CN117396486A - Compound, light-emitting material, and light-emitting element - Google Patents
Compound, light-emitting material, and light-emitting element Download PDFInfo
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- CN117396486A CN117396486A CN202280039330.4A CN202280039330A CN117396486A CN 117396486 A CN117396486 A CN 117396486A CN 202280039330 A CN202280039330 A CN 202280039330A CN 117396486 A CN117396486 A CN 117396486A
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- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000007647 flexography Methods 0.000 description 1
- OGTUEBCOVPUEJF-UHFFFAOYSA-N fluoranthene Chemical class C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1.C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 OGTUEBCOVPUEJF-UHFFFAOYSA-N 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical class C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical class N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004370 n-butenyl group Chemical group [H]\C([H])=C(/[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 238000003077 quantum chemistry computational method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical class C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 125000005579 tetracene group Chemical group 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- 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
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- 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
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- 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
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- Electroluminescent Light Sources (AREA)
Abstract
The compound represented by the following general formula is a luminescent material having a short lifetime for delayed fluorescence. R is R 1 ～R 4 Wherein more than 1 of them are ring-condensed indol-1-yl, R 1 ～R 4 1 to 2 of them are aryl or heteroaryl, the remainder R 1 ～R 4 Is a hydrogen atom or a deuterium atom.
Description
Technical Field
The present invention relates to a compound useful as a light-emitting material and a light-emitting element using the same.
Background
Research is actively being conducted to improve the light emission efficiency of light emitting elements such as organic electroluminescent elements (organic EL elements). In particular, there has been much effort in improving the luminous efficiency by newly developing and combining an electron transporting material, a hole transporting material, a light emitting material, and the like constituting an organic electroluminescent element. Among them, studies on organic electroluminescent devices using delayed fluorescent materials have also been made.
The delayed fluorescent material is a material that emits fluorescence when returning from an excited triplet state to a ground state after an intersystem crossing from the excited triplet state to the excited singlet state occurs in the excited state. Fluorescence generated by this approach is observed later than fluorescence from an excited singlet state (normal fluorescence) generated directly from the ground state, and is therefore referred to as delayed fluorescence. Here, for example, in the case where a luminescent compound is excited by injection of a carrier, the probability of occurrence of an excited singlet state and an excited triplet state is 25% to 75% in total, and therefore, there is a limit in improving the luminous efficiency by fluorescence from only the excited singlet state that is directly generated. On the other hand, in the delayed fluorescent material, in addition to the excited singlet state, the excited triplet state can be used for fluorescence emission by passing through the above-described pathway of intersystem crossing, and therefore, a high emission efficiency can be obtained compared with a usual fluorescent material.
After this principle is clarified, various delayed fluorescent materials have been found through various studies. However, it is not just a material that emits delayed fluorescence but is immediately useful as a light-emitting material. Among the delayed fluorescent materials, there are materials that are relatively difficult to generate a reverse intersystem crossing, and materials that have a long lifetime of delayed fluorescence. Also, there are materials in which excitons accumulate in a high current density region to decrease light emission efficiency or rapidly deteriorate if driven continuously for a long period of time. Therefore, in practice, there is room for improvement in terms of practicality in the case of a very large number of delayed fluorescent materials. In recent years, the characteristics required for fluorescent materials have also been increasing. Therefore, even a delayed fluorescent material excellent in the following structure is required to have further improved characteristics (see patent document 1).
[ chemical formula 1]
Technical literature of the prior art
Patent literature
Patent document 1: WO2019/004254
Disclosure of Invention
Technical problem to be solved by the invention
The relationship between the chemical structure and the characteristics of the delayed fluorescent material has heretofore been hardly explained. Therefore, it is difficult to widen the chemical structure of a compound useful as a light-emitting material in the present situation, and there are many points of uncertainty.
Under such circumstances, the present inventors have conducted studies with a view to providing a compound more useful as a light-emitting material for a light-emitting element. Further, intensive studies have been made with a view to deriving general formulae of compounds more useful as light-emitting materials and making them broader.
Means for solving the technical problems
As a result of intensive studies to achieve the above object, the present inventors have found that a compound having a structure satisfying specific conditions among terephthalonitrile derivatives is useful as a light emitting material. The present invention has been made in view of such an observation, and specifically has the following structure.
[1] A compound represented by the following general formula (1).
[ chemical formula 2]
General formula 1
In the general formula (1), the amino acid sequence of the compound,
R 1 ～R 4 wherein at least 1 is a ring-fused indol-1-yl group which forms a fused ring having a ring number of 4 or more by being fused with the ring of indole, the fused ring may be substituted,
R 1 ～R 4 each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group bonded via a carbon atom,
the remainder R 1 ～R 4 Represents a hydrogen atom or a deuterium atom.
[2] The compound according to [1], wherein,
R 1 ～R 4 each independently a donor group, at least 1 of which is indol-1-yl fused to the ring,
R 1 ～R 4 is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group bonded via a carbon atom,
the remainder R 1 ～R 4 Is a hydrogen atom or a deuterium atom.
[3] The compound according to [1], wherein,
R 1 ～R 4 each independently a donor group, at least 1 of which is indol-1-yl fused to the ring,
R 1 ～R 4 is a substituted or unsubstituted aryl or a carbon atom bonded substituted or unsubstituted heteroaryl.
[4] The compound according to [1], wherein,
R 1 ～R 4 each independently a donor group, at least 1 of which is indol-1-yl fused to the ring,
R 1 ～R 4 is a substituted or unsubstituted aryl or a carbon atom bonded substituted or unsubstituted heteroaryl.
[5] The compound according to any one of [1] to [4], wherein,
R 1 r is R 4 Each independently is a donor group,
R 3 is a substituted or unsubstituted aryl or a carbon atom bonded substituted or unsubstituted heteroaryl.
[6] The compound according to any one of [1] to [4], wherein,
R 2 R is R 4 Each independently is a donor group,
R 3 is a substituted or unsubstituted aryl or a carbon atom bonded substituted or unsubstituted heteroaryl.
[7] The compound according to any one of [1] to [6], wherein,
the number of fused rings is 5 or more.
[8] The compound according to [7], wherein,
the carbon atoms constituting the skeleton of the condensed ring having 4 or more rings are substituted with a substituted or unsubstituted aryl group.
[9] The compound according to [7], wherein,
the fused ring having 4 or more rings has a nitrogen atom in the skeleton, and the nitrogen atom is substituted with a substituted or unsubstituted aryl group.
[10] The compound according to any one of [1] to [9], wherein,
the ring condensed with the benzene ring constituting the indol-1-yl group is a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring or a substituted or unsubstituted pyrrole ring, and other rings may be further condensed on the furan ring, the thiophene ring and the pyrrole ring.
[11] The compound according to any one of [1] to [10], wherein,
the ring-fused indol-1-yl has any one of the following fused rings,
[ chemical formula 3]
In each of the above structures, a hydrogen atom may be substituted, and a ring may be further condensed.
[12] The compound according to any one of [1] to [10], wherein,
the ring-fused indol-1-yl has any one of the following fused ring backbones,
[ chemical formula 4]
In each of the above structures, a hydrogen atom may be substituted, and a ring may be further condensed.
[13] The compound according to any one of [1] to [12], wherein,
the ring-fused indol-1-yl has a structure that is heterocycle-fused at the 4,5 position of the indole ring.
[14] The compound according to any one of [1] to [13], wherein,
ar is a substituted or unsubstituted phenyl group or a substituted or unsubstituted pyridyl group.
[15] The compound according to any one of [1] to [14], which is composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom and a sulfur atom.
[16] A light-emitting material composed of the compound according to any one of [1] to [15 ].
[17] A light-emitting element is characterized in that,
comprising the compound of any one of [1] to [15 ].
[18] The light-emitting element according to [17], wherein,
the light-emitting element has a light-emitting layer containing the compound and a host material.
[19] The light-emitting element according to [18], wherein,
the light-emitting element has a light-emitting layer that contains the compound and a light-emitting material, and emits light mainly from the light-emitting material.
Effects of the invention
The compound of the present invention is useful as a light-emitting material. The compound of the present invention also includes a compound having a short fluorescence-delayed lifetime. Further, an organic light-emitting element using the compound of the present invention is useful because it has high durability.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a layer structure of an organic electroluminescent element.
Detailed Description
The following describes the present invention in detail. The following description of the constituent elements may be based on the representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples. In the present specification, the numerical range indicated by "to" is a range including the numerical values described before and after "to" as the lower limit value and the upper limit value. In addition, part or all of hydrogen atoms present in the molecule of the compound used in the present invention may be replaced with deuterium atoms [ (] 2 H. Deuterium D). In the chemical structural formula in the present specification, a hydrogen atom is represented by H or a representation thereof is omitted. For example, when an atom bonded to a carbon atom constituting a ring skeleton of a benzene ring is omitted, it is assumed that the atom is bonded to the carbon atom constituting the ring skeleton at a position H indicated by the omitted atom. In the chemical structural formula in the present specification, deuterium atoms are denoted as D.
[ Compound represented by the general formula (1) ]
[ chemical formula 5]
General formula 1
R of the general formula (1) 1 ～R 4 Wherein 2 to 3 of the monomers independently represent a donor group. At least 1 of the donor groups is a substituted or unsubstituted indol-1-yl group, and a ring is condensed on an indole ring constituting the indol-1-yl group, thereby forming a condensed ring having a ring number of 4 or more. Hereinafter, in this specification, a group satisfying this condition is referred to as "ring-condensed indol-1-yl".
In the ring-condensed indol-1-yl group, the benzene ring constituting the indol-1-yl group or the ring condensed with the pyrrole ring may be 1 polycyclic ring or may be 2 or more polycyclic rings or monocyclic rings. For example, in the case of 2 fusions, 1 fused to a benzene ring and 1 fused to a pyrrole ring are preferred. The fused 2 rings may be the same or different. The fused ring having 4 or more, 5 or more, or 6 or more rings, preferably 5 or more rings, can be formed by fusing the ring with the indole ring. For example, a compound forming a condensed ring having a ring number of 4, a compound forming a condensed ring having a ring number of 5, a compound forming a condensed ring having a ring number of 6, a compound forming a condensed ring having a ring number of 8 may be used.
The ring may be fused to only the 2,3 position (b), to only the 4,5 position (e), to only the 5,6 position (f), to only the 6,7 position (g), and to both the 4,5 position (e) and the 6,7 position (g) of the indole ring. And, any 1 of the 4, 5-position (e), 5, 6-position (f), 6, 7-position (g) may be condensed with the 2, 3-position (b) (refer to the following formula, which represents a bonding position).
[ chemical formula 6]
The ring directly condensed with the benzene ring or pyrrole ring constituting the indol-1-yl group (condensed ring is a polycyclic ring, meaning a ring directly condensed with only the ring constituting the polycyclic ring), and may be any of an aromatic hydrocarbon ring, an aromatic heterocyclic ring, an aliphatic hydrocarbon ring, and an aliphatic heterocyclic ring. It is preferable that 1 or more rings selected from the group consisting of benzene rings and aromatic heterocyclic rings are directly condensed.
The heterocyclic ring as described herein is a heteroatom-containing ring. The hetero atom is preferably selected from an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, more preferably from an oxygen atom, a sulfur atom and a nitrogen atom. In a preferred aspect, the heteroatom is an oxygen atom. In a preferred further aspect, the heteroatom is a sulfur atom. In a preferred further aspect, the heteroatom is a nitrogen atom. The number of hetero atoms included in the ring skeleton constituting atoms of the heterocycle is 1 or more, preferably 1 to 3, more preferably 1 or 2. In a preferred aspect, the number of heteroatoms is 1. When the number of heteroatoms is 2 or more, they are preferably the same heteroatom, but may be constituted of different kinds of heteroatoms. For example, more than 2 heteroatoms may each be a nitrogen atom. The ring skeleton constituent atoms other than the hetero atoms are carbon atoms. The number of ring skeleton constituting a heterocyclic ring directly condensed with the benzene ring constituting the indol-1-yl group is preferably 4 to 8, more preferably 5 to 7, still more preferably 5 or 6. In a preferred aspect, the number of ring members constituting the heterocyclic ring is 5. Preferably, there are 2 or more conjugated double bonds in the heterocycle, preferably by heterocycle fusion to extend the conjugated system of the indole ring (that is, preferably having aromatic character). Preferred examples of the heterocyclic ring may include furan ring, thiophene ring, pyrrole ring.
On the ring directly condensed with the benzene ring or pyrrole ring constituting the indol-1-yl group, other rings may be further condensed. The condensed ring may be a single ring or a condensed ring. The fused ring may include an aromatic hydrocarbon ring, an aromatic heterocyclic ring, an aliphatic hydrocarbon ring, an aliphatic heterocyclic ring.
In a preferred aspect of the invention, at least 1 heterocycle is directly fused to the benzene or pyrrole ring constituting the indol-1-yl. In a preferred aspect of the present invention, the fused ring constituting the ring fused indol-1-yl group contains 2 or more heterocyclic rings. For example, a case where 2 heterocycles are included or a case where 3 heterocycles are included can be cited.
The aromatic hydrocarbon ring in the present specification may include a benzene ring. The aromatic heterocyclic ring may include a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyrazole ring, an imidazole ring. The aliphatic hydrocarbon ring may include a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. Aliphatic heterocycles, which may include piperidine rings, pyrrolidine rings, imidazoline rings. Specific examples of the condensed ring may include naphthalene ring, anthracene ring, phenanthrene ring, pyran ring, tetracene ring, indole ring, isoindole ring, benzimidazole ring, benzotriazole ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, cinnoline ring.
In a preferred aspect of the invention, the ring-fused indol-1-yl is benzofuranfused indol-1-yl, benzothiophene fused indol-1-yl, indol fused indol-1-yl or silane indene fused indol-1-yl. In a more preferred aspect of the invention, the indol-1-yl is benzofuran-fused indol-1-yl, benzothiophene-fused indol-1-yl or indol-fused indol-1-yl.
In the present invention, as the benzofuran-condensed indol-1-yl group, a substituted or unsubstituted benzofuran [2,3-e ] indol-1-yl group may be employed. Also, substituted or unsubstituted benzofuran [3,2-e ] indol-1-yl may be employed. Also, substituted or unsubstituted benzofuran [2,3-f ] indol-1-yl may be employed. Also, substituted or unsubstituted benzofuran [3,2-f ] indol-1-yl may be employed. Also, substituted or unsubstituted benzofuran [2,3-g ] indol-1-yl may be employed. Also, substituted or unsubstituted benzofuran [3,2-g ] indol-1-yl may be employed. The condensed rings constituting these groups may or may not be condensed with other rings.
In the present invention, as the benzofuran-condensed indol-1-yl group, a substituted or unsubstituted benzofuran [2,3-a ] carbazol-9-yl group may be employed. Also, substituted or unsubstituted benzo [3,2-a ] carbazol-9-yl groups may be used. Also, substituted or unsubstituted benzo [2,3-b ] carbazol-9-yl groups may be used. Also, substituted or unsubstituted benzo [3,2-b ] carbazol-9-yl groups may be used. Also, substituted or unsubstituted benzo [2,3-c ] carbazol-9-yl groups may be used. Also, substituted or unsubstituted benzo [3,2-c ] carbazol-9-yl groups may be used. The condensed rings constituting these groups may or may not be condensed with other rings.
Preferred benzofuran-condensed indol-1-yl groups may include groups having any of the structures described below, wherein a hydrogen atom may or may not be substituted. For example, a group substituted with an aryl group such as a phenyl group or a group substituted at the 3-position of a carbazole ring can be preferably exemplified. The benzene ring in the following structure may or may not be further condensed with a ring.
[ chemical formula 7]
It is also possible to use carbazol-9-yl in which the benzofuran ring is fused in the 2-and 3-positions. Specifically, the hydrogen atom in the following structure may be substituted or unsubstituted. The benzene ring in the following structure may or may not be further condensed with a ring.
[ chemical formula 8]
In the present invention, as the benzothiophene-fused indol-1-yl group, a substituted or unsubstituted benzothiophene [2,3-e ] indol-1-yl group may be employed. Also, substituted or unsubstituted benzothieno [3,2-e ] indol-1-yl groups may be employed. Also, substituted or unsubstituted benzothieno [2,3-f ] indol-1-yl groups may be employed. Also, substituted or unsubstituted benzothieno [3,2-f ] indol-1-yl groups may be employed. Also, substituted or unsubstituted benzothieno [2,3-g ] indol-1-yl may be employed. Also, substituted or unsubstituted benzothieno [3,2-g ] indol-1-yl groups may be employed. The condensed rings constituting these groups may or may not be condensed with other rings.
In the present invention, as the benzothiophene-fused indol-1-yl group, a substituted or unsubstituted benzothiophene [2,3-a ] carbazol-9-yl group may be employed. Also, substituted or unsubstituted benzothieno [3,2-a ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted benzothieno [2,3-b ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted benzothieno [3,2-b ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted benzothieno [2,3-c ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted benzothieno [3,2-c ] carbazol-9-yl groups may be employed. The condensed rings constituting these groups may or may not be condensed with other rings.
Preferred benzothiophene-fused indol-1-yl groups may include groups having any of the structures described below, the hydrogen atoms of which may or may not be substituted. For example, a group substituted with an aryl group such as a phenyl group or a group substituted at the 3-position of a carbazole ring can be preferably exemplified. The benzene ring in the following structure may or may not be further condensed with a ring.
[ chemical formula 9]
2 carbazol-9-yl fused to the 2,3 position of the benzothiophene ring may also be used. Specifically, the hydrogen atom in the following structure may be substituted or unsubstituted. The benzene ring in the following structure may or may not be further condensed with a ring.
[ chemical formula 10]
In the present invention, as the indole fused indol-1-yl group, a substituted or unsubstituted indolo [2,3-e ] indol-1-yl group may be used. Also, substituted or unsubstituted indolo [3,2-e ] indol-1-yl groups may be employed. Also, substituted or unsubstituted indolo [2,3-f ] indol-1-yl groups may be employed. Also, substituted or unsubstituted indolo [3,2-f ] indol-1-yl groups may be employed. Also, substituted or unsubstituted indolo [2,3-g ] indol-1-yl may be employed. Also, substituted or unsubstituted indolo [3,2-g ] indol-1-yl may be employed. The condensed rings constituting these groups may or may not be condensed with other rings.
In the present invention, as the indole fused indol-1-yl group, a substituted or unsubstituted indolo [2,3-a ] carbazol-9-yl group may be used. Also, substituted or unsubstituted indolo [3,2-a ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted indolo [2,3-b ] carbazol-9-yl may be used. Also, substituted or unsubstituted indolo [3,2-b ] carbazol-9-yl may be used. Also, substituted or unsubstituted indolo [2,3-c ] carbazol-9-yl groups may be employed. Also, substituted or unsubstituted indolo [3,2-c ] carbazol-9-yl groups may be employed. The condensed rings constituting these groups may or may not be condensed with other rings.
Preferred indole fused indol-1-yl groups may include groups having any of the structures described below, wherein a hydrogen atom may or may not be substituted. For example, a group substituted with an aryl group such as a phenyl group or a group substituted at the 3-position of a carbazole ring can be preferably exemplified. The benzene ring in the following structure may or may not be further condensed with a ring.
[ chemical formula 11]
The "alkyl" as described herein may be any of straight chain, branched chain, cyclic. Further, 2 or more kinds of the linear moiety, the cyclic moiety, and the branched moiety may be mixed. The number of carbon atoms of the alkyl group can be 1 or more, 2 or more, or 4 or more, for example. The number of carbon atoms may be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of the alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, cyclopentyl, cyclohexyl, cycloheptyl. The alkyl group of the substituent may be further substituted with a deuterium atom, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom.
The "alkenyl" may be any of straight-chain, branched, and cyclic. Further, 2 or more kinds of the linear moiety, the cyclic moiety, and the branched moiety may be mixed. The number of carbon atoms of the alkenyl group can be, for example, 2 or more and 4 or more. The number of carbon atoms may be 30 or less, 20 or less, 10 or less, 6 or less, or 4 or less. Specific examples of the alkenyl group may include vinyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, n-pentenyl group, isopentenyl group, n-hexenyl group, methacryl group, 2-ethylhexenyl group. Alkenyl groups of the substituents may be further substituted.
The "aryl" and "heteroaryl" may be a single ring or a condensed ring formed by condensing 2 or more rings. In the case of fused rings, the number of fused rings is preferably 2 to 6, and can be selected from 2 to 4, for example. Specific examples of the ring may include a benzene ring, a pyridine ring, a pyrimidine ring, a triazine ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a quinoline ring, a pyrazine ring, a quinoxaline ring, and a naphthyridine ring. Specific examples of arylene or heteroarylene groups may include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 2-pyridyl, 3-pyridyl, 4-pyridyl.
For the alkyl moiety of "alkoxy" and "alkylthio", reference can be made to the description and specific examples of the alkyl groups described above. For the aryl moiety of "aryloxy" and "arylthio", reference can be made to the description and specific examples of the aryl groups described above. For the heteroaryl moiety of "heteroaryloxy" and "heteroarylthio", reference can be made to the description and specific examples of heteroaryl groups described above.
The number of atoms of the ring-condensed indol-1-yl group other than the hydrogen atom and the deuterium atom is preferably 16 or more, more preferably 20 or more, and for example, 26 or more may be used. Further, the number is preferably 80 or less, more preferably 50 or less, and still more preferably 30 or less.
In the general formula (1), the ring-condensed indol-1-yl group may be R alone 1 ～R 4 The number of 1 may be 2 or 3. When the number of the ring-fused indol-1-yl groups is only 1, the number of donor groups other than the ring-fused indol-1-yl groups (hereinafter referred to as "other donor groups") may be 1 or 2. When the number is 2, the number may be the same as or different from each other. When the number of the ring-condensed indol-1-yl groups is 2, other donor groups may be absent or 1. When the number of ring-fused indol-1-yl groups is 3, no other donor groups are present.
Other donor groups are those with a negative sigma p value of Hammett. Here, "hamite σp value" is proposed by l.p. hammett, and the influence of the substituent on the reaction rate or balance of the para-substituted benzene derivative is quantified. Specifically, the following formula holds between the substituent in the para-substituted benzene derivative and the reaction rate constant or equilibrium constant:
log(k/k 0 )＝ρσp
or (b)
log(K/K 0 )＝ρσp
A constant (σp) specific to the substituent in (a). In the above formula, k represents a velocity constant, k, of a benzene derivative having no substituent 0 Represents the rate constant of the benzene derivative substituted with a substituent, K represents the equilibrium constant of the benzene derivative having no substituent, K 0 The equilibrium constant of the benzene derivative substituted with the substituent is represented by ρ, and the reaction constant is determined by the type and condition of the reaction. For the description relating to the "sigma p value of hamite" and the numerical values of the substituents in the present invention, reference can be made to the description relating to the sigma p value of Hansch, c.et al, chem.rev.,91,165-195 (1991). There is a tendency that: the group with negative sigma p value of Hammett shows electron donating property (donor property), and the group with positive sigma p value of Hammett shows electron withdrawing property (acceptor property).
Other donor groups in the present invention are preferably groups containing substituted amino groups. 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, more preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. The substituted amino group is particularly preferably a substituted or unsubstituted diarylamino group or a substituted or unsubstituted diheteroarylamino group. The 2 aryl groups constituting the diarylamino group described herein may be bonded to each other, and the 2 heteroaryl groups constituting the diheteroarylamino group may be bonded to each other. The other donor group in the present invention may be a group bonded to a nitrogen atom of a substituted amino group, or may be a group bonded to a group to which a substituted amino group is bonded. The group to which the substituted amino group is bonded is preferably a pi conjugated group. More preferred is a group bonded to a nitrogen atom of a substituted amino group.
Particularly preferred groups as further donor groups in the present invention are substituted or unsubstituted carbazol-9-yl groups. There are no fused rings on the 2 benzene rings constituting the carbazol-9-yl group. Substituents for the carbazol-9-yl group may include alkyl, alkenyl, aryl, heteroaryl, alkoxy, alkylthio, aryloxy, arylthio, heteroaryloxy, heteroarylthio, substituted amino, and preferred substituents may include alkyl, aryl, substituted amino. For the description of the substituted amino group, reference can be made to the description in the previous paragraph. And, the substituted amino group described herein includes a substituted or unsubstituted carbazolyl group, for example, includes a substituted or unsubstituted carbazol-3-yl group or a substituted or unsubstituted carbazol-9-yl group.
The number of atoms of the other donor group other than the hydrogen atom and the deuterium atom in the present invention is preferably 8 or more, more preferably 12 or more, and for example, 16 or more. The number is preferably 80 or less, more preferably 60 or less, and even more preferably 40 or less.
In a preferred aspect of the present invention, the ring-fused indol-1-yl group is limited to a group having 2 or more hetero rings in the fused ring constituting the group, and the other donor group is referred to as "other donor group". Examples of the group containing 2 or more heterocyclic rings in the condensed ring include D13 to D152 described below.
In another preferred aspect of the invention, the ring-fused indol-1-yl is limited to groups in which at least 1 heterocycle is directly fused to the benzene ring or pyrrole ring of the indole, the remainder of the donor groups being referred to as "other donor groups".
D of the general formula (1) is shown below 1 And D 2 Specific examples of donor groups that may be employed. Specific examples of D7 to D152 are ring-condensed indol-1-yl groups, and specific examples of D1 to D6 are other donor groups. In the following structural formula, ph represents phenyl, and x represents a bonding position. And the methyl group omits CH 3 For example, D2 represents 3-methylcarbazol-9-yl.
[ chemical formula 12-1]
[ chemical formula 12-2]
[ chemical formula 12-3]
[ chemical formula 12-4]
[ chemical formula 12-5]
[ chemical formula 12-6]
The substitution of all hydrogen atoms of D1 to D152 with deuterium atoms is disclosed as D1D to D152D.
The phenyl groups denoted by "Ph" in D31 to D42 and D61 to D79 are substituted with pentadecadeuterated phenyl groups (groups in which all hydrogen atoms of the phenyl groups are replaced with deuterium atoms), and are herein disclosed as D31D1 to D42D1 and D61D1 to D79D1.
R in the general formula (1) 1 ～R 4 Wherein 1 to 2 of the radicals independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group bonded via a carbon atom, R 1 ～R 4 In (2), a group other than a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group bonded via a carbon atom, or a ring-condensed indol-1-yl group represents a hydrogen atom or a deuterium atom, and can be, for example, a hydrogen atom.
R 1 ～R 4 In which only 1 may be substituted or unsubstituted aryl, R 1 ～R 4 May be a substituted or unsubstituted heteroaryl group bonded via a carbon atom. R is R 1 ～R 4 May be the same substituted or unsubstituted aryl group, or may be substituted or unsubstituted aryl groups different from each other. R is R 1 ～R 4 May be the same substituted or unsubstituted heteroaryl group, or may be substituted or unsubstituted heteroaryl groups different from each other. R is R 1 ～R 4 In which only 1 is a substituted or unsubstituted aryl group and the other 1 may be a substituted or unsubstituted heteroaryl group bonded via a carbon atom. In a preferred embodiment of the present invention, R 1 ～R 4 Only 1 of which is substituted or unsubstituted aryl, or R 1 ～R 4 Each independently being a substituted or unsubstituted aryl group. According to the present invention, by using Ar as a substituent, the ΔE of the donor-substituted terephthalonitrile is reduced ST (difference between lowest excited singlet energy and lowest excited triplet energy) and can improve usefulness (light emission efficiency, etc.) as a delayed phosphor.
For the description and preferred ranges of aryl and heteroaryl groups that may be employed for R and Ar, reference can be made to the description of aryl and heteroaryl groups in the substituents of the ring-fused indol-1-yl group. Wherein heteroaryl is a heteroaryl bonded via a carbon atom. Substituents for aryl and heteroaryl groups may include alkyl, alkenyl, aryl, heteroaryl, alkoxy, alkylthio, aryloxy, arylthio, heteroaryloxy, heteroarylthio, cyano and combinations thereof. Preferred groups of substituents may include alkyl, aryl, alkoxy, alkylthio, cyano. In one aspect of the invention, aryl and heteroaryl groups are substituted or unsubstituted with alkyl groups. For example, unsubstituted phenyl groups and phenyl groups substituted with alkyl groups can be exemplified.
Specific examples of the substituted or unsubstituted aryl group and the carbon atom-bonded substituted or unsubstituted heteroaryl group that can be used for Ar of the general formula (1) are shown below. In the following structural formula, t-Bu represents tert-butyl, and x represents a bonding position.
[ chemical formula 13-1]
[ chemical formula 13-2]
[ chemical formula 13-3]
Compounds in which all hydrogen atoms of Ar1 to Ar81 are substituted with deuterium atoms are disclosed as Ar1d to Ar81d.
The compound represented by the general formula (1) preferably does not contain a metal atom, and may be a compound composed of only an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom, and a sulfur atom. In a preferred aspect of the present invention, the compound represented by the general formula (1) is composed of only an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom and an oxygen atom. The compound represented by the general formula (1) may be a compound composed of only atoms selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom and a sulfur atom. The compound represented by the general formula (1) may be a compound composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms and nitrogen atoms. The compound represented by the general formula (1) may be a compound composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, and nitrogen atoms. Further, the compound represented by the general formula (1) may be a compound containing deuterium atoms and not containing hydrogen atoms. For example, the compound represented by the general formula (1) may be a compound composed of only atoms selected from the group consisting of carbon atoms, deuterium atoms, nitrogen atoms, oxygen atoms, and sulfur atoms.
In one embodiment of the present invention, the compound represented by the general formula (1) has a symmetrical structure. For example, the structure may have a line symmetrical structure or a rotation symmetrical structure.
Specific examples of the compounds represented by the general formula (1) are shown in tables 1 to 6 below. In tables 1 to 6, D was determined by determining for each compound 1 、D 2 、D 3 、Ar、Ar 1 And Ar is a group 2 To show the structure of the compounds. For example, in the case of compounds 1 to 125 in Table 1, ar is fixed to Ar1, and D 1 And D 2 The same structure. And, D is 1 And D 2 The compounds D7 to D20, D22 to D30, D36 to D48, D50 to D60, D67 to D73 and D79 to D149 are shown as compounds 1 to 125 in this order. In the case of compounds 856 to 2451, D is 1 And D 2 As compounds 856 to 931, D21 and Ar is Ar2 to Ar21, ar25 to Ar52, ar54 to Ar81 in this order, D 1 And D 2 Compound numbers are assigned as compounds 931 to 1006 in which Ar is Ar2 to Ar21, ar25 to Ar52, and Ar54 to Ar81 in this order, and finally D is given 1 And D 2 As compounds 2376 to 2451, D152 and Ar2 to Ar21, ar25 to Ar52, and Ar54 to Ar81 in this order. In tables 1 to 6, the structures of the compounds 1 to 25053 are individually determined, and are specifically disclosed in the present specification. And, it is disclosed that the catalyst will exist in the chemical reaction The compounds 1d to 25053d are compounds in which all hydrogen atoms in the molecules of the compounds 1 to 25053 are replaced with deuterium atoms. In addition, in the case where rotamers are present in the following compounds, a mixture of rotamers and each of the separated rotamers are disclosed in the present specification. In tables 1 to 6 below, ar82 represents the same structure as Ar1d (a structure in which all hydrogen atoms of Ar1 are replaced with deuterium atoms).
The molecular weight of the compound represented by the general formula (1) is preferably 1500 or less, more preferably 1200 or less, even more preferably 1000 or less, and even more preferably 900 or less, when the compound represented by the general formula (1) is used in an attempt to form a film of an organic layer containing the compound represented by the general formula (1) by vapor deposition. The lower limit of the molecular weight is the molecular weight of the smallest compound represented by the general formula (1).
The compound represented by the general formula (1) can be formed into a film by a coating method regardless of the molecular weight. When the coating method is used, a film can be formed even with a compound having a relatively large molecular weight. The compound represented by the general formula (1) has an advantage that it is easily dissolved in an organic solvent in a cyanobenzene compound. Therefore, the compound represented by the general formula (1) can be easily applied to a coating method, and can be easily purified to improve the purity.
The compound represented by the general formula (1) has a short delayed fluorescence lifetime (τ2), and therefore can improve the luminous efficiency of the element or suppress roll-off when used in an organic light-emitting element. Therefore, an organic light-emitting element having good efficiency and excellent stability (durability) can be provided.
It is also possible to consider that the present invention is applied to use a compound containing a plurality of structures represented by the general formula (1) in the molecule as a light-emitting material.
For example, a polymer obtained by pre-existing a polymerizable group in a structure represented by the general formula (1) and polymerizing the polymerizable group can be considered as a light-emitting material. Specifically, R prepared in the general formula (1) can be considered 1 ～R 4 The monomer having a polymerizable functional group in any one of them is polymerized alone or copolymerized with other monomers to obtain a polymer having a repeating unit, and the polymer is used as a light-emitting material. Alternatively, it is also conceivable to obtain a dimer or trimer by coupling compounds having a structure represented by the general formula (1) to each other, and use these as a light-emitting material.
Examples of the polymer having a repeating unit including the structure represented by the general formula (1) may include polymers including structures represented by the following general formula (2) or (3).
[ chemical formula 14]
In the general formula (2) or (3), Q represents a group comprising a structure represented by the general formula (1), L 1 L and L 2 Representing a linking group. The number of carbon atoms of the linking group is preferably 0 to 20, more preferably 1 to 15, and still more preferably 2 to 10. The linking group preferably has the formula-X 11 -L 11 -a linking group of the represented structure. Here, X is 11 Represents an oxygen atom or a sulfur atom, preferably an oxygen atom. L (L) 11 Represents a linking group, preferably a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, more preferably a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted phenylene group.
In the general formula (2) or (3), R 101 、R 102 、R 103 R is R 104 Each independently represents a substituent. Preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, or a chlorine atom, and still more preferably a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms.
L 1 L and L 2 The linking group represented by formula (1) is capable of bonding to R constituting Q 1 ～R 4 Any one of them. More than 2 linking groups may be linked to 1Q to form a cross-linked structure or a network structure.
Specific examples of the structure of the repeating unit may include structures represented by the following formulas (4) to (7).
[ chemical formula 15]
The polymer having the repeating unit containing these formulae (4) to (7) can be synthesized by: pre-feedingR of the general formula (1) 1 ～R 4 Any one of the compounds is introduced with a hydroxyl group as a linking group, and the compound is reacted with a polymerizable group to polymerize the polymerizable group.
[ chemical formula 16]
The polymer having a structure represented by the general formula (1) in the molecule may be a polymer composed of only repeating units having a structure represented by the general formula (1), or may be a polymer having repeating units having other structures. The repeating unit having the structure represented by the general formula (1) contained in the polymer may be one kind or 2 or more kinds. The repeating unit not having the structure represented by the general formula (1) may include a repeating unit derived from a monomer commonly used for copolymerization. For example, a repeating unit derived from a monomer having an ethylenic unsaturated bond such as ethylene or styrene may be mentioned.
In one embodiment, the compound represented by the general formula (1) is a light-emitting material.
In one embodiment, the compound represented by the general formula (1) is a compound capable of emitting delayed fluorescence.
In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the UV region, blue, green, yellow, orange, red region (e.g., about 420nm to about 500nm, about 500nm to about 600nm, or about 600nm to about 700 nm) or near infrared region in the visible spectrum when excited by heat or an electronic device.
In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the red or orange region (e.g., about 620nm to about 780nm, about 650 nm) in the visible spectrum when excited by heat or an electronic device.
In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the orange or yellow region (e.g., about 570nm to about 620nm, about 590nm, about 570 nm) of the visible spectrum when excited by heat or an electronic device.
In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the green region (e.g., about 490nm to about 575nm, about 510 nm) of the visible spectrum when excited by heat or an electronic device.
In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the blue region (e.g., about 400nm to about 490nm, about 475 nm) of the visible spectrum when excited by heat or an electronic device.
In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the ultraviolet spectrum region (for example, 280 to 400 nm) when excited by heat or an electronic device.
In one embodiment of the present invention, the compound represented by the general formula (1) is capable of emitting light in the infrared spectrum region (for example, 780nm to 2 μm) when excited by heat or an electronic device.
The electron characteristics of a chemical substance library of small molecules can be calculated using quantum chemical calculations based on the well-known ab-rule. For example, as a basis group, the Hartree-Fock equation (TD-DFT/B3 LYP/6-31G) was analyzed using a time-dependent density functional theory using a set of functions known as a 3-parameter, lee-Yang-Parr mixed functional of 6-31G and beck (beck), and molecular fragments (portions) having HOMO above a specific threshold and LUMO below a specific threshold could be screened.
Thus, for example, the donor moiety ("D") can be selected in the presence of HOMO energy (e.g., ionization potential) of greater than-6.5 eV. Further, for example, when LUMO energy (e.g., electron affinity) of-0.5 eV or less is present, the acceptor moiety ("a") can be selected. The bridge moiety ("B") is, for example, a strong conjugated system capable of tightly confining the acceptor and donor moieties to unique steric structures, thereby preventing duplication between the pi conjugated systems of the donor and acceptor moieties.
In one embodiment, the library of compounds is screened using more than 1 of the following characteristics.
1. Luminescence around a specific wavelength
2. Triplet states above the calculated specific energy level
3.ΔE below a specific value ST Value of
4. Quantum yield above a particular value
HOMO level
Lumo level
In one embodiment, the difference between the lowest singlet excited state and the lowest triplet excited state in 77K (ΔE ST ) Less than about 0.5eV, less than about 0.4eV, less than about 0.3eV, less than about 0.2eV, or less than about 0.1eV. In one embodiment, ΔE ST Values of less than about 0.09eV, less than about 0.08eV, less than about 0.07eV, less than about 0.06eV, less than about 0.05eV, less than about 0.04eV, less than about 0.03eV, less than about 0.02eV, or less than about 0.01eV.
In one embodiment, the compound represented by formula (1) represents a quantum yield of greater than 25%, e.g., about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, or more.
[ method for synthesizing Compound represented by general formula (1) ]
The compound represented by the general formula (1) is a novel compound.
The compound represented by the general formula (1) can be synthesized by combining known reactions. For example, D can be obtained by reacting D in the presence of sodium hydride 1 -H and D 2 -H is synthesized by reaction with (hetero) aryl difluoro terephthalonitrile, which is desired to introduce a donor group D, in tetrahydrofuran 1 、D 2 Is substituted with a fluorine atom. When D is 1 And D 2 Different from each other, with D 1 -H、D 2 The reaction of H can be carried out in two stages. For specific conditions and reaction steps of the reaction, reference can be made to the examples described below.
[ Structure Using the Compound represented by the general formula (1) ]
In one embodiment, the compound is dispersed in combination with the compound represented by the general formula (1), covalently bonded to the compound, coated with the compound, and used together with 1 or more materials (e.g., small molecules, polymers, metals, metal complexes, etc.) supporting or associated with the compound to form a solid film or layer. For example, the compound represented by the general formula (1) can be combined with an electroactive material to form a thin film. In some cases, the compound represented by the general formula (1) may also be combined with a hole-transporting polymer. In some cases, the compound represented by the general formula (1) may also be combined with an electron transport polymer. In some cases, the compound represented by the general formula (1) may be combined with a hole-transporting polymer and an electron-transporting polymer. In some cases, the compound represented by the general formula (1) may also be combined with a copolymer having both a hole transporting portion and an electron transporting portion. By the above embodiment, electrons and/or holes formed in the solid thin film or layer can be made to interact with the compound represented by the general formula (1).
[ formation of film ]
In one embodiment, the thin film containing the compound of the present invention represented by the general formula (1) can be formed by a wet process. In the wet process, a solution in which a composition containing the compound of the present invention is dissolved is applied to a surface, and a thin film is formed after the solvent is removed. The wet process may include spin coating, slit coating, inkjet (spray) printing, gravure printing, offset printing, and flexography, but is not limited thereto. In the wet process, an appropriate organic solvent capable of dissolving the composition containing the compound of the present invention is selected and used. In one embodiment, a substituent (e.g., an alkyl group) that improves solubility in an organic solvent can be introduced into the compound contained in the composition.
In one embodiment, the thin film containing the compound of the present invention can be formed by a dry process. In one embodiment, a vacuum deposition method may be used as the dry process, but the present invention is not limited thereto. In the case of using the vacuum vapor deposition method, the compound constituting the thin film may be co-deposited from a single vapor deposition source, or co-deposited from a single vapor deposition source mixed with the compound. When a single vapor deposition source is used, a mixed powder of powders of the compounds may be used, a compression molded product obtained by compressing the mixed powder may be used, or a mixture obtained by heating, melting and cooling the respective compounds may be used. In one embodiment, the co-evaporation is performed under a condition that the evaporation rates (weight reduction rates) of the plurality of compounds contained in the single evaporation source are uniform or substantially uniform, whereby a thin film having a composition ratio corresponding to the composition ratio of the plurality of compounds contained in the evaporation source can be formed. If a plurality of compounds are mixed as vapor deposition sources in the same composition ratio as the formed thin film, a thin film having a desired composition ratio can be formed easily. In one embodiment, the temperature at which the weight reduction rate of each compound by co-evaporation is the same can be determined, and this temperature can be used as the temperature at the time of co-evaporation.
[ examples of use of the Compound represented by the general formula (1) ]
An organic light emitting diode:
an aspect of the present invention refers to the use of the compound represented by the general formula (1) of the present invention in the form of a luminescent material of an organic light emitting device. In one embodiment, the compound represented by the general formula (1) of the present invention can be effectively used as a light emitting material in a light emitting layer of an organic light emitting device. In one embodiment, the compound represented by the general formula (1) contains delayed fluorescence (delayed phosphor) that emits delayed fluorescence. In one embodiment, the present invention provides a delayed phosphor having a structure represented by general formula (1). In one embodiment, the present invention refers to the use of a compound represented by the general formula (1) as a delayed phosphor. In one embodiment, the compound represented by the general formula (1) of the present invention can be used as a host material and can be used together with one or more light-emitting materials, and the light-emitting materials may be fluorescent materials, phosphorescent materials, or TADF. In one embodiment, the compound represented by the general formula (1) can also be used as a hole transporting material. In one embodiment, the compound represented by the general formula (1) can be used as an electron transport material. In one embodiment, the present invention refers to a method of generating delayed fluorescence from a compound represented by the general formula (1). In one embodiment, an organic light emitting device including a compound as a light emitting material emits delayed fluorescence and exhibits high light emitting efficiency.
In one embodiment, the light-emitting layer includes a compound represented by the general formula (1), and the compound represented by the general formula (1) is oriented parallel to the substrate. In one embodiment, the substrate is a film forming surface. In one embodiment, the orientation of the compound represented by the general formula (1) on the film-forming surface affects or determines the propagation direction of light emitted by the aligned compound. In one embodiment, by arranging in the propagation direction of light emitted by the compound represented by the general formula (1), the light extraction efficiency from the light emitting layer is improved.
An aspect of the present invention relates to an organic light emitting device. In one embodiment, an organic light emitting device includes a light emitting layer. In one embodiment, the light-emitting layer contains a compound represented by the general formula (1) as a light-emitting material. In one embodiment, the organic light emitting device is an organic photoluminescent device (organic PL device). In one embodiment, the organic light emitting device is an organic electroluminescent device (organic EL device). In one embodiment, the compound represented by the general formula (1) assists light emission of other light emitting materials contained in the light emitting layer (as a so-called auxiliary dopant). In one embodiment, the compound represented by the general formula (1) contained in the light emitting layer is at its lowest excited singlet energy level, which is contained between the lowest excited singlet energy level of the host material contained in the light emitting layer and the lowest excited singlet energy level of another light emitting material contained in the light emitting layer.
In one embodiment, the organic photoluminescent device comprises at least one light emitting layer. In one embodiment, an organic electroluminescent device comprises at least an anode, a cathode, and an organic layer between the anode and the cathode. In one embodiment, the organic layer comprises at least a light emitting layer. In one embodiment, the organic layer comprises only the light emitting layer. In one embodiment, the organic layer includes one or more organic layers other than the light emitting layer. Examples of the organic layer include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. In an embodiment, the hole transport layer may be a hole injection and transport layer having a hole injection function, and the electron transport layer may be an electron injection and transport layer having an electron injection function. An example of an organic electroluminescent device is shown in fig. 1.
Light emitting layer:
in one embodiment, the light emitting layer is a layer in which holes and electrons injected from the anode and cathode, respectively, are recombined to form excitons. In one embodiment, the layer emits light.
In one embodiment, only a light-emitting material is used as the light-emitting layer. In one embodiment, the light emitting layer comprises a light emitting material and a host material. In one embodiment, the luminescent material is one or more compounds of formula (1). In one embodiment, in order for the organic electroluminescent device and the organic photoluminescent device to exhibit high luminous efficiency, singlet excitons and triplet excitons generated in the light emitting material are confined in the light emitting material. In one embodiment, a host material is used in addition to the light-emitting material in the light-emitting layer. In one embodiment, the host material is an organic compound. In one embodiment, the organic compound has an excited singlet state energy and an excited triplet state energy, at least one of which is higher than those of the light emitting material of the present invention. In one embodiment, singlet excitons and triplet excitons generated in the light emitting material of the present invention are bound in the molecules of the light emitting material of the present invention. In one embodiment, singlet and triplet excitons are sufficiently constrained to promote luminous efficiency. In an embodiment, singlet excitons and triplet excitons are not sufficiently constrained, but higher luminous efficiency is still obtained, i.e., host materials capable of achieving higher luminous efficiency may be used in the present invention without particular limitation. In one embodiment, luminescence occurs in the luminescent material in the luminescent layer of the device of the invention. In an embodiment, the emitted light includes both fluorescence and delayed fluorescence. In one embodiment, the emitted light comprises light emitted from a host material. In one embodiment, the emitted light consists of light emitted from the host material. In one embodiment, the emitted light includes light emitted from the compound represented by the general formula (1) and light emitted from the host material. In one embodiment, TADF molecules and host materials are used. In one embodiment, TADF is an auxiliary dopant.
When the compound represented by the general formula (1) is used as an auxiliary dopant, various compounds can be used as a light-emitting material (preferably, a fluorescent material). As a luminescent material of this kind, it is possible to use a material selected from anthracene (anthracene) derivatives, tetracenE (TetracenE) derivatives, tetracenE (napthcene) derivatives, pyrene derivatives, perylene derivatives,Derivatives, rubrene derivatives, coumarin derivatives, pyran derivatives, stilbene derivatives, fluorene derivatives, anthracene (anthracenyl) derivatives, pyrrole methylene derivatives, terphenyl (terphenyl) derivatives, fluoranthene (Fluoranthene) derivatives, amine derivatives, quinacridone derivatives, oxadiazole derivatives, malononitrile derivatives, carbazole derivatives, julolidine (Julolidine) derivatives, thiazole derivatives, derivatives with metals (Al, zn), and the like. These exemplary backbones may or may not have substituents. Further, these example skeletons may be combined with each other.
The following exemplifies a light emitting material that can be used in combination with an auxiliary dopant represented by the general formula (1).
[ chemical formula 17-1]
[ chemical formula 17-2]
[ chemical formula 17-3]
In addition, the compounds described in paragraphs 0220 to 0239 of WO2015/022974 may be particularly preferably used as the light-emitting material used together with the auxiliary dopant represented by the general formula (1).
In one embodiment, when a host material is used, the amount of the compound of the present invention in the form of a light-emitting material contained in the light-emitting layer is 0.1% by weight or more. In one embodiment, when a host material is used, the amount of the compound of the present invention in the form of a light-emitting material contained in the light-emitting layer is 1% by weight or more. In one embodiment, when a host material is used, the amount of the compound of the present invention in the form of a light-emitting material contained in the light-emitting layer is 50% by weight or less. In one embodiment, when a host material is used, the amount of the compound of the present invention in the form of a light-emitting material contained in the light-emitting layer is 20% by weight or less. In one embodiment, when a host material is used, the amount of the compound of the present invention in the form of a light-emitting material contained in the light-emitting layer is 10% by weight or less.
In one embodiment, the host material in the light-emitting layer is an organic compound that includes a hole transport function and an electron transport function. In one embodiment, the host material in the light emitting layer is an organic compound that prevents an increase in the wavelength of the emitted light. In one embodiment, the host material in the light-emitting layer is an organic compound having a high glass transition temperature.
In some embodiments, the host material is selected from the group consisting of:
[ chemical formula 18-1]
[ chemical formula 18-2]
In one embodiment, the light emitting layer comprises 2More than one structurally different TADF molecule. For example, a light-emitting layer including 3 materials having high excited singlet energy levels in the order of host material, 1 st TADF molecule, and 2 nd TADF molecule can be provided. At this time, the difference ΔE between the lowest excited singlet energy level of the 1 st TADF molecule and the 2 nd TADF molecule and the lowest excited triplet energy level of 77K ST All are preferably 0.3eV or less, more preferably 0.25eV or less, more preferably 0.2eV or less, more preferably 0.15eV or less, more preferably 0.1eV or less, more preferably 0.07eV or less, still more preferably 0.05eV or less, still more preferably 0.03eV or less, and particularly preferably 0.01eV or less. The content of 1 st TADF molecules in the light-emitting layer is preferably more than the content of 2 nd TADF molecules. And, the content of the host material in the light emitting layer is preferably more than the content of the 2 nd TADF molecule. The content of the 1 st TADF molecule in the light-emitting layer may be more than that of the host material, or may be less than that of the host material, or may be the same. In one embodiment, the composition in the light emitting layer may be set as follows: the host material is 10 to 70 wt%, the 1 st TADF molecule is 10 to 80 wt% and the 2 nd TADF molecule is 0.1 to 30 wt%. In one embodiment, the composition in the light emitting layer may be set as follows: the host material is 20 to 45 wt%, the 1 st TADF molecule is 50 to 75 wt%, and the 2 nd TADF molecule is 5 to 20 wt%. In one embodiment, the light emission quantum yield Φpl1 (a) caused by light excitation of the co-deposited film of the 1 st TADF molecule and the host material (the content of the 1 st TADF molecule in the co-deposited film=a wt%) and the light emission quantum yield Φpl2 (a) caused by light excitation of the co-deposited film of the 2 nd TADF molecule and the host material (the content of the 2 nd TADF molecule in the co-deposited film=a wt%) satisfy the relational expression of Φpl1 (a) > Φpl2 (a). In one embodiment, the light emission quantum yield Φpl2 (B) caused by light excitation of the co-deposited film of the 2 nd TADF molecule and the host material (the content of the 2 nd TADF molecule in the co-deposited film=b wt%) and the light emission quantum yield Φpl2 (100) caused by light excitation of the individual film of the 2 nd TADF molecule satisfy the relational expression of Φpl2 (B) > Φpl2 (100). In one embodiment, the light emitting layer can comprise 3 structurally different TADF molecules. Compounds of the invention Any one of a plurality of TADF compounds contained in the light-emitting layer may be used.
In an embodiment, the light emitting layer can be composed of a material selected from the group consisting of a host material, an auxiliary dopant, and a light emitting material. In one embodiment, the light emitting layer does not contain a metal element. In an embodiment, the light emitting layer can be composed of a material composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. Alternatively, the light-emitting layer may be formed of a material composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, deuterium atoms, nitrogen atoms, and oxygen atoms. Alternatively, the light-emitting layer may be formed of a material composed of only atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms, and oxygen atoms.
When the light emitting layer contains a TADF material other than the compound of the present invention, the TADF material may be a known delayed fluorescent material. Preferred delayed fluorescent materials may include 0008 to 0048 and 0095 to 0133 of WO2013/154064, 0007 to 0047 and 0073 to 0085 of WO 2013/01954, 0007 to 0033 and 0059 to 0066 of WO 2013/01955, 0008 to 0071 and 0118 to 0133 of WO2013/081088, 0009 to 0046 and 0093 to 0134 of Japanese patent application publication No. 2013-256490, 0008 to 0020 and 0038 to 0040 of Japanese patent application publication No. 2013-116975, 0007 to 0032 and 0079 to 0084 of WO2013/133359, 0008 to 0034 and 0101 to 0121 of WO 2013/437, and 0101 to 0121 of WO 2013/437; the compounds contained in the general formulae described in paragraphs 0007 to 0041 and 0060 to 0069 of Japanese patent application laid-open No. 2014-9252, paragraphs 0008 to 0048 and 0067 to 0076 of Japanese patent application laid-open No. 2017-119663, paragraphs 0013 to 0025 of Japanese patent application laid-open No. 2017-119664, paragraphs 0012 to 0025 of Japanese patent application laid-open No. 2017-222623, paragraphs 0010 to 0050 of Japanese patent application laid-open No. 2017-226838, paragraphs 0012 to 0043 of Japanese patent application laid-open No. 2018-100411, and paragraphs 0016 to 0044 of WO2018/047853, are particularly exemplified compounds and can emit delayed fluorescence. And, in addition, the processing unit, the light-emitting materials of the publication Nos. 2013-253121, 2013/133359, WO2014/034535, WO2014/115743, WO2014/122895, WO2014/126200, WO2014/136758, WO2014/133121, WO2014/136860, WO2014/196585, WO2014/189122, WO 2014/1681101, WO2015/008580, WO2014/203840, WO2015/002213, WO2015/016200, WO2015/019725, WO 201470/072725, WO2015/108049, WO2015/080182, WO2015/072537, WO 2015/136240, WO2014/196585, WO2014/189122, WO2014/168101, WO 2012012015/203180, WO 2012012015/203714, WO 2015/12913720, WO 2015/12914, WO 13720, WO 2015/129137202, WO 13720, and the light-emitting materials can be preferably used. In addition, the above-mentioned publications described in this paragraph are incorporated herein by reference as part of this document.
The components of the organic electroluminescent element and the layers other than the light-emitting layer will be described below.
A substrate:
in some embodiments, the organic electroluminescent element of the present invention is supported by a substrate, wherein the substrate is not particularly limited and may be any of those substrates that have been commonly used in organic electroluminescent elements, such as those formed of glass, transparent plastic, quartz, and silicon.
Anode:
in some embodiments, the anode of the organic electroluminescent device is made of a metal, an alloy, a conductive compound, or a combination thereof. In some embodiments, the metal, alloy, or conductive compound has a large work function (above 4 eV). In some embodiments, the metal is Au. In some embodiments, the conductive transparent material is selected from CuI, indium Tin Oxide (ITO), snO 2 And ZnO. In some embodiments, amorphous materials capable of forming transparent conductive films such as IDIXO (In 2 O 3 -ZnO) and the like. In some implementationsIn an embodiment, the anode is a thin film. In some embodiments, the thin film is made by evaporation or sputtering. In some embodiments, the film is patterned by photolithography. In some embodiments, when a pattern may not require high precision (e.g., above about 100 μm), the pattern may be formed with a mask having a desired shape upon evaporation or sputtering of the electrode material. In some embodiments, when a material (e.g., an organic conductive compound) can be coated, wet film forming methods, such as printing and coating methods, are used. In some embodiments, the transmittance of the anode is greater than 10% and the sheet resistance of the anode is less than hundreds of ohms per square when the emitted light passes through the anode. In some embodiments, the anode has a thickness of 10 to 1,000nm. In some embodiments, the anode has a thickness of 10 to 200nm. In some embodiments, the thickness of the anode varies depending on the material used.
And (3) cathode:
in some embodiments, the cathode is fabricated from a metal (4 eV or less) with a small work function of the electrode material (referred to as an electron injecting metal), an alloy, a conductive compound, or a combination thereof. In some embodiments, the electrode material is selected from sodium, sodium-potassium alloy, magnesium, lithium, magnesium-copper mixture, magnesium-silver mixture, magnesium-aluminum mixture, magnesium-indium mixture, aluminum-aluminum oxide (Al 2 O 3 ) The mixture, indium, lithium-aluminum mixture and rare earth metal are selected. In some embodiments, a mixture of an electron injection metal and a 2 nd metal is used, the 2 nd metal being a stable metal having a work function greater than the electron injection metal. In some embodiments, the mixture is selected from the group consisting of magnesium-silver mixtures, magnesium-aluminum mixtures, magnesium-indium mixtures, aluminum-aluminum oxide (Al 2 O 3 ) The mixture, lithium-aluminum mixture and aluminum are selected. In some embodiments, the mixture increases electron injection characteristics and durability against oxidation. In some embodiments, the cathode is fabricated by forming the electrode material into a thin film by evaporation or sputtering. In some embodiments, the cathode has a sheet resistance of less than several hundred ohms per square. In some embodiments, the The thickness of the cathode is in the range of 10nm to 5 μm. In some embodiments, the cathode has a thickness in the range of 50 to 200 nm. In some embodiments, any one of the anode and the cathode of the organic electroluminescent element is transparent or translucent in order to transmit the emitted light. In some embodiments, the transparent or translucent electroluminescent element enhances the brightness of the emitted light.
In some embodiments, the cathode is formed with a conductive transparent material as described for the anode to form a transparent or translucent cathode. In some embodiments, the element comprises an anode and a cathode that are both transparent or translucent.
And (2) an injection layer:
the injection layer is a layer between the electrode and the organic layer. In some embodiments, the injection layer reduces a driving voltage and enhances light emission luminance. In some embodiments, the injection layer includes a hole injection layer and an electron injection layer. The injection layer may be disposed between the anode and the light emitting layer or the hole transporting layer, and between the cathode and the light emitting layer or the electron transporting layer. In some embodiments, an injection layer is present. In some embodiments, no implanted layer is present.
Examples of preferred compounds that can be used as the hole injecting material are included below.
[ chemical formula 19]
Next, a preferable compound which can be used as an electron injection material is exemplified.
[ chemical formula 20]
Barrier layer:
the blocking layer is a layer capable of suppressing diffusion of charges (electrons or holes) and/or excitons in the light emitting layer to the outside of the light emitting layer. In some embodiments, an electron blocking layer is between the light emitting layer and the hole transporting layer, and inhibits electrons from passing through the light emitting layer toward the hole transporting layer. In some embodiments, a hole blocking layer is between the light emitting layer and the electron transport layer and inhibits holes from passing through the light emitting layer toward the electron transport layer. In some embodiments, the blocking layer inhibits excitons from diffusing outside the light emitting layer. In some embodiments, the electron blocking layer and the hole blocking layer constitute an exciton blocking layer. The term "electron blocking layer" or "exciton blocking layer" as used herein includes a layer having the function of both an electron blocking layer and an exciton blocking layer.
Hole blocking layer:
the hole blocking layer functions as an electron transport layer. In some embodiments, the hole blocking layer inhibits holes from reaching the electron transport layer while transporting electrons. In some embodiments, the hole blocking layer enhances the probability of recombination of electrons and holes in the light emitting layer. The material for the hole blocking layer may be the same material as described for the electron transport layer.
Examples of preferred compounds that can be used for the hole blocking layer are included below.
[ chemical formula 21]
Electron blocking layer:
holes are transported by the electron blocking layer. In some embodiments, the electron blocking layer inhibits electrons from reaching the hole transport layer while transporting holes. In some embodiments, the electron blocking layer enhances the probability of recombination of electrons and holes in the light emitting layer. The material for the electron blocking layer may be the same material as described for the hole transport layer.
Specific examples of preferred compounds that can be used as the electron blocking material are included below.
[ chemical formula 22]
Exciton blocking layer:
the exciton blocking layer inhibits diffusion of excitons generated via recombination of holes and electrons in the light emitting layer to the electron transport layer. In some embodiments, the exciton blocking layer enables effective confinement (confinement) of excitons in the light emitting layer. In some embodiments, the luminous efficiency of the device is enhanced. In some embodiments, the exciton blocking layer is adjacent to the light emitting layer on either of the anode side and the cathode side and on both sides. In some embodiments, when the exciton blocking layer is on the anode side, the layer may be between and adjacent to the hole transport layer and the light emitting layer. In some embodiments, when the exciton blocking layer is on the cathode side, the layer may be between and adjacent to the light emitting layer and the cathode. In some embodiments, a hole injection layer, an electron blocking layer, or the same layer is 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, an electron blocking layer, a hole blocking layer, or the same layer is between the cathode and an exciton blocking layer adjacent to the light emitting layer on the cathode side. In some embodiments, the exciton blocking layer comprises an excited singlet state energy and an excited triplet state energy, at least one of which is higher than the excited singlet state energy and the excited triplet state energy, respectively, of the light emitting material.
Hole transport layer:
the hole transport layer comprises a hole transport material. In some embodiments, the hole transport layer is a single layer. In some embodiments, the hole transport layer has multiple layers.
In some embodiments, the hole transport material has one of an injection or transport property of holes and a blocking property of electrons. In some embodiments, the hole transport material is an organic material. In some embodiments, the hole transport material is an inorganic material. Examples of known hole transport materials that may 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, dihydropyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene (stillene) derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers (especially thiophene oligomers), or combinations thereof. In some embodiments, the hole transporting material is selected from porphyrin compounds, aromatic tertiary amines, 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 transport material are included below.
[ chemical formula 23]
Electron transport layer:
the electron transport layer comprises an electron transport material. In some embodiments, the electron transport layer is a single layer. In some embodiments, the electron transport layer has multiple layers.
In some embodiments, the electron transport material need only have a function of transporting electrons, which are injected from the cathode into the light emitting layer. In some embodiments, the electron transport material also functions as a hole blocking material. Examples of electron transport layers that may be used in the present invention include, but are not limited to, nitro-substituted fluorene derivatives, dibenzoquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylmethane derivatives, anthraquinone dimethanes, anthrone derivatives, oxadiazole derivatives, oxazole derivatives, oxazine derivatives, or combinations thereof or polymers thereof. In some embodiments, the electron transport material is a thiadiazole derivative or a quinoxaline derivative. In some embodiments, the electron transport material is a polymeric material. Specific examples of preferred compounds that can be used as the electron transport material are included below.
[ chemical formula 24]
Examples of the compound include compounds which are preferable as materials that can be added to each organic layer. For example, addition as a stabilizing material or the like can be considered.
[ chemical formula 25]
Preferred materials that can be used for the organic electroluminescent element are specifically exemplified, but the materials that can be used in the present invention are not limitedly explained by the exemplified compounds below. Further, even a compound exemplified as a material having a specific function can be used as a material having another function.
The device comprises:
in some embodiments, the light emitting layer is incorporated into a device. For example, devices include, but are not limited to, OLED bulbs, OLED lamps, television screens, computer monitors, mobile phones, and tablet computers.
In some embodiments, an electronic device includes an OLED having an anode, a cathode, and at least one organic layer including a light emitting layer between the anode and the cathode.
In some embodiments, the compositions described herein may be incorporated into a variety of photosensitive or photoactivated devices, such as OLED or photovoltaic devices. In some embodiments, the compositions may be suitable for facilitating charge transfer or energy transfer within a device and/or for use as hole transport materials. The devices include, for example, organic Light Emitting Diodes (OLEDs), organic Integrated Circuits (OIC), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic photodetectors, organic photoreceptors, organic field-quench devices (O-FQDs), light emitting electrochemical cells (LECs), or organic laser diodes (O-lasers).
Bulb or lamp:
in some embodiments, an electronic device comprises an OLED comprising an anode, a cathode, and at least one organic layer comprising a light emitting layer between the anode and the cathode.
In some embodiments, the device comprises OLEDs of different colors. In some embodiments, the device comprises an array comprising OLED combinations. In some embodiments, the combination of OLEDs is a combination of 3 colors (e.g., RGB). In some embodiments, the combination of OLEDs is a combination of colors that are not red, green, or blue (e.g., orange and yellow-green). In some embodiments, the combination of OLEDs is a combination of 2, 4, or more than 4 colors.
In some embodiments, the device is an OLED lamp, the OLED lamp having:
a circuit board having a 1 st surface having a mounting surface and a 2 nd surface opposite thereto, and defining at least one opening;
at least one OLED disposed on the mounting surface and having a structure in which the at least one OLED includes an anode, a cathode, and at least one organic layer including a light emitting layer between the anode and the cathode and emits light;
a housing for a circuit substrate; and
At least one connector is disposed at an end of the housing, and the housing and the connector define a package adapted to be mounted to a lighting device.
In some embodiments, an OLED lamp includes a plurality of OLEDs mounted on a circuit board such that light is emitted in multiple directions. In some embodiments, a portion of the light emitted in the 1 st direction is deflected to be emitted in the 2 nd direction. In some embodiments, the reflector is used to deflect light emitted in the 1 st direction.
A display or screen:
in some embodiments, the light emitting layer of the present invention may be used in a screen or display. In some embodiments, methods including, but not limited to, vacuum evaporation, deposition, evaporation, or Chemical Vapor Deposition (CVD) are used to deposit the compounds of the present invention onto a substrate. In some embodiments, the substrate is a photo negative (photo plate) structure suitable for double sided etching, providing unique aspect ratio pixels. The screen (which may also be referred to as a mask) is used in a method of manufacturing an OLED display. The corresponding artwork pattern design promotes extremely steep and narrow tie-bars (tie-bars) between pixels in the vertical direction and larger sweep bevel openings in the horizontal direction. Thereby allowing for the pixel tight patterning required for high definition displays while optimizing chemical vapor deposition onto the TFT backplane.
The internal patterning of the pixels allows the construction of 3-dimensional pixel openings with aspect ratio variations in the horizontal and vertical directions. Furthermore, the use of imaged "stripes" or halftone circles within the pixel regions inhibits etching in certain areas until such time as these certain patterns are undercut and leave the substrate. At this time, all pixel regions are processed at the same etching rate, but the depth varies depending on the halftone pattern. Changing the size and spacing of the halftone patterns allows etching to be suppressed at different rates within the pixel, allowing localized deeper etching required to form steep vertical bevel angles.
A preferred material for the vapor deposition mask is constant-volume steel (innor). Constant-gauge steel is a metal alloy that is cold rolled into long sheets in a steelworks. Constant-gauge steel cannot be electrodeposited onto a spinning mandrel as a nickel mask. A suitable and low cost method for forming the opening region in the evaporation mask is a wet chemical etching-based method.
In some embodiments, the screen or display pattern is a matrix of pixels on a substrate. In some embodiments, the screen or display pattern is fabricated using photolithography (e.g., photolithography) and e-beam lithography. In some embodiments, the screen or display pattern is fabricated using wet chemical etching. In further embodiments, the screen or display pattern is fabricated using plasma etching.
The manufacturing method of the device comprises the following steps:
OLED displays are typically manufactured by forming a larger motherboard and then cutting the motherboard into unit panels. In general, each cell board on the motherboard is formed by: a Thin Film Transistor (TFT) including an active layer and source/drain electrodes is formed on a base substrate, a planarization film is coated on the TFT, and a pixel electrode, a light emitting layer, a counter electrode, and an encapsulation layer are sequentially formed and cut from the mother substrate.
In another aspect of the present invention, there is provided a method of manufacturing an Organic Light Emitting Diode (OLED) display, the method including:
forming a barrier layer on a base substrate of a motherboard;
forming a plurality of display units from a unit of a unit panel on the barrier layer;
forming an encapsulation layer on each of the display units of the unit panels; and
And a step of coating an organic film on the interface portion between the unit plates.
In some embodiments, the barrier layer is an inorganic film formed of, for example, siNx, and an edge portion of the barrier layer is covered with an organic film formed of polyimide or acryl. In some embodiments, the organic film aids in gently cutting the master into unit panels.
In some embodiments, a Thin Film Transistor (TFT) layer has a light emitting layer, a gate electrode, and source/drain electrodes. Each of the plurality of display units may include a Thin Film Transistor (TFT), a planarization film formed on the TFT layer, and a light emitting unit formed on the planarization film, wherein the organic film coated on the interface portion is formed of the same material as that of the planarization film and is formed at the same time as the planarization film is formed. In some embodiments, the light emitting unit is connected to the TFT layer with a passivation layer, a planarization film, and an encapsulation layer therebetween, and the encapsulation layer covers and protects the light emitting unit. In some embodiments of the method of manufacture, the organic film contacts neither the display unit nor the encapsulation layer.
Each of the organic film and the planarization film may include any one of polyimide and acryl. In some embodiments, the barrier layer may be an inorganic film. In some embodiments, the base substrate may be formed of polyimide. The method may further include mounting a carrier substrate formed of a glass material onto one surface of a base substrate formed of polyimide before forming the barrier layer on the other surface, and separating the carrier substrate from the base substrate before cutting along the interface portion. In some embodiments, the OLED display is a flexible display.
In some implementations, the passivation layer is an organic film disposed on the TFT layer to cover the TFT layer. In some embodiments, the planarization film is an organic film formed on the passivation layer. In some embodiments, the planarization film is formed of polyimide or acryl, as is an organic film formed on an edge portion of the barrier layer. In some embodiments, the planarization film and the organic film are formed simultaneously when the OLED display is manufactured. In some embodiments, the organic film may be formed on an edge portion of the barrier layer such that a portion of the organic film directly contacts the base substrate and the remaining portion of the organic film contacts the barrier layer while surrounding the edge portion of the barrier layer.
In some embodiments, the light emitting layer has a pixel electrode, an opposite electrode, and an organic light emitting layer disposed between the pixel electrode and the opposite electrode. In some embodiments, the pixel electrode is connected to a source/drain electrode of the TFT layer.
In some embodiments, when a voltage is applied to the pixel electrode via the TFT layer, an appropriate voltage is formed between the pixel electrode and the opposite electrode, whereby the organic light emitting layer emits light, thereby forming an image. Hereinafter, an image forming unit having a TFT layer and a light emitting unit is referred to as a display unit.
In some embodiments, the encapsulation layer that covers the display unit and prevents external moisture from penetrating may be formed to have a thin film encapsulation structure in which organic films and inorganic films are alternately laminated. In some embodiments, the encapsulation layer has a film encapsulation structure in which a plurality of films are laminated. In some embodiments, the organic film coated on the interface portion is spaced apart from each of the plurality of display units. In some embodiments, the organic film is formed such that a portion of the organic film directly contacts the base substrate, and a remaining portion of the organic film contacts the barrier layer while surrounding an edge portion of the barrier layer.
In one embodiment, the OLED display is flexible and uses a soft base substrate formed of polyimide. In some embodiments, the base substrate is formed on a carrier substrate formed of a glass material, and then the carrier substrate is separated.
In some embodiments, a barrier layer is formed on a surface of the base substrate on a side opposite the carrier substrate. In one embodiment, the barrier layer is patterned according to the size of each cell plate. For example, a barrier layer is formed according to the size of each cell plate while a base substrate is formed over the entire surface of the motherboard, thereby forming a groove at an interface portion between the cell plate barrier layers. Each cell plate may be cut along the grooves.
In some embodiments, the method of manufacturing further comprises a step of cutting along the interface portion, wherein a groove is formed in the barrier layer, at least a portion of the organic film is formed in the groove, and the groove does not penetrate into the base substrate. In some embodiments, a TFT layer of each unit plate is formed, and a passivation layer (i.e., an inorganic film) and a planarization film (i.e., an organic film) are disposed on the TFT layer to cover the TFT layer. The grooves at the interface portion are covered with an organic film formed of, for example, polyimide or acryl, while forming a planarization film formed of, for example, polyimide or acryl. This is when cracking is prevented from occurring by allowing the organic film to absorb an impact that is generated when each unit plate is cut along the groove at the interface portion. That is, if the entire barrier layer is completely exposed without an organic film, an impact generated when each unit plate is cut along the groove at the interface portion is transferred to the barrier layer, thereby increasing the risk of cracking. However, in one embodiment, since the grooves at the interface portion between the barrier layers are covered with the organic film, and the organic film absorbs the impact that would otherwise be transferred to the barrier layers, each cell plate may be gently cut, and cracks may be prevented from occurring in the barrier layers. In one embodiment, the organic film and the planarizing film covering the recess at the interface portion are spaced apart from each other. For example, if an organic film and a planarization film are connected to each other as a single layer, the organic film and the planarization film are spaced apart from each other such that the organic film is spaced apart from the display unit because external moisture may penetrate into the display unit via the planarization film and a portion of the remaining organic film.
In some embodiments, a display unit is formed by forming a light emitting unit, and an encapsulation layer is disposed on the display unit to cover the display unit. Thereby, after the motherboard is completely manufactured, the carrier substrate supporting the base substrate is separated from the base substrate. In some implementations, when the laser beam is emitted toward the carrier substrate, the carrier substrate is separated from the base substrate due to a difference in thermal expansion coefficient between the carrier substrate and the base substrate.
In some embodiments, the motherboard is cut into unit boards. In some embodiments, the motherboard is cut along the interface portion between the unit boards by using a cutter. In some embodiments, since the grooves at the interface portion along which the motherboard is cut are covered with an organic film, the organic film absorbs impact during cutting. In some embodiments, cracking may be prevented from occurring in the barrier layer during dicing.
In some embodiments, the method reduces the defect rate of the product and stabilizes its quality.
Another aspect is an OLED display having: a barrier layer formed on the base substrate; a display unit formed on the barrier layer; an encapsulation layer formed on the display unit; and an organic film coated on an edge portion of the barrier layer.
Examples
The features of the present invention will be further specifically described with reference to examples. The materials, processing contents, processing steps, and the like described below can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limited manner by the following examples. The light emission characteristics were evaluated by using a source meter (2400 series, manufactured by Keithley corporation), a semiconductor parameter analyzer (Agilent Technologies Japan, manufactured by ltd.: E5273A), an optical power meter measuring device (Newport Corporation: 1930C), a spectrometer (USB 2000, manufactured by Ocean Optics corporation), a spectroradiometer (TOPCON CORPORATION: SR-3), and a streak camera (Hamamatsu Photonics k.k. Manufactured by C4334).
In the following examples, the compounds contained in the general formula (1) were synthesized.
Example 1
[ chemical formula 26]
2, 6-difluoro-3-phenyl-1, 4-phthalonitrile (0.32 g,2.0 mmol), 5, 8-dihydro-5-phenylindolo [3,2-c ] under nitrogen]Carbazole (0.91 g,4.3 mmol) and Cs 2 CO 3 A solution of (1.75 g,8.33 mmol) dimethylformamide (15 mL) was stirred at 150℃for 14 h. After that, the reaction was returned to room temperature, and stopped with water and methanol. The precipitate obtained was filtered and the filtrate was purified by column chromatography (toluene/hexane/CHCl 3 =8/1/1) and reprecipitation (CHCl) 3 Purification with MeOH gave an orange solid (0.86 g,0.99mmol, 49%).
1 H NMR(400MHz,CDCl 3 ,d):8.36-8.29(m,2H),8.24-8.13(m,3H),7.72-7.56(m,10H),7.42-7.38(m,10H),7.46-7.02(m,7H),6.94-6.86(m,1H)6.79-6.73(m,1H),5.94(d,J＝8.0Hz,1H),5.79(d,J＝8.0Hz,1H).
MS(ASAP):865.47[M+H] + ComputingValue C62H36N6:864.30
Example 2
[ chemical formula 27]
The synthesis was carried out by the same method as in example 1 to obtain a yield of 25%.
1 H NMR(400MHz,CDCl 3 ,d):8.98(d,J＝8.0Hz,1H),8.92(d,J＝7.6Hz,1H),8.82(t,J＝7.6Hz,2H),8.23(s,1H),7.68-7.40(m,25H),7.21-7.14(m,4H),7.10-7.01(m,3H).
MS(ASAP):865.37[M+H] + Calculated C62H36N6:864.30
Example 3
[ chemical formula 28]
The synthesis was carried out by the same method as in example 1 to obtain a yield of 50%.
1 H NMR(400MHz,CDCl 3 ,d):8.87-8.83(m,4H),7.66-7.59(m,8H),7.55-7.42(m,14H),7.33-7.28(m,2H),7.17-7.15(m,4H),7.06-6.96(m,6H).
MS(ASAP):941.46[M+H] + Calculated C68H40N6:940.33
Example 4
[ chemical formula 29]
The synthesis was carried out by the same method as in example 1 to obtain 34% yield.
1 H NMR(400MHz,CDCl 3 ,d):8.26-8.21(m,2H),8.18-8.14(m,2H),7.65-7.56(m,10H),7.34-7.22(m,8H),7.19-7.10(m,4H),6.80-6.74(m,2H),5.81(d,J＝8.0Hz,2H).
MS(ASAP):951.36[M+H] + Calculated C68H30D10N6:950.39
Example 5
[ chemical formula 30]
2, 5-difluoro-3, 6-diphenyl-1, 4-phthalonitrile (0.60 g,1.9 mmol), 2-phenyl-5H-benzofuro [3,2-c ] under nitrogen]Carbazole (1.58 g,4.7 mmol) and K 2 CO 3 A solution of (0.79 g,5.7 mmol) dimethylformamide (30 mL) was stirred at 130℃for 22 hours. After that, the reaction was returned to room temperature, and stopped with water and methanol. The obtained precipitate was filtered, and the filtrate was purified by column chromatography (toluene/hexane=2/1) and reprecipitation (toluene/hexane) to obtain an orange solid (1.07 g,1.13mmol, 60%).
1 H NMR(400MHz,CDCl 3 ,d):8.69(s,2H),8.03-8.00(m,4H),7.82-7.75(m,8H),7.57-7.35(m,12H),7.59-7.21(m,6H),7.11-7.04(m,6H).
MS(ASAP):943.58[M+H] + .Calcd for.C68H38N4O2:942.30
Example 6
[ chemical formula 31]
The synthesis was carried out by the same method as in example 5 to obtain 80% yield.
1 H NMR(400MHz,CDCl 3 ,d):8.67(s,2H),8.02-7.99(m,4H),7.81-7.74(m,8H),7.55-7.34(m,12H),7.26-7.20(m,2H).
MS(ASAP):953.58[M+H] + Calculated C68H28D10N4O2:952.36
Example 7
[ chemical formula 32]
The synthesis was carried out by the same method as in example 5 to obtain a yield of 82%.
1 H NMR(400MHz,CDCl 3 ,d):8.67(s,2H),8.02-7.99(m,4H),7.77-7.74(m,4H),7.51-7.33(m,6H),7.26-7.21(m,2H).
MS(ASAP):963.63[M+H] + Calculated C68H18D20N4O2:962.43
Example 8
[ chemical formula 33]
The synthesis was carried out by the same method as in example 5 to obtain a yield of 48%.
1 H NMR(400MHz,CDCl 3 ,d):8.44(d,J＝8.0Hz,2H),8.32(d,J＝8.4Hz,2H),8.26-8.21(m,4H),8.09-7.95(m,6H),7.90-7.86(m,4H),7.77-7.75(m,2H),7.55-7.45(m,4H),7.21-7.12(m,4H),7.02-6.94(m,6H).
MS(ASAP):891.41[M+H] + Calculated C64H34N4O2:890.27
Example 9
[ chemical formula 34]
The synthesis was carried out by the same method as in example 5 to obtain a yield of 71%.
MS(ASAP):890.2[M] + Calculated C64H34N4O2:890.2
Example 10
[ chemical formula 35]
The synthesis was carried out by the same method as in example 5 to obtain a yield of 45%.
1 H NMR(400MHz,CDCl 3 ,d):9.85(d,J＝8,8Hz,2H),8.36(dd,J＝8.4,2.4Hz,2H),8.29(d,J＝7,2Hz,2H),8.26-8.16(m,6H),8.09-8.02(m,4H),7.93(t,J＝6,8Hz,2H),7.65(t,J＝7,2Hz,2H),7.59(t,J＝6,8Hz,2H),7.52(t,J＝7,2Hz,2H),7.38(d,J＝8,4Hz,4H),7.11-7.03(m,6H),
MS(ASAP):891.33[M+H] + Calculated C64H35N4O2:891.28
The compounds of examples 1 to 10 were purified by sublimation and then used for the formation of thin films and the production of devices.
(production and evaluation of film)
Vacuum evaporation method is adopted, vacuum degree is less than 1×10 -3 The compound of example 1 and mCBP were vapor-deposited on a quartz substrate from different vapor deposition sources under Pa conditions, and a film having a concentration of 20 wt% of the compound of example 1 was formed at a thickness of 100nm, and this was defined as a doped film. In addition, a doped thin film was formed in the same manner using each of the compounds of examples 2 to 10 instead of example 1. Further, a doped thin film was formed in the same manner using the compound of comparative example 1 having the following structure instead of example 1.
When each of the obtained films was irradiated with excitation light of 300nm, photoluminescence was observed in each film, and thus the maximum luminescence wavelength was measured. And, the lifetime (τ) of the delayed fluorescence is obtained from the transient decay curve of the luminescence 2 ). The results are shown in Table 8. The results of measuring the energy of HOMO and the energy of LUMO of each compound are also shown in table 8.
From the results in Table 8, it was confirmed that the delayed fluorescence lifetime (. Tau.) of each of the compounds of examples 1 to 10 was higher than that of the compound of comparative example 1 2 ) Much shorter.
TABLE 8
[ chemical formula 36]
(production of organic electroluminescent device)
Vacuum evaporation method is adopted to make the vacuum degree 1 multiplied by 10 -6 Pa each thin film was laminated on a glass substrate on which an anode composed of Indium Tin Oxide (ITO) having a film thickness of 100nm was formed. First, HATCN was formed on ITO to a thickness of 10nm, and NPD was formed thereon to a thickness of 30 nm. Next, trisPCz was further formed thereon with a thickness of 10nm, and H1 was further formed thereon with a thickness of 5 nm. Next, the compound of example 1 and H1 were co-evaporated from different evaporation sources, respectively, to form a light-emitting layer having a thickness of 30 nm. At this time, the concentration of the compound of example 1 was set to 35 wt%. SF3TRZ was formed thereon to a thickness of 10nm, SF3TRZ and Liq were co-evaporated from different evaporation sources to further form thereon a thickness of 30 nm. At this time, SF3TRZ to Liq (weight ratio) was set to 7:3. Further, liq was formed to a thickness of 2nm, and then aluminum (Al) was evaporated to a thickness of 100nm, thereby forming a cathode.
An organic electroluminescent device was produced in the same manner using the respective compounds of examples 2 to 10 instead of the compound of example 1.
The lifetime (τ2) of delayed fluorescence of the organic electroluminescent element is short.
[ chemical formula 37]
Symbol description
1-substrate, 2-anode, 3-hole injection layer, 4-hole transport layer, 5-luminescent layer, 6-electron transport layer, 7-cathode.
Claims (19)
1. A compound represented by the following general formula (1),
[ chemical formula 1]
General formula 1
In the general formula (1), the amino acid sequence of the compound,
R 1 ～R 4 wherein at least 1 is a ring-fused indol-1-yl group which forms a fused ring having a ring number of 4 or more by being fused with the ring of indole, the fused ring may be substituted,
R 1 ～R 4 each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group bonded via a carbon atom,
the remainder R 1 ～R 4 Represents a hydrogen atom or a deuterium atom.
2. The compound according to claim 1, wherein,
R 1 ～R 4 each independently a donor group, at least 1 of which is indol-1-yl fused to the ring,
R 1 ～R 4 is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group bonded via a carbon atom,
The remainder R 1 ～R 4 Is a hydrogen atom or a deuterium atom.
3. The compound according to claim 1, wherein,
R 1 ～R 4 each independently a donor group, at least 1 of which is indol-1-yl fused to the ring,
R 1 ～R 4 is a substituted or unsubstituted aryl or a carbon atom bonded substituted or unsubstituted heteroaryl.
4. The compound according to claim 1, wherein,
R 1 ～R 4 each independently a donor group, at least 1 of which is indol-1-yl fused to the ring,
R 1 ～R 4 is a substituted or unsubstituted aryl or a carbon atom bonded substituted or unsubstituted heteroaryl.
5. The compound according to any one of claims 1 to 4, wherein,
R 1 r is R 4 Each independently is a donor group,
R 3 is a substituted or unsubstituted aryl or a carbon atom bonded substituted or unsubstituted heteroaryl.
6. The compound according to any one of claims 1 to 4, wherein,
R 2 r is R 4 Each independently is a donor group,
R 3 is a substituted or unsubstituted aryl or a carbon atom bonded substituted or unsubstituted heteroaryl.
7. The compound according to any one of claims 1 to 6, wherein,
The number of fused rings is 5 or more.
8. The compound according to claim 7, wherein,
the carbon atoms constituting the skeleton of the condensed ring having 4 or more rings are substituted with a substituted or unsubstituted aryl group.
9. The compound according to claim 7, wherein,
the fused ring having 4 or more rings has a nitrogen atom in the skeleton, and the nitrogen atom is substituted with a substituted or unsubstituted aryl group.
10. The compound according to any one of claims 1 to 9, wherein,
the ring condensed with the benzene ring constituting the indol-1-yl group is a substituted or unsubstituted furan ring, a substituted or unsubstituted thiophene ring or a substituted or unsubstituted pyrrole ring, and other rings may be further condensed on the furan ring, the thiophene ring and the pyrrole ring.
11. The compound according to any one of claims 1 to 10, wherein,
the ring-fused indol-1-yl has any one of the following fused rings,
[ chemical formula 2]
In each of the above structures, a hydrogen atom may be substituted, and a ring may be further condensed.
12. The compound according to any one of claims 1 to 10, wherein,
the ring-fused indol-1-yl has any one of the following fused ring backbones,
[ chemical formula 3]
In each of the above structures, a hydrogen atom may be substituted, and a ring may be further condensed.
13. The compound according to any one of claims 1 to 12, wherein,
the ring-fused indol-1-yl has a structure that is heterocycle-fused at the 4,5 position of the indole ring.
14. The compound according to any one of claims 1 to 13, wherein,
ar is a substituted or unsubstituted phenyl group or a substituted or unsubstituted pyridyl group.
15. The compound according to any one of claims 1 to 14, which consists of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a deuterium atom, a nitrogen atom, an oxygen atom and a sulfur atom.
16. A luminescent material consisting of the compound according to any one of claims 1 to 15.
17. A light-emitting element is characterized in that,
comprising a compound according to any one of claims 1 to 15.
18. The light-emitting element according to claim 17, wherein,
the light-emitting element has a light-emitting layer containing the compound and a host material.
19. The light-emitting element according to claim 18, wherein,
the light-emitting element has a light-emitting layer that contains the compound and a light-emitting material, and emits light mainly from the light-emitting material.
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| WO2019107932A1 (en) * | 2017-11-28 | 2019-06-06 | 주식회사 엘지화학 | Compound and organic light emitting device comprising same |
| US20220123249A1 (en) * | 2018-11-30 | 2022-04-21 | Kyulux, Inc. | Organic light emitting element |
| JPWO2021066059A1 (en) * | 2019-10-01 | 2021-04-08 | ||
| US20230106096A1 (en) * | 2020-02-05 | 2023-04-06 | Kyulux, Inc. | Compound, light-emitting material, delayed fluorescence material, and organic optical device |
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