorescence spectrum of this sample was measured at room temperature (300K).
  • a fluorescence spectrum having a luminescence intensity on the vertical axis and a wavelength on the horizontal axis was obtained.
  • the vertical axis represents light emission and the horizontal axis represents wavelength.
  • a tangent line was drawn with respect to the short-wave rise of the emission spectrum, and the wavelength value ⁇ edge [nm] at the intersection of the tangent line and the horizontal axis was obtained.
  • a value obtained by converting this wavelength value into an energy value by the following conversion formula was defined as E S1 .
  • E S1 [eV] 1239.85 / ⁇ edge
  • a nitrogen laser Lasertechnik Berlin, MNL200
  • a streak camera Hamamatsu Photonics, C4334
  • E T1 Triplet energy
  • tangents at each point on the curve are considered toward the long wavelength side.
  • the slope of this tangent line increases as the curve rises (that is, as the vertical axis increases).
  • the tangent drawn at the point where the value of the slope takes the maximum value was taken as the tangent to the rising edge of the phosphorescence spectrum on the short wavelength side.
  • the maximum point having a peak intensity of 10% or less of the maximum peak intensity of the spectrum is not included in the above-mentioned maximum value on the shortest wavelength side, and has the maximum slope value closest to the maximum value on the shortest wavelength side.
  • the tangent drawn at the point where the value was taken was taken as the tangent to the rising edge of the phosphorescence spectrum on the short wavelength side.
  • the obtained solid was purified by column chromatography.
  • the eluted crude exemplary compound (1) was dissolved in a mixed solvent of boiling tetrahydrofuran and ethanol, and then cooled to room temperature to precipitate the exemplary compound (1).
  • the exemplary compound (1) was obtained in a yield of 1.66 g and a yield of 42%.
  • Example 1 Preparation and evaluation of organic photoluminescence device using exemplary compound (1)
  • a toluene solution (concentration 10 -4 mol / L) of exemplary compound (1) was prepared in a glove box under an Ar atmosphere.
  • the exemplified compound (1) and CBP were deposited from different vapor deposition sources on a quartz substrate by a vacuum vapor deposition method under a vacuum degree of 3 ⁇ 10 ⁇ 4 Pa or less, and the concentration of the exemplified compound (1) was 6
  • a thin film having a thickness of 0.0% by weight was formed to a thickness of 100 nm to obtain an organic photoluminescence element.
  • the emission spectrum and absorption spectrum by 330 nm excitation light were measured.
  • the emission absorption spectrum of the toluene solution of the exemplified compound (1) is shown in FIG. 2, and the emission absorption spectrum of the organic photoluminescence device having the thin film of the exemplified compound (1) and CBP is shown in FIG.
  • the emission wavelength ⁇ max of the toluene solution of the exemplary compound (1) was 515 nm, and the photoluminescence quantum efficiency was 12.9% without bubbling and 19.5% with nitrogen bubbling.
  • the emission wavelength ⁇ max of the organic photoluminescence device having the thin film of Example Compound (1) and CBP was 521 nm, and the photoluminescence quantum efficiency was 20.5% under the atmosphere and 38.1% under the nitrogen stream.
  • FIG. 1 The emission absorption spectrum of the toluene solution of the exemplified compound (1) is shown in FIG. 2, and the emission absorption spectrum of the organic photoluminescence device having the thin film of the exemplified compound (1) and CBP is shown in FIG.
  • This transient decay curve shows the result of measuring the luminescence lifetime obtained by measuring the process in which the emission intensity is deactivated by applying excitation light to the compound.
  • the light emission intensity decays in a single exponential manner. This means that if the vertical axis of the graph is semi-log, it will decay linearly.
  • the transient attenuation curve of this example such a linear component (fluorescence) is observed at the initial stage of observation, but a component deviating from linearity appears after several microseconds.
  • the exemplary compound (1) is a light emitter containing a delay component in addition to the fluorescent component.
  • the excited singlet state calculated with the stable structure of the ground state
  • the energy difference ⁇ E st value between (S 1 ) and the excited triplet state (T 1 ) was 0.437 eV
  • the frequency factor f value for the S 0 ⁇ S 1 transition was 0.09.
  • the ⁇ E st value was used as a measure of the probability of thermal activation, and it was considered that the smaller the value, the more likely the thermal activation delayed fluorescence occurs.
  • the f value is the ease of the transition from S 0 (ground state) to S 1 (excited singlet state). In this calculation, the f value is used as a measure of the ease of light emission (fluorescence intensity). It was considered that the larger this value, the stronger the fluorescence.
  • Example 2 Preparation and evaluation of organic photoluminescence device using exemplary compound (2) Except for using exemplary compound (2) instead of exemplary compound (1), exemplary compound ( A toluene solution of 2) was prepared.
  • organic photoluminescence having a thin film of exemplary compound (2) and mCBP was used in the same manner as in Example 1 except that exemplary compound (2) was used instead of exemplary compound (1) and mCBP was used instead of CBP.
  • An element was produced.
  • FIG. 5 shows the results of measuring the emission spectrum and the absorption spectrum of the exemplary compound (2) with a 430 nm excitation light, and the organic photoluminescence device having the thin film of the exemplary compound (2) and mCBP with a 342 nm excitation light.
  • the results of measuring the emission spectrum and absorption spectrum are shown in FIG.
  • the emission wavelength ⁇ max of the toluene solution of the exemplary compound (2) was 634 nm, and the photoluminescence quantum efficiency was 6.1% without bubbling and 12.5% with nitrogen bubbling.
  • the emission wavelength ⁇ max of the organic photoluminescence device having a thin film of Example Compound (2) and mCBP was 585 nm, and the photoluminescence quantum efficiency was 56.0% under the atmosphere and 62.8% under the nitrogen stream.
  • the result of having measured the transient decay curve by 405 nm excitation light about the toluene solution of exemplary compound (2) is shown in FIG.
  • the energy difference ⁇ E st value between the excited singlet state and the excited triplet state is 0.0567 eV, and the f value is 0.0339.
  • Met The ⁇ E st value was smaller than the exemplified compound (1), which was expected to be advantageous for thermally activated delayed fluorescence, but the f value was smaller than the exemplified compound (1), so the results were interesting.
  • the compound (2) exhibited strong delayed fluorescence, it was found that a small ⁇ E st value is important for expressing strong thermally activated delayed fluorescence.
  • Example 3 Production and evaluation of organic electroluminescence device using exemplary compound (2) Each thin film was vacuum-deposited on a glass substrate on which an anode made of indium tin oxide (ITO) having a thickness of 100 nm was formed. In this way, the layers were laminated at a degree of vacuum of 3 ⁇ 10 ⁇ 4 Pa. First, ⁇ -NPD was formed on ITO to a thickness of 35 nm. Next, Exemplified Compound (2) and mCBP were co-evaporated from different vapor deposition sources to form a layer having a thickness of 15 nm as a light emitting layer. At this time, the concentration of the exemplary compound (2) was 6.0% by weight.
  • ITO indium tin oxide
  • FIG. 9 shows an emission spectrum of the manufactured organic electroluminescence device measured at 1 mA / cm 2 , 10 mA / cm 2 , 100 mA / cm 2 , and FIG. 10 shows voltage-current density characteristics.
  • FIG. 11 shows the current density-external quantum efficiency characteristics
  • FIG. 12 shows the current density-power efficiency characteristics
  • FIG. 13 shows the current density-current efficiency characteristics.
  • the organic electroluminescence device using the exemplified compound (2) as the light emitting material had an external quantum efficiency of 9.14% at 0.07 mA / cm 2 and was able to obtain high light emission efficiency. Assuming that an ideal organic electroluminescence device balanced using a fluorescent material having a light emission quantum efficiency of 100% is prototyped, if the light extraction efficiency is 20 to 30%, the external quantum efficiency of fluorescence emission is 5%. 7.5%. This value is generally regarded as a theoretical limit value of the external quantum efficiency of an organic electroluminescence device using a fluorescent material. The organic electroluminescence device of the present invention using the exemplified compound (2) is extremely excellent in that high external quantum efficiency exceeding the theoretical limit value is realized.
  • the organic electroluminescence device of the present embodiment is a power efficiency 10.0lm / W at 0.003mA / cm 2, current efficiency at 0.008mA / cm 2 is 10.1cd / A, higher power Efficiency and high current efficiency could be obtained.
  • the compound of the present invention is useful as a luminescent material. For this reason, the compound of this invention is effectively used as a luminescent material for organic light emitting elements, such as an organic electroluminescent element. Since the compounds of the present invention include those that emit delayed fluorescence, it is also possible to provide an organic light-emitting device with high luminous efficiency. For this reason, this invention has high industrial applicability.

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Abstract

Cette invention concerne un composé représenté par la formule générale (1), utile en tant que substance électroluminescente. Dans ladite formule, R1 et R2 représente chacun indépendamment un groupe aryle substitué ou non substitué, et R1 et/ou R2 représente un groupe aryle substitué par un groupe N, N-diarylamino.
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US11476435B2 (en) 2017-08-24 2022-10-18 Kyushu University, National University Corporation Film and organic light-emitting device containing perovskite-type compound and organic light-emitting material
WO2020076796A1 (fr) 2018-10-09 2020-04-16 Kyulux, Inc. Nouvelle composition de matière destinée à être utilisée dans des diodes électroluminescentes organiques
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WO2022244503A1 (fr) 2021-05-20 2022-11-24 株式会社Kyulux Elément électroluminescent organique
WO2022270354A1 (fr) 2021-06-23 2022-12-29 株式会社Kyulux Composé, matériau électroluminescent et élément électroluminescent organique
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WO2023282224A1 (fr) 2021-07-06 2023-01-12 株式会社Kyulux Élément émetteur de lumière organique et son procédé de conception
WO2023053835A1 (fr) 2021-09-28 2023-04-06 株式会社Kyulux Composé, composition, matériau hôte, matériau barrière aux électrons et élément électroluminescent organique
WO2023090288A1 (fr) 2021-11-19 2023-05-25 株式会社Kyulux Composé, matériau électroluminescent et élément électroluminescent
WO2023140130A1 (fr) 2022-01-19 2023-07-27 株式会社Kyulux Composé, matériau électroluminescent et dispositif électroluminescent organique
WO2024111223A1 (fr) 2022-11-22 2024-05-30 株式会社Kyulux Composé, matériau électroluminescent et élément électroluminescent
EP4624468A1 (fr) 2022-11-22 2025-10-01 Kyulux, Inc. Composé, matériau électroluminescent et élément électroluminescent
WO2024166785A1 (fr) 2023-02-10 2024-08-15 株式会社Kyulux Composé, matériau électroluminescent et élément électroluminescent
EP4663634A1 (fr) 2023-02-10 2025-12-17 Kyulux, Inc. Composé, matériau électroluminescent et élément électroluminescent

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