WO2023276918A1 - 化合物、電子障壁材料、有機半導体素子および化合物 - Google Patents

化合物、電子障壁材料、有機半導体素子および化合物 Download PDF

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WO2023276918A1
WO2023276918A1 PCT/JP2022/025463 JP2022025463W WO2023276918A1 WO 2023276918 A1 WO2023276918 A1 WO 2023276918A1 JP 2022025463 W JP2022025463 W JP 2022025463W WO 2023276918 A1 WO2023276918 A1 WO 2023276918A1
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adjacent
group
general formula
integer
ring
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French (fr)
Japanese (ja)
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寛晃 小澤
桃子 森尾
亜衣子 後藤
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Kyulux Inc
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Kyulux Inc
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Priority to JP2023531915A priority patent/JPWO2023276918A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • 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
    • 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]
    • H10K50/18—Carrier blocking layers
    • H10K50/181—Electron blocking layers
    • 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
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/20—Delayed fluorescence emission
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a compound useful as an electron barrier material and an organic semiconductor device using the same.
  • organic electroluminescence devices organic electroluminescence devices
  • the electron blocking material is provided between the light-emitting layer and the hole-transporting layer to prevent electrons present in the light-emitting layer from escaping from the light-emitting layer to the hole-transporting layer. It is a material for the electron blocking layer that has the function of transporting the holes of the electrons to the light-emitting layer.
  • Patent Document 1 proposes a compound having the following structure.
  • organic electroluminescence devices using the above compounds as electron barrier materials have room for improvement in terms of device life.
  • the present inventors have made intensive studies to provide an electron barrier material that can extend the device life when used in an organic electroluminescence device.
  • a compound represented by the following general formula (1) [In general formula (1), X represents a donor group, and R 1 to R 6 each independently represent a deuterium atom or a substituent. n1 and n2 are each independently an integer of 0 to 4, n3 is an integer of 0 to 2, n4 and n6 are each independently an integer of 0 to 3, n5 is an integer of 0 to 5 represents an integer.
  • R 1 to R 8 each independently represent a deuterium atom or a substituent.
  • n1, n2, n7 and n8 are each independently an integer of 0 to 4
  • n3 is an integer of 0 to 2
  • n4 and n6 are each independently an integer of 0 to 3
  • n5 is 0 Represents any integer from ⁇ 5.
  • n1, n4, n6, n7 and n8 are each independently an integer of 0 to 3
  • n2 is an integer of 0 to 4
  • n3 is an integer of 0 to 2
  • the compound according to [1] represented by the following general formula (3B).
  • R 1 to R 11 each independently represent a deuterium atom or a substituent.
  • n1, n4, n6 and n8 are each independently an integer of 0 to 3
  • n2 and n9 are each independently an integer of 0 to 4
  • n3 and n7 are each independently an integer of 0 to 2
  • the organic semiconductor element is an organic electroluminescence element having at least two organic layers including an anode, a cathode, and a light-emitting layer between the anode and the cathode. element.
  • the light-emitting layer contains a host material and a delayed fluorescence material.
  • the compound of the present invention is useful as an electron barrier material and can be effectively used in organic semiconductor devices.
  • the life of the device can be lengthened by using the compound of the present invention in the electron barrier layer of the organic electroluminescence device.
  • substituted means an atom or group of atoms other than a hydrogen atom and a deuterium atom.
  • substituted or unsubstituted means that hydrogen atoms may be replaced with deuterium atoms or substituents.
  • the compound of the present invention is a compound represented by the following general formula (1).
  • X represents a donor group.
  • the donor group referred to herein is a group having a negative Hammett's ⁇ p value.
  • 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.
  • a group having a positive Hammett ⁇ p value tends to exhibit electron-withdrawing properties (acceptor properties). Note that in one embodiment of the present invention, the compound represented by General Formula (1) does not contain a substituent having a ⁇ p value of 0.2 or more.
  • the donor group is preferably a group containing a substituted amino group.
  • the substituent bonded to the nitrogen atom of the amino group is preferably 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. , a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, more preferably a substituted or unsubstituted aryl group.
  • the substituted amino group is particularly preferably a substituted or unsubstituted diarylamino group or a substituted or unsubstituted diheteroarylamino group.
  • Two atomic groups bonded to the nitrogen atom of the substituted amino group may bond together to form a cyclic structure.
  • the donor group in the present invention may be a group that binds through the nitrogen atom of the substituted amino group, or a group that binds through the group to which the substituted amino group is bound.
  • the group to which the substituted amino group is bonded is preferably a ⁇ -conjugated group.
  • a group that binds through the nitrogen atom of a substituted amino group or a group that binds the nitrogen atom of the substituted amino group to a benzene ring and binds through the benzene ring, and more preferred is a substituted amino group. It is a group attached at the nitrogen atom of the group.
  • a substituted or unsubstituted carbazol-9-yl group is particularly preferred as the donor group in the present invention.
  • the carbazol-9-yl group may be further condensed with a benzene ring or hetero ring.
  • the substituent of the carbazol-9-yl group may be, for example, a substituent selected from the following substituent group a, a substituent selected from the following substituent group b, or the following substituent group It may be a substituent selected from c or a substituent selected from the following substituent group d.
  • the two benzene rings constituting the carbazol-9-yl group may be independently condensed with other rings.
  • the condensed ring may be an aromatic ring, a heteroaromatic ring, an aliphatic hydrocarbon ring, or an aliphatic heterocyclic ring, or a ring in which these are further condensed.
  • An aromatic ring, a heteroaromatic ring, or a condensed ring thereof is preferred.
  • a benzene ring can be mentioned as an aromatic ring.
  • the heteroaromatic ring means an aromatic ring containing a heteroatom as a ring skeleton-constituting atom, and is preferably a 5- to 7-membered ring, such as a 5-membered ring or a 6-membered ring. can be adopted.
  • a furan ring, a thiophene ring, a pyrrole ring, or a pyridine ring can be employed as the heteroaromatic ring.
  • the cyclic structure is a benzene ring, which may be substituted with a substituent selected from any one of the following substituent groups a to d, such as a benzene ring and a furan ring.
  • a substituent selected from any one of the following substituent groups a to d such as a benzene ring and a furan ring.
  • One or more other cyclic structures may be condensed.
  • the benzene ring may be unsubstituted.
  • the cyclic structure is a furan ring, which may be substituted with a substituent selected from any one of the following substituent groups a to d, such as a benzene ring and a furan ring.
  • One or more other cyclic structures may be condensed.
  • Preferred carbazol-9-yl groups include an unsubstituted carbazol-9-yl group, a carbazol-9-yl group substituted at least one of the 3- and 6-positions, and a carbazole substituted at both the 3- and 6-positions.
  • -9-yl group can be exemplified.
  • the donor group that can be taken by X preferably has 13 or more atoms other than hydrogen atoms and deuterium atoms. You can also choose what is
  • the donor group that X can take may be composed only of atoms selected from, for example, a hydrogen atom, a deuterium atom, a carbon atom, a nitrogen atom and an oxygen atom. It may be composed only of atoms selected from nitrogen atoms, for example, it may be composed only of atoms selected from hydrogen atoms, carbon atoms and nitrogen atoms.
  • the donor group that can take is not limitedly interpreted by these specific examples.
  • the methyl group is indicated by omitting the notation of CH3 .
  • D4 represents a 3,6-dimethylcarbazol-9-yl group.
  • D represents a deuterium atom.
  • R 1 to R 6 are atoms or atomic groups capable of substituting a hydrogen atom bonded to a benzene ring, specifically each independently deuterium atom or a substituent. show.
  • n1 to n6 are integers of 2 or more, a plurality of R 1 to R 6 may be the same or different.
  • R 1 may be the same as or different from R 2 to R 6 .
  • Any of R 1 to R 6 may be a deuterium atom, and any of R 1 to R 6 may be a substituent.
  • R 1 to R 6 may be, for example, a substituent selected from the following substituent group a, a substituent selected from the following substituent group b, or a substituent selected from the following substituent group c. or a substituent selected from the following substituent group d.
  • R 1 to R 6 are one group or a combination of two or more groups selected from the group consisting of alkyl groups and aryl groups. In one aspect of the present invention, it is an aryl group optionally substituted with one group or a combination of two or more groups selected from the group consisting of an alkyl group and an aryl group.
  • R 1 -R 6 are phenyl or naphthyl groups, for example phenyl groups may be selected. Specific examples of the substituents that R 1 to R 6 can take are given below, but the substituents that can be employed as R 1 to R 6 are not limited to these specific examples.
  • the methyl group is indicated by omitting the notation of CH3 .
  • N8 represents a 4-methylphenyl group.
  • D represents a deuterium atom.
  • n1 to n6 represent any integers equal to or greater than 0 and equal to or less than the maximum number of substituents that the substituents R 1 to R 6 can bond to. That is, n1 and n2 are each independently an integer of 0 to 4, n3 is an integer of 0 to 2, n4 and n6 are each independently an integer of 0 to 3, n5 is 0 to 5 represents an integer In one aspect of the invention, n1 is zero. In one aspect of the invention, n1 is one. In one aspect of the invention, n2 is zero. In one aspect of the invention, n2 is 1 or 2. In one aspect of the invention, n5 is zero. In one aspect of the invention, n5 is one.
  • n3, n4 and n6 are zero.
  • each of n1-n6 is independently an integer of 0-2.
  • n1-n6 are each independently 0 or 1.
  • n1-n6 are zero.
  • the sum of n1 to n6 is any of 0 to 10, may be any of 0 to 6, may be any of 0 to 4, may be any of 0 to 2 It may be either, for example, it may be one or it may be two.
  • two adjacent R 1 , two adjacent R 2 , two adjacent R 3 , two adjacent R 4 , two adjacent R 5 , two Adjacent R6 may be bonded to each other to form a cyclic structure.
  • the cyclic structure may be an aromatic ring, a heteroaromatic ring, an aliphatic hydrocarbon ring, or an aliphatic heterocyclic ring, or a condensed ring thereof.
  • aromatic ring, heteroaromatic ring, aliphatic hydrocarbon ring, and aliphatic heterocyclic ring refer to the description of the ring condensed to the two benzene rings constituting the carbazol-9-yl group above. can be done.
  • two adjacent R1 's are not bonded to each other and do not form a ring structure.
  • two adjacent R 2 are not bonded to each other and do not form a ring structure.
  • two adjacent R3's are not bonded to each other and do not form a cyclic structure.
  • two adjacent R4 's are not bonded to each other and do not form a ring structure.
  • two adjacent R5's are not bonded to each other and do not form a ring structure.
  • two adjacent R6 are not bonded to each other and do not form a ring structure.
  • two adjacent R 1 , two adjacent R 2 , two adjacent R 3 , two adjacent R 4 , two adjacent R 5 , two adjacent None of adjacent R6 are bonded to each other and do not form a cyclic structure.
  • the benzofuro structure containing the benzene ring to which (R 2 ) n2 is bonded is condensed in any position and orientation with respect to the benzene ring to which (R 3 ) n3 is bonded. good.
  • a substituted or unsubstituted benzofuro[2,3-a]carbazol-9-yl group can be employed as the benzofuran-condensed carbazol-9-yl group formed by condensation of benzofuro structures (partial structure 1). .
  • a substituted or unsubstituted benzofuro[3,2-a]carbazol-9-yl group can also be employed (partial structure 2).
  • a substituted or unsubstituted benzofuro[2,3-b]carbazol-9-yl group can also be employed (partial structure 3).
  • a substituted or unsubstituted benzofuro[3,2-b]carbazol-9-yl group can also be employed (partial structure 4).
  • a substituted or unsubstituted benzofuro[2,3-c]carbazol-9-yl group can also be employed (partial structure 5).
  • a substituted or unsubstituted benzofuro[3,2-c]carbazol-9-yl group can also be employed (partial structure 6).
  • either partial structure 1 or partial structure 2 is selected.
  • either substructure 3 or substructure 4 is selected.
  • either substructure 5 or substructure 6 is selected.
  • either partial structure 1, partial structure 3, or partial structure 5 is selected.
  • either substructure 2, substructure 4, or substructure 6 is selected.
  • the compound represented by general formula (1) has 2 or 3 carbazole structures in the molecule.
  • the number may be two, or for example, three.
  • the compound represented by general formula (1) has one or two dibenzofuran structures in the molecule.
  • it may be one, or it may be two.
  • the compound represented by general formula (1) has three carbazole structures and one or two dibenzofuran structures in the molecule.
  • the number of dibenzofuran structures may be one, for example, or two.
  • one benzene ring of the dibenzofuran structure is preferably one benzene ring of the carbazole structure.
  • the compound represented by general formula (1) does not have a pyrrole ring that does not form a carbazole structure. In one aspect of the present invention, the compound represented by general formula (1) does not have a furan ring that does not form a dibenzofuran structure. In one aspect of the present invention, the compound represented by general formula (1) does not have a thiophene ring, an indene ring and a silaindene ring. In one aspect of the present invention, the compound represented by the general formula (1) has no heterocycles other than the heterocycles constituting the carbazole structure and the dibenzofuran structure. In one aspect of the present invention, the compound represented by the general formula (1) does not have condensed rings in which six or more rings are condensed.
  • R 1 to R 8 each independently represent a deuterium atom or a substituent.
  • n1, n2, n7 and n8 are each independently an integer of 0 to 4
  • n3 is an integer of 0 to 2
  • n4 and n6 are each independently an integer of 0 to 3
  • n5 is 0
  • Two adjacent R 7 and two adjacent R 8 may be bonded to each other to form a cyclic structure.
  • the corresponding descriptions in general formula (1) can be referred to.
  • n7 and n8 are integers anywhere from 0 to 2, for example n7 and n8 may be 0, n7 and n8 may be 1, n7 and n8 may be 2 may be
  • R 1 to R 9 each independently represent a deuterium atom or a substituent.
  • n1, n2, n8 and n9 are each independently an integer of 0 to 4
  • n3 and n7 are each independently an integer of 0 to 2
  • n4 and n6 are each independently an integer of 0 to 3
  • n5 represents any integer from 0 to 5.
  • 2 adjacent R 1 , 2 adjacent R 2 , 2 adjacent R 3 , 2 adjacent R 4 , 2 adjacent R 5 , 2 adjacent R 6 , 2 adjacent R 7 , two adjacent R 8 , and two adjacent R 9 may be bonded to each other to form a cyclic structure.
  • n7-n9 are integers, for example any integer from 0-2, eg n7-n9 may be 0 or 1, eg n7-n9 may be 0.
  • R 1 to R 11 each independently represent a deuterium atom or a substituent.
  • n1, n4, n6, n7 and n8 are each independently an integer of 0 to 3
  • n2 is an integer of 0 to 4
  • n3 is an integer of 0 to 2
  • R 1 to R 6 and n2 to n6 in general formula (3A) the corresponding descriptions in general formula (1) can be referred to.
  • R 7 and R 8 the description of R 1 in general formula (1) can be referred to.
  • R 9 , R 10 and R 11 the description of R 5 in general formula (1) can be referred to.
  • n1, n7, n8 may be any integer from 0 to 2, eg n1, n7, n8 may be 0 or 1, eg n1, n7, n8 may be 0; n5, n9 to n11 may be any integer from 0 to 2, for example n5, n9 to n11 may be 0 or 1, for example n5, n9 to n11 may be 0.
  • R 1 to R 11 each independently represent a deuterium atom or a substituent.
  • n1, n4, n6 and n8 are each independently an integer of 0 to 3
  • n2 and n9 are each independently an integer of 0 to 4
  • n3 and n7 are each independently an integer of 0 to 2
  • n7 and n8 may be any integers from 0 to 2, for example n7 and n8 may be 0 or 1, for example n7 and n8 may be 0.
  • n9 to n11 may be any integer from 0 to 2, eg n9 to n11 may be 0 or 1, eg n9 to n11 may be zero.
  • the compound represented by general formula (1) preferably has, for example, any one of the following ring skeletons. At least one hydrogen atom in the skeleton below may be substituted with a deuterium atom or a substituent, and the skeleton below may be further condensed with a ring. In addition, the skeleton does not have to be further condensed with a ring.
  • substituents reference can be made to the description of the substituents in the description of R 1 to R 11 above.
  • a compound having an axisymmetric structure is selected as the compound represented by general formula (1). In one embodiment of the present invention, a compound having an asymmetric structure is selected as the compound represented by general formula (1).
  • 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 a vapor deposition method and used. It is preferably 1200 or less, more preferably 1000 or less, and even more preferably 900 or less. The lower limit of the molecular weight is the molecular weight of the smallest compound in the group of compounds represented by general formula (1).
  • the compound represented by general formula (1) 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 (1) has the advantage of being easily dissolved in an organic solvent. Therefore, the compound represented by the general formula (1) can be easily applied to the coating method, and can be easily purified to increase its purity.
  • the compound represented by general formula (1) preferably does not contain metal atoms or boron atoms.
  • a compound composed of atoms selected from the group consisting of carbon, hydrogen, deuterium, nitrogen, oxygen 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 atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms and oxygen atoms can be selected.
  • 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),
  • substituted group b refers to 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 (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).
  • 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 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
  • 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, a ring skeleton having 5 to 20 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 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.
  • 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, or may be selected from Substituent Group d.
  • 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 straight chain 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
  • a compound represented by the general formula (1) can be preferably applied to an organic semiconductor device.
  • a CMOS complementary metal oxide semiconductor
  • the compound represented by formula (1) can be used to fabricate organic optical devices such as organic electroluminescence devices and solid-state imaging devices (for example, CMOS image sensors).
  • the compound represented by the general formula (1) of the present invention can be used for organic light-emitting devices such as organic electroluminescence devices (organic EL devices).
  • organic EL devices organic electroluminescence devices
  • the compound represented by the general formula (1) of the present invention can be effectively used as an electron barrier material for organic light emitting devices.
  • the life of the device can be lengthened by using the compound represented by the general formula (1) of the present invention for the electron barrier layer.
  • An organic electroluminescence element has a structure in which at least an anode, a cathode, and an organic layer are formed between the anode and the cathode.
  • the organic layer includes at least a light-emitting layer, and preferably has one or more organic layers (especially an electron barrier layer) in addition to the light-emitting layer.
  • Organic layers constituting an organic electroluminescence device include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transporting layer, an exciton blocking layer, a base layer for a light emitting layer, and the like. can be mentioned.
  • 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 structural example of a specific 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 an electron blocking layer
  • 6 is a base layer
  • 7 is a light emitting layer
  • 8 is a hole blocking layer
  • 9 denotes an electron transport layer
  • 10 an electron injection layer
  • 11 a cathode.
  • the description of the substrate and the light-emitting layer also applies to the substrate and the light-emitting layer of the organic photoluminescence device.
  • the compound represented by general formula (1) is used for an electron barrier layer of an organic electroluminescence device.
  • the electron barrier layer may contain only the compound represented by the general formula (1), or may contain compounds other than the compound represented by the general formula (1).
  • the concentration of the compound represented by general formula (1) in the electron barrier layer is preferably 50% by weight or more, more preferably 90% by weight or more, and may be, for example, 99% by weight or more. .9% by weight or more.
  • the thickness of the electron barrier layer is preferably 1 nm or more, more preferably 3 nm or more, and can be, for example, 5 nm or more, or, for example, 10 nm or more.
  • the thickness of the electron barrier layer is preferably less than 30 nm, more preferably less than 20 nm, and can be, for example, 15 nm or less.
  • the thickness of the electron barrier layer is preferably smaller than the thickness of the light emitting layer.
  • the thickness of the electron barrier layer is preferably one-half or less, more preferably one-third or less, and can be, for example, one-fourth or less of the thickness of the light-emitting layer. Moreover, it is preferably 1/20 or more, and can be, for example, 1/10 or more, or, for example, 1/6 or more.
  • the electron barrier layer containing the compound represented by formula (1) is preferably provided between the light-emitting layer and the anode.
  • the light-emitting layer and the electron blocking layer are stacked so as to be in direct contact with each other.
  • One embodiment of the present invention includes a stacked structure in which an electron blocking layer containing the compound represented by general formula (1), a base layer, and a light-emitting layer are stacked in this order from the anode side.
  • the electron barrier layer and the base layer are laminated so as to be in direct contact, and the base layer and the light-emitting layer are laminated so as to be in direct contact, but the electron barrier layer and the light-emitting layer are not in contact.
  • the underlayer is formed for the purpose of improving the orientation of the light-emitting layer, and is a layer containing a hole-transporting material.
  • the base layer contains a compound having a common partial structure with the compound contained in the light-emitting layer.
  • the common partial structure here means that a partial structure consisting of 12 or more atoms other than hydrogen atoms and deuterium atoms is common, and 16 or more atoms other than hydrogen atoms and deuterium atoms
  • a partial structure consisting of 20 or more atoms other than a hydrogen atom and a deuterium atom may be common.
  • the base layer contains the same compound as the compound contained in the light-emitting layer.
  • the underlayer contains only the same compounds as those contained in the light-emitting layer.
  • the underlayer contains the same compound as the host material contained in the light-emitting layer.
  • the thickness of the underlayer is preferably 1 nm or more, more preferably 3 nm or more, and can be, for example, 5 nm or more.
  • the thickness of the adjacent layer is preferably less than 30 nm, more preferably less than 20 nm, and can be, for example, 10 nm or less, or 7 nm or less.
  • the thickness of the underlayer is preferably smaller than the thickness of the light-emitting layer.
  • the thickness of the underlayer is preferably one-half or less, more preferably one-third or less, and can be, for example, one-fourth or less of the thickness of the light-emitting layer. Moreover, it is preferably 1/20 or more, and can be, for example, 1/10 or more.
  • the thickness of the underlayer is preferably smaller than the thickness of the electron barrier layer.
  • the thickness of the underlayer can be, for example, three-fourths or less, for example, two-thirds or less, or, for example, one-half or less of the thickness of the electron barrier layer. Moreover, it is preferably 1/20 or more, and can be, for example, 1/10 or more, or, for example, 1/4 or more.
  • the light-emitting layer is a layer that emits light after recombination of holes and electrons injected from the anode and the cathode to generate excitons.
  • the light-emitting layer contains at least a light-emitting material.
  • a host material In order for an organic electroluminescence device to exhibit high luminous efficiency, it is important to confine the singlet excitons and triplet excitons of the luminescent material in the luminescent material. Therefore, it is preferable to use a host material in addition to the light-emitting material in the light-emitting layer.
  • an organic compound having an excited singlet energy higher than that of the light-emitting material of the present invention can be used, and an organic compound having both excited singlet energy and excited triplet energy higher than those of the light-emitting material. is preferably used.
  • the host material singlet excitons and triplet excitons generated in the light-emitting material can be confined in the molecules of the light-emitting material, and the light emission efficiency can be fully exploited. However, even if singlet excitons and triplet excitons cannot be confined sufficiently, it is possible to obtain high luminous efficiency in some cases.
  • the maximum amount of light emitted from the device is emitted from the light-emitting material contained in the light-emitting layer.
  • This emission includes fluorescence emission and may also include delayed fluorescence. However, the emission may be partly or partially emitted from the host material.
  • the concentration of the light-emitting material in the light-emitting layer is preferably 0.1% by weight or more, more preferably 1% by weight or more, and preferably 50% by weight or less. It is more preferably 10% by weight or less, more preferably 10% by weight or less.
  • an assist dopant may be used in the light-emitting layer.
  • the light-emitting layer is composed of a host material, an assist dopant, and a light-emitting material.
  • a host material having a higher lowest excited singlet energy level than the assist dopant is used, and a light-emitting material having a lower lowest excited singlet energy level than the assist dopant is used.
  • a delayed fluorescence material is the fluorescence emitted when a compound in an excited state returns from the excited singlet state to the ground state after reverse intersystem crossing occurs from the excited triplet state to the excited singlet state.
  • the target compound is the delayed fluorescence material.
  • the delayed fluorescent material is preferably a thermally activated delayed fluorescent material capable of causing reverse intersystem crossing by absorption of thermal energy.
  • a thermally activated delayed fluorescence material can be confirmed by the fact that the emission lifetime obtained by measuring the transient decay curve of emission becomes longer depending on the measurement temperature.
  • a delayed fluorescence material as an assist dopant, the energy of the excited singlet state generated by the direct transition from the ground state and the excited singlet energy due to the reverse intersystem crossing in the assist dopant are efficiently transferred to the light-emitting material. , can effectively assist the luminescence of the luminescent material.
  • the concentration of the assist dopant in the light-emitting layer is preferably lower than the content of the host material.
  • the content of the host material is 15% by weight or more and 99.9% by weight or less.
  • the content of the assist dopant is preferably 5.0% by weight or more and 50% by weight or less, and the content of the light-emitting material is 0.5% by weight or more and 5.0% by weight or less. is preferred.
  • the light-emitting layer does not contain an inorganic compound. Further, in one embodiment of the present invention, the light-emitting layer does not contain a metal atom. In one embodiment of the present invention, no phosphorescence is observed from the emissive layer at 300K.
  • the host material used in the light-emitting layer is preferably an organic compound that has hole-transporting ability and electron-transporting ability, prevents emission from becoming longer in wavelength, and has a high glass transition temperature.
  • a compound containing a carbazole structure can be preferably selected as the host material.
  • the host material contains two or more structures selected from the group consisting of a carbazole structure, a dibenzofuran structure and a dibenzothiophene structure, for example a compound containing two structures or a compound containing three structures.
  • a compound can be selected.
  • a compound containing a 1,3-phenylene structure can be selected as the host material.
  • a compound containing a biphenylene structure can be selected as the host material.
  • a compound having 5 to 8 benzene rings contained in the molecule can be selected as the host material. or a compound with 7 may be selected.
  • Preferred compounds that can be used as host materials are listed below, but the host materials that can be employed in the present invention are not limitedly interpreted by the following specific examples.
  • a delayed fluorescence material can be used as a light-emitting material or an assist dopant in the light-emitting layer. Also, different delayed fluorescence materials can be used as the light-emitting material and the assist dopant.
  • a fluorescence lifetime measurement system such as a streak camera system manufactured by Hamamatsu Photonics
  • fluorescence with an emission lifetime of 100 ns (nanoseconds) or more is usually observed.
  • the difference ⁇ EST between the lowest excited singlet energy and the lowest excited triplet energy at 77K is preferably 0.3 eV or less, more preferably 0.25 eV or less, and 0.2 eV or less.
  • thermoly activated delayed fluorescence material absorbs the heat emitted by the device and undergoes reverse intersystem crossing from the excited triplet state to the excited singlet relatively easily, and the excited triplet energy efficiently contributes 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 delayed fluorescence material preferably does not contain metal atoms.
  • a compound composed 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 composed of carbon atoms, hydrogen atoms and nitrogen atoms may be selected as the delayed fluorescence material.
  • Typical delayed fluorescence materials include compounds having a structure in which one or two acceptor groups and at least one donor group are bonded to a benzene ring.
  • acceptor group examples include groups containing a heteroaryl ring containing a nitrogen atom as a ring skeleton-constituting atom, such as a cyano group and a triazinyl ring.
  • a preferred example of the donor group is a substituted or unsubstituted carbazol-9-yl group.
  • a benzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted indene ring, a substituted or unsubstituted silaindene ring, and the like. be able to.
  • a compound that is represented by the following general formula (4) and emits delayed fluorescence can be preferably used as the delayed fluorescence material.
  • 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 (5) is particularly preferable among the compounds represented by the general formula (4).
  • General formula (5) is particularly preferable among the compounds represented by the general formula (4).
  • 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 cyano group 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.
  • 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 (4) and (5) is preferably, for example, a group represented by general formula (6) below.
  • general formula (6)
  • R 31 and R 32 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 31 and R 32 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 containing a structure represented by general formula (4) or general formula (5), or general formulas (7) to It may be a group represented by (9). These groups may be introduced into L up to the maximum number of substituents that can be introduced. Also, when a plurality of substituents 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 (4) or general formula (5).
  • Substituent means a monovalent group capable of substituting a hydrogen atom, for example, selected from substituent group A described later, selected from substituent group B described later, or selected from substituent group C described later or selected from Substituent Group D described later.
  • the compound represented by the general formula (6) is preferably a compound represented by any one of the following general formulas (7) to (9).
  • general formula (7) general formula (8)
  • 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 (7) to (9).
  • the number of substituents in general formulas (7) to (9) is not particularly limited. It is also preferred if all are unsubstituted (ie hydrogen or deuterium atoms).
  • substituents in each of the general formulas (7) to (9) may be the same or different.
  • the substituent is preferably any one of R 52 to R 59 in general formula (7), and general formula (8) Any one of R 62 to R 67 is preferred in the case of general formula (9), and any one of R 72 to R 77 is preferred in the case of general formula (9).
  • 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, 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.
  • Substituents are selected, for example, from substituent group A described below, selected from substituent group B described later, selected from substituent group C described later, or selected from substituent group D described later. can be done.
  • 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 (7) to (9).
  • the groups represented by formulas (7) to (9) may be introduced into L 11 to L 14 up to the maximum number of substituents that can be introduced. Further, when a plurality of groups represented by general formulas (7) to (9) 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 (4) or general formula (5).
  • 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 (4) and (5) 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 (7) to (9). More preferred are groups represented by the following general formulas (8a) to (8f) condensed with general formula (8).
  • 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 general formula (9) 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 (8a) to (8f) may be selected from within the range of 5 to 7, and may be 5.
  • R 41 to R 110 it is possible to select a group of the following substituent group B, select a group of the following substituent group C, or select a group of the following substituent group D. can.
  • 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 (8a) to (8f) may each independently be substituted with a nitrogen atom. That is, C—R 41 to C—R 110 in general formulas (8a) to (8f) may each independently be substituted with N.
  • the number of nitrogen atoms substituted is preferably 0 to 4, more preferably 1 to 2 in the groups represented by formulas (8a) to (8f). In one aspect of the present invention, the number of nitrogen atoms substituted is 0. Moreover, 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.
  • X 1 -X 6 are oxygen atoms.
  • X 1 -X 6 are sulfur atoms.
  • X 1 -X 6 are NR.
  • R represents a hydrogen atom or a substituent, preferably a substituent. As the substituent, a group of the following substituent group A is selected, a group of the following substituent group B is selected, a group of the following substituent group C is selected, or a group of the substituent group D is selected.
  • a compound that is represented by the following general formula (10) and emits delayed fluorescence can be particularly preferably used as the delayed fluorescence material.
  • a compound represented by general formula (10) can be employed as the delayed fluorescence material.
  • 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 referred to here include the following substituent group A.
  • substituent group A Preferable examples of the substituent when the aryl group of the above diarylamino group is substituted include the substituents of the following substituent group A, and further include a cyano group and a substituted amino group.
  • substituent group B it is also possible to select from the substituent group B, select from the substituent group C, or select from the substituent group D.
  • Specific examples of the compound group and compounds encompassed by the general formula (10) 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 (11) contains at least two carbazole structures in its molecule.
  • Substituents that Z 1 and Z 2 can take are, for example, selected from the following substituent group A, selected from the following substituent group B, selected from the following substituent group C, and selected from the following substituent group D.
  • You can Specific examples of the substituents that R 11 to R 18 , the arylamino group, and the carbazolyl group can take include the following substituent group A, cyano group, substituted arylamino group, and substituted alkylamino group. can be done.
  • 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.
  • compounds represented by general formula (12) 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 substituents of the following substituent group A, substituents of the following substituent group B, substituents of the following substituent group C, and substituents of the following substituent group D. can be done.
  • R 11 to R 18 , R 21 to R 28 , the above arylamino group and carbazolyl group can take include substituents of the following substituent group A, cyano group, 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.
  • a compound that is represented by the following general formula (13) and emits delayed fluorescence can also be particularly preferably used as the delayed fluorescence material of the present invention.
  • 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 above 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 corresponding explanation and preferred range of general formula (4) can be referred to.
  • the donor group is preferably represented by the general formula (6)
  • the acceptor group is preferably represented by a cyano group or the following general formula (14).
  • 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 (6) can be referred to.
  • L15 in general formula ( 14 ) is a single bond. * represents the bonding position to the carbon atom (C) constituting the ring skeleton of the ring in general formula (13).
  • t-Bu represents a tertiary butyl group (tert-butyl group).
  • the delayed fluorescence material known delayed fluorescence materials other than those described above can be used in combination as appropriate. Moreover, even unknown delayed fluorescence materials can be used.
  • the delayed fluorescence material paragraphs 0008 to 0048 and 0095 to 0133 of WO2013/154064, paragraphs 0007 to 0047 and 0073 to 0085 of WO2013/011954, paragraphs 0007 to 0033 and 0059 to 0066 of WO2013/011955, Paragraphs 0008 to 0071 and 0118 to 0133 of WO2013/081088, paragraphs 0009 to 0046 and 0093 to 0134 of JP 2013-256490, paragraphs 0008 to 0020 and 0038 to 0040 of JP 2013-116975, WO2013 / Paragraphs 0007 to 0032 and 0079 to 0084 of 133359, paragraphs 0008 to 0054 and 0101 to 0121 of WO2013/161437, paragraphs 0007 to 0041 and 0060 to 0069
  • 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.
  • a compound having a lowest excited singlet energy lower than that of the assist dopant is used as the light-emitting material.
  • the light-emitting material used in combination with the assist dopant include compounds having multiple resonance effects of boron atoms and nitrogen atoms, and compounds containing condensed aromatic ring structures such as anthracene, pyrene, and perylene.
  • the delayed fluorescence materials exemplified so far can also be used.
  • a compound represented by the following general formula (15) is used as a light-emitting material used in combination with an assist dopant.
  • 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 may be 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 (15) 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 (15) may be present in the compound.
  • it may have a structure in which skeletons represented by general formula (15) are bonded to each other via a single bond or a linking group.
  • the skeleton represented by the general formula (15) may be added with a structure exhibiting a multiple resonance effect in which benzene rings are linked 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 a light-emitting material used in combination with an assist dopant.
  • a compound represented by the following general formula (16) 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 the following general formula (17).
  • general formula (17) In general formula (17), 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 (17) may be one, two, or three of R 1 to R 7 in general formula (16). 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 (17).
  • R 1 , R 3 , R 5 and R 7 are groups represented by general formula (17). 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 (17). 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 (17), 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 (17).
  • 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 .
  • Substituents that can be taken by R 11 to R 15 in general formula (17) are, for example, selected from the following substituent group A, selected from the following substituent group B, or selected from the following substituent group C. , or the following substituent group D.
  • a substituted amino group is selected as a substituent, a disubstituted amino group is preferred, 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 Alternatively, it is preferably an unsubstituted alkyl group, and particularly preferably a substituted or unsubstituted aryl group (diarylamino group).
  • Substituents that can be taken by the two aryl groups of the diarylamino group are, for example, selected from the following substituent group A, selected from the following substituent group B, selected from the following substituent group C, and the following substituents You can choose from group D.
  • 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.
  • Examples of substituted or unsubstituted carbazol-9-yl groups include groups in which L 11 in the general formula (9) is a single bond.
  • R 13 in general formula (17) is a substituent
  • R 11 , R 12 , R 14 and R 15 are hydrogen atoms.
  • R 11 in general formula (17) is a substituent
  • R 12 , R 13 , R 14 and R 15 are hydrogen atoms.
  • R 11 and R 13 in general formula (17) are substituents
  • R 12 , R 14 and R 15 are hydrogen atoms.
  • R 1 to R 7 of general formula (16) may include a group in which all of R 11 to R 15 of general formula (17) 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 (16) 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 of general formula (16) 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 (16) 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 (16) 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 (16) 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 (16) 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.
  • a compound containing a carbazole structure may be selected as a light-emitting material used in combination with an assist dopant.
  • a compound that does not contain any of the carbazole structure, the dibenzofuran structure, and the dibenzothiophene structure may be selected as the light-emitting material used in combination with the assist dopant.
  • t-Bu represents a tertiary butyl group (tert-butyl group).
  • Derivatives of the above-exemplified compounds include compounds in which at least one hydrogen atom is replaced with a deuterium atom, an alkyl group, an aryl group, a heteroaryl group, or a diarylamino group.
  • compounds described in paragraphs 0220 to 0239 of WO2015/022974 can also be preferably used as a light-emitting material used in combination with an assist dopant.
  • 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 material 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.
  • a hole blocking layer functions as an electron transport layer.
  • the hole blocking layer blocks holes from reaching the electron transport layer during electron transport.
  • 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.
  • 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.
  • Each organic layer of the organic electroluminescence device can be formed by a wet process.
  • a solution in which a composition containing a compound constituting the organic layer is dissolved is applied to the surface, and the layer is formed after removing the solvent.
  • wet processes include spin coating, slit coating, inkjet (spray), gravure printing, offset printing, and flexographic printing, but are not limited to these.
  • an appropriate organic solvent capable of dissolving the compound constituting the organic layer is selected and used.
  • a substituent for example, an alkyl group
  • the organic layer can be formed in a dry process.
  • the dry process can be vacuum deposition, but is not limited to this.
  • the compounds constituting the organic layer may be co-deposited from separate deposition sources, or may be co-deposited from a single deposition source in which the compounds are mixed.
  • the composition ratio of the plurality of compounds contained in the vapor deposition source is reduced by performing co-deposition under conditions in which the vapor deposition rates (weight reduction rates) of the plurality of compounds contained in the single vapor deposition source match or substantially match.
  • the vapor deposition rates (weight reduction rates) of the plurality of compounds contained in the single vapor deposition source match or substantially match.
  • can form an organic layer having a composition ratio corresponding to An organic layer having a desired composition ratio can be easily formed by mixing a plurality of compounds at the same composition ratio as that of the organic layer to be formed as a vapor deposition source.
  • the temperature at which each of the co-deposited compounds has the same weight loss rate can be identified and used as the temperature during co-deposition.
  • 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 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 the mother panel forms a thin film transistor (TFT) having an active layer and source/drain electrodes on a base substrate, and the TFT is coated with a planarization film, a pixel electrode, 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 the mother panel forms a thin film transistor (TFT) having an active layer and source/drain electrodes on a base substrate, and the TFT is coated with a planarization film, a pixel electrode, 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. In some embodiments, 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 emission characteristics were evaluated using a source meter (manufactured by Keithley: 2400 series), a semiconductor parameter analyzer (manufactured by Agilent Technologies: E5273A), an optical power meter measuring device (manufactured by Newport: 1930C), and an optical spectrometer. (Ocean Optics: USB2000), a spectroradiometer (Topcon: SR-3) and a streak camera (Hamamatsu Photonics, Model C4334).
  • Example 1 Each thin film was laminated at a degree of vacuum of 5.0 ⁇ 10 ⁇ 5 Pa by a vacuum deposition method on a glass substrate on which an anode made of indium tin oxide (ITO) with a thickness of 50 nm was formed.
  • ITO indium tin oxide
  • HAT-CN was formed to a thickness of 10 nm on ITO, and NPD was formed thereon to a thickness of 30 nm.
  • compound 1a was formed to a thickness of 10 nm, and H1 was formed thereon to a thickness of 5 nm.
  • T63 and H1 were co-deposited from different vapor deposition sources to form a layer with a thickness of 40 nm, which was used as a light-emitting layer.
  • the concentrations of T63 and H1 in the light-emitting layer were 45 wt% and 55 wt%, respectively.
  • Liq and SF3-TRZ were co-deposited from different vapor deposition sources to form a layer with a thickness of 30 nm.
  • the concentrations of Liq and SF3-TRZ in this layer were 30% and 70% by weight, respectively.
  • Liq was formed to a thickness of 2 nm, and then aluminum (Al) was vapor-deposited to a thickness of 100 nm to form a cathode, thereby obtaining an organic electroluminescence device (EL device 1).
  • Comparative example 1 An organic electroluminescence device (comparative EL device 1) was produced by carrying out the same steps as in Example 1, except that the comparative compound 1 was used instead of the compound 1a.
  • Example 2 An organic electroluminescence device (EL device 2) was produced by performing the same steps as in Example 1, except that compound 2a was used instead of compound 1a. It was confirmed that the EL device 2 also had a longer device life than the comparative EL device 1.
  • Example 3 An organic electroluminescence device (EL device 3) was produced by performing the same steps as in Example 1 except that compound 2b was used instead of compound 1a and T63 was changed to T64. EL device 3 had a 15% longer device life than the EL device using compound 1a instead of compound 2b.
  • the compound of the present invention is useful as an electron barrier material and can be used in organic semiconductor devices.
  • the compound of the present invention in the electron barrier layer of an organic electroluminescence device, the life of the device can be extended. Therefore, the present invention has high industrial applicability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Electroluminescent Light Sources (AREA)
PCT/JP2022/025463 2021-06-29 2022-06-27 化合物、電子障壁材料、有機半導体素子および化合物 Ceased WO2023276918A1 (ja)

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WO2013109045A1 (en) * 2012-01-16 2013-07-25 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
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KR20240022512A (ko) * 2021-06-15 2024-02-20 가부시키가이샤 큐럭스 유기 발광 소자 및 그 제조 방법

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WO2013109045A1 (en) * 2012-01-16 2013-07-25 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
US20140158992A1 (en) * 2012-12-07 2014-06-12 Universal Display Corporation Carbazole Compounds For Delayed Fluorescence
CN104650118A (zh) * 2014-07-01 2015-05-27 吉林奥来德光电材料股份有限公司 一种以二苯并呋喃为骨架核心的衍生物制备及其应用
CN108586453A (zh) * 2018-01-17 2018-09-28 长春海谱润斯科技有限公司 一种苯并咔唑类衍生物及其有机电致发光器件
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