WO2011013783A1 - 有機電界発光素子 - Google Patents
有機電界発光素子 Download PDFInfo
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- WO2011013783A1 WO2011013783A1 PCT/JP2010/062859 JP2010062859W WO2011013783A1 WO 2011013783 A1 WO2011013783 A1 WO 2011013783A1 JP 2010062859 W JP2010062859 W JP 2010062859W WO 2011013783 A1 WO2011013783 A1 WO 2011013783A1
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- AZUFZIHFAYSGDN-UHFFFAOYSA-N Brc1nc(Cc2cccc(Br)n2)ccc1 Chemical compound Brc1nc(Cc2cccc(Br)n2)ccc1 AZUFZIHFAYSGDN-UHFFFAOYSA-N 0.000 description 1
- YJXUBBUEBWQKLX-UHFFFAOYSA-N C(C(C=C1)c2nc(-c3ccccc3)cc(-c3cccc(-c4ccccc4)c3)n2)C=C1[n]1c(cccc2)c2c2c1cccc2 Chemical compound C(C(C=C1)c2nc(-c3ccccc3)cc(-c3cccc(-c4ccccc4)c3)n2)C=C1[n]1c(cccc2)c2c2c1cccc2 YJXUBBUEBWQKLX-UHFFFAOYSA-N 0.000 description 1
- VAXMNYAWJFVUNK-FLRGHGKASA-N C/C=C(\C=C(/C)\[n]1c(ccc(-c2ccccc2)c2)c2c2c1cccc2)/c1cc(-c2nc(-c3ccccc3)nc(-c3ccccc3)c2)cc(-c2nc(-c3ccccc3)nc(-c3ccccc3)c2)c1 Chemical compound C/C=C(\C=C(/C)\[n]1c(ccc(-c2ccccc2)c2)c2c2c1cccc2)/c1cc(-c2nc(-c3ccccc3)nc(-c3ccccc3)c2)cc(-c2nc(-c3ccccc3)nc(-c3ccccc3)c2)c1 VAXMNYAWJFVUNK-FLRGHGKASA-N 0.000 description 1
- MZLJBWWMGMKGQW-UHFFFAOYSA-N CC(C)(C)c(cc1c2c3cccc2)ccc1[n]3-c1cccc(-c2cccc(-c3nc(-c4cccc(-[n]5c6ccc(C(C)(C)C)cc6c6c5cccc6)c4)nc(-c4ccccc4)c3)c2)c1 Chemical compound CC(C)(C)c(cc1c2c3cccc2)ccc1[n]3-c1cccc(-c2cccc(-c3nc(-c4cccc(-[n]5c6ccc(C(C)(C)C)cc6c6c5cccc6)c4)nc(-c4ccccc4)c3)c2)c1 MZLJBWWMGMKGQW-UHFFFAOYSA-N 0.000 description 1
- HGTWQUNIJYFCNM-UHFFFAOYSA-N CC(C1C=C2)(C=C2[n]2c3ccccc3c3c2cccc3)c2cc(-[n]3c(cccc4)c4c4c3cccc4)ccc2N1c1cccc(C)c1 Chemical compound CC(C1C=C2)(C=C2[n]2c3ccccc3c3c2cccc3)c2cc(-[n]3c(cccc4)c4c4c3cccc4)ccc2N1c1cccc(C)c1 HGTWQUNIJYFCNM-UHFFFAOYSA-N 0.000 description 1
- AMSYBIUVNPYJFP-UHFFFAOYSA-N CC(CC([n]1c(ccc(C(C)(C)C)c2)c2c2ccccc12)=C1)c2c1c(C=C(C(C)C1)[n]3c(ccc(C(C)(C)C)c4)c4c4ccccc34)c1[n]2-c1ccccc1 Chemical compound CC(CC([n]1c(ccc(C(C)(C)C)c2)c2c2ccccc12)=C1)c2c1c(C=C(C(C)C1)[n]3c(ccc(C(C)(C)C)c4)c4c4ccccc34)c1[n]2-c1ccccc1 AMSYBIUVNPYJFP-UHFFFAOYSA-N 0.000 description 1
- GBZCLPTXYGSJTN-UHFFFAOYSA-N CC(CC([n]1c2ccccc2c2c1cccc2)=C1)c2c1c(cc(cc1)-[n]3c4ccccc4c4c3cccc4)c1[n]2-c1ccc(C(C)(C)C)cc1 Chemical compound CC(CC([n]1c2ccccc2c2c1cccc2)=C1)c2c1c(cc(cc1)-[n]3c4ccccc4c4c3cccc4)c1[n]2-c1ccc(C(C)(C)C)cc1 GBZCLPTXYGSJTN-UHFFFAOYSA-N 0.000 description 1
- SCMFBIMSARBEJX-UHFFFAOYSA-N CC(CC(c(cc1)ccc1-[n]1c(ccc(F)c2)c2c2cc(C(C)(C)C)ccc12)=C1)C=C1c1nc(-c2ccccc2)nc(-c2ccccc2)c1 Chemical compound CC(CC(c(cc1)ccc1-[n]1c(ccc(F)c2)c2c2cc(C(C)(C)C)ccc12)=C1)C=C1c1nc(-c2ccccc2)nc(-c2ccccc2)c1 SCMFBIMSARBEJX-UHFFFAOYSA-N 0.000 description 1
- XQDIYHLRTXYUCY-UHFFFAOYSA-N CC(CC=C1)C(C2)=C3C1N1C=CN(C4)C1CC3C1(C)C3N2C=CN3Cc2cccc4c2C1 Chemical compound CC(CC=C1)C(C2)=C3C1N1C=CN(C4)C1CC3C1(C)C3N2C=CN3Cc2cccc4c2C1 XQDIYHLRTXYUCY-UHFFFAOYSA-N 0.000 description 1
- UZFDDDKQYDWPOL-UHFFFAOYSA-N CC(CC=C1)c(c2c3cccc2)c1[n]3-c(cc1)cc(c2c3CCC([n]4c5ccccc5c5c4cccc5)=C2)c1[n]3-c1cccc(-c2ccccc2)c1 Chemical compound CC(CC=C1)c(c2c3cccc2)c1[n]3-c(cc1)cc(c2c3CCC([n]4c5ccccc5c5c4cccc5)=C2)c1[n]3-c1cccc(-c2ccccc2)c1 UZFDDDKQYDWPOL-UHFFFAOYSA-N 0.000 description 1
- YXRWHCUYMGEGLL-UHFFFAOYSA-N CC(CC=C1)c2c1c(cccc1)c1[n]2-c(cc1)ccc1-c(cc1)ccc1-c1cc(-c2nc(-c3ccccc3)cc(-c3ccccc3)n2)ccc1 Chemical compound CC(CC=C1)c2c1c(cccc1)c1[n]2-c(cc1)ccc1-c(cc1)ccc1-c1cc(-c2nc(-c3ccccc3)cc(-c3ccccc3)n2)ccc1 YXRWHCUYMGEGLL-UHFFFAOYSA-N 0.000 description 1
- LKTWHVZRARCXEK-UHFFFAOYSA-N CC(CC=C1)c2c1c(cccc1)c1[n]2C(C(C)C1)=Cc(c2cc(-[n]3c4ccccc4c4c3cccc4)ccc22)c1[n]2-c1ccccc1 Chemical compound CC(CC=C1)c2c1c(cccc1)c1[n]2C(C(C)C1)=Cc(c2cc(-[n]3c4ccccc4c4c3cccc4)ccc22)c1[n]2-c1ccccc1 LKTWHVZRARCXEK-UHFFFAOYSA-N 0.000 description 1
- RUKVZUWGXIILHB-UHFFFAOYSA-N CC(CC=C1)c2c1c1ccccc1[n]2C(C(C)C1)=Cc(c2c3ccc(-[n]4c5ccccc5c5ccccc45)c2)c1[n]3-c1cccc(CC(C)(C)C)c1 Chemical compound CC(CC=C1)c2c1c1ccccc1[n]2C(C(C)C1)=Cc(c2c3ccc(-[n]4c5ccccc5c5ccccc45)c2)c1[n]3-c1cccc(CC(C)(C)C)c1 RUKVZUWGXIILHB-UHFFFAOYSA-N 0.000 description 1
- AJJWQDVXRLONFL-UHFFFAOYSA-N CN1C(c2cc(-c3cccc(-[n]4c(cccc5)c5c5c4cccc5)c3)cc(-c3nc(-c4ccccc4)nc(-c4ccccc4)c3)c2)=CC(c2ccccc2)=NC1C1C=CC=CC1 Chemical compound CN1C(c2cc(-c3cccc(-[n]4c(cccc5)c5c5c4cccc5)c3)cc(-c3nc(-c4ccccc4)nc(-c4ccccc4)c3)c2)=CC(c2ccccc2)=NC1C1C=CC=CC1 AJJWQDVXRLONFL-UHFFFAOYSA-N 0.000 description 1
- 0 Fc(cc1c2c3ccc(F)c2)ccc1[n]3-c(cc1)ccc1-c1c*(-c2nc(-c3ccccc3)nc(-c3ccccc3)c2)ccc1 Chemical compound Fc(cc1c2c3ccc(F)c2)ccc1[n]3-c(cc1)ccc1-c1c*(-c2nc(-c3ccccc3)nc(-c3ccccc3)c2)ccc1 0.000 description 1
- OJVVRCPLLVHVDO-UHFFFAOYSA-N Fc1cc(-c2cc(-c3cc(-c4cc(-c5ccccc5)cc(-[n]5c6ccccc6c6c5cccc6)c4)ccc3)nc(-c3cc(F)cc(F)c3)n2)cc(F)c1 Chemical compound Fc1cc(-c2cc(-c3cc(-c4cc(-c5ccccc5)cc(-[n]5c6ccccc6c6c5cccc6)c4)ccc3)nc(-c3cc(F)cc(F)c3)n2)cc(F)c1 OJVVRCPLLVHVDO-UHFFFAOYSA-N 0.000 description 1
- DJYUUSMWVLLPQN-UHFFFAOYSA-N N#Cc(cc1)cc(c2c3ccc(C#N)c2)c1[n]3-c(cc1)ccc1-c1cccc(-c2nc(-c3ccccc3)nc(-c3ccccc3)c2)c1 Chemical compound N#Cc(cc1)cc(c2c3ccc(C#N)c2)c1[n]3-c(cc1)ccc1-c1cccc(-c2nc(-c3ccccc3)nc(-c3ccccc3)c2)c1 DJYUUSMWVLLPQN-UHFFFAOYSA-N 0.000 description 1
- ZEGYQBGJQMTXKA-UHFFFAOYSA-N c(cc1)ccc1-[n](c(ccc(-[n]1c2ccccc2c2c1cccc2)c1)c1c1c2)c1ccc2-[n]1c2ccccc2c2ccccc12 Chemical compound c(cc1)ccc1-[n](c(ccc(-[n]1c2ccccc2c2c1cccc2)c1)c1c1c2)c1ccc2-[n]1c2ccccc2c2ccccc12 ZEGYQBGJQMTXKA-UHFFFAOYSA-N 0.000 description 1
- LYTWITKTCMAKFQ-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)cc(c2cc(-c3ccccc3)ccc22)c1[n]2-c(cc1)ccc1-c1nc(-c2ccccc2)nc(-c2ncccc2)c1 Chemical compound c(cc1)ccc1-c(cc1)cc(c2cc(-c3ccccc3)ccc22)c1[n]2-c(cc1)ccc1-c1nc(-c2ccccc2)nc(-c2ncccc2)c1 LYTWITKTCMAKFQ-UHFFFAOYSA-N 0.000 description 1
- KSYXRMMASGFNRB-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-c(cc2)ccc2-[n]2c3ccccc3c3c2cccc3)cc(-c(cc2)ccc2-c2nc(-c3ccccc3)cc(-c3ccccc3)n2)c1 Chemical compound c(cc1)ccc1-c1cc(-c(cc2)ccc2-[n]2c3ccccc3c3c2cccc3)cc(-c(cc2)ccc2-c2nc(-c3ccccc3)cc(-c3ccccc3)n2)c1 KSYXRMMASGFNRB-UHFFFAOYSA-N 0.000 description 1
- HRZRKGVYCDXJJF-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-c(cc2)ccc2-c(cc2)ccc2-[n]2c3ccccc3c3c2cccc3)cc(-c2nc(-c3ccccc3)cc(-c3ccccc3)n2)c1 Chemical compound c(cc1)ccc1-c1cc(-c(cc2)ccc2-c(cc2)ccc2-[n]2c3ccccc3c3c2cccc3)cc(-c2nc(-c3ccccc3)cc(-c3ccccc3)n2)c1 HRZRKGVYCDXJJF-UHFFFAOYSA-N 0.000 description 1
- PBTLDGDMAZQTHN-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-c2cccc(-c3nc(-c4ccccc4)cc(-c4ccccc4)n3)c2)cc(-c(cc2)ccc2-[n]2c3ccccc3c3c2cccc3)c1 Chemical compound c(cc1)ccc1-c1cc(-c2cccc(-c3nc(-c4ccccc4)cc(-c4ccccc4)n3)c2)cc(-c(cc2)ccc2-[n]2c3ccccc3c3c2cccc3)c1 PBTLDGDMAZQTHN-UHFFFAOYSA-N 0.000 description 1
- TZYVINRQNDVVMB-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-c2ccccc2)nc(-c(cc2)ccc2-c2cc(-c(cc3)ccc3-[n]3c4ccccc4c4ccccc34)ccc2)n1 Chemical compound c(cc1)ccc1-c1cc(-c2ccccc2)nc(-c(cc2)ccc2-c2cc(-c(cc3)ccc3-[n]3c4ccccc4c4ccccc34)ccc2)n1 TZYVINRQNDVVMB-UHFFFAOYSA-N 0.000 description 1
- CPFOOPDGWZSGBA-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-c2nc(-c3cccc(-c4cc(-[n]5c(cccc6)c6c6ccccc56)ccc4)c3)cc(-c3ccccc3)n2)cc(-c2ccccc2)c1 Chemical compound c(cc1)ccc1-c1cc(-c2nc(-c3cccc(-c4cc(-[n]5c(cccc6)c6c6ccccc56)ccc4)c3)cc(-c3ccccc3)n2)cc(-c2ccccc2)c1 CPFOOPDGWZSGBA-UHFFFAOYSA-N 0.000 description 1
- HOSVLFKZZBUWKW-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-c2cccc(-c3cc(-c(cc4)ccc4-[n]4c5ccccc5c5c4cccc5)ccc3)c2)nc(-c2ccccc2)c1 Chemical compound c(cc1)ccc1-c1nc(-c2cccc(-c3cc(-c(cc4)ccc4-[n]4c5ccccc5c5c4cccc5)ccc3)c2)nc(-c2ccccc2)c1 HOSVLFKZZBUWKW-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
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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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
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- H—ELECTRICITY
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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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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/1018—Heterocyclic compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Definitions
- the present invention relates to an organic electroluminescent element (hereinafter also referred to as “element” or “organic EL element”), which is highly efficient, highly durable, and excellent in suppressing chromaticity change during high temperature driving. It relates to an element.
- organic electroluminescence devices have been actively researched and developed in recent years because they can emit light with high brightness when driven at a low voltage.
- an organic electroluminescent element is composed of an organic layer including a light emitting layer and a pair of electrodes sandwiching the layer, and electrons injected from the cathode and holes injected from the anode are recombined in the light emitting layer, The generated exciton energy is used for light emission.
- phosphorescent materials include iridium complexes and platinum complexes (see, for example, Patent Document 1).
- Ir (btp) 2 (acac) is known as a red phosphorescent material.
- a doped element using a light emitting layer in which a light emitting material is doped in a host material is widely used.
- the development of host materials has also been actively conducted.
- CBP 4,4′-bis (N-carbazolyl) biphenyl
- Balq Alluminum (III) bis (2-methyl-8) are used.
- Patent Document 2 discloses an invention in which an aromatic polycyclic fused ring material is used as a host material of a red phosphorescent material for the purpose of producing a highly efficient and long-life device. Durability at high temperature is not sufficient. Furthermore, when a display or lighting application is considered, there is a problem that chromaticity changes with driving, and improvement is required. Conventionally, in evaluating the durability of an element, a change in chromaticity accompanying driving along with an increase in driving voltage or a decrease in efficiency has been cited as an evaluation item. The environmental temperature has also been evaluated from room temperature (mainly in the sense of accelerated testing).
- Patent Document 2 it is known that the introduction of a carbazole group that is vulnerable to oxidation is not preferable for the durability of the device, and the aspect of the present invention improves the durability in light of the common sense. I could not expect it to be effective. Also, in the case of phosphorescent materials based on iridium complexes, it is presumed that the decomposition and generation of quenching materials that are triggered by the release of the ligand, which is the fate of the complex materials, will deteriorate the device performance, making it difficult to put to practical use. It is known to accompany.
- an object of the present invention is to provide an organic electroluminescence device having excellent light emission characteristics, suppressing a change in chromaticity when driven at high temperature, and having excellent durability.
- Another object of the present invention is to provide a composition and a light emitting layer useful for an organic electroluminescent device.
- another object of the present invention is to provide a compound film forming method useful for an organic electroluminescent device.
- Another object of the present invention is to provide a light emitting device, a display device, and a lighting device including an organic electroluminescent element.
- An organic electroluminescent device having a pair of electrodes on a substrate and a light emitting layer between the electrodes, the compound represented by the following general formula (1) in the light emitting layer, and a general formula (PQ-1)
- Cz represents a substituted or unsubstituted arylcarbazolyl group or a substituted or unsubstituted carbazolylaryl group.
- L represents a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted aromatic heterocyclic ring.
- A is a substituted or unsubstituted nitrogen-containing aromatic hetero 6-membered ring, and p and q are each independently an integer of 1 to 6.
- R 1 to R 10 each independently represents a hydrogen atom or a substituent.
- the substituents may be bonded to each other to form a ring, if possible.
- [2] The organic electroluminescence device according to [1], wherein in the general formula (PQ-1), n 3.
- the organic electroluminescence device according to [1], wherein n 2.
- R 1 to R 6 are hydrogen atoms.
- Cz represents a substituted or unsubstituted arylcarbazolyl group or a substituted or unsubstituted carbazolylaryl group.
- L represents a single bond, a substituted or unsubstituted arylene group, substituted or unsubstituted Represents an unsubstituted cycloalkylene group or a substituted or unsubstituted aromatic heterocycle, and is linked to a carbon atom of Ar 1 , Ar 2 , X 1 , X 2 or X 3 , each independently Ar 1 and Ar 2 Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted aromatic heterocyclic group, and X 1 , X 2 and X 3 each independently represent a nitrogen atom, a hydrogen atom or a carbon atom to which a substituent is bonded; P and q each independently represents an integer of 1 to 6) [7]
- the organic electroluminescence device
- X 4 and X 5 each independently represent a nitrogen atom, a hydrogen atom or a carbon atom to which a substituent is bonded, and one of X 4 and X 5 is nitrogen, and the other Represents a hydrogen atom or a carbon atom to which a substituent is bonded, and L ′ represents a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted aromatic heterocycle.
- R 1 to R 5 each independently represents a substituent, n1 to n5 each independently represents an integer of 0 to 5, and p ′ and q ′ each independently represents an integer of 1 to 4.
- (XY) is any one of acetylacetonate (acac), picolinate (pic), and derivatives thereof.
- Q 1 , Q 2 , Q 3 and Q 4 each independently represent a ligand coordinated to Pt.
- L 1 , L 2 and L 3 each independently represents a single bond or a divalent linking group.
- L 21 represents a single bond or a divalent linking group.
- a 21 and A 22 each independently represent a carbon atom or a nitrogen atom.
- Z 21 and Z 22 each independently represent a nitrogen-containing aromatic heterocycle.
- Z 23 and Z 24 each independently represent a benzene ring or an aromatic heterocycle.
- the compound represented by the general formula (1) according to any one of [1] to [11] and the compound represented by the general formula (PQ-1) are sublimated by heating simultaneously.
- a film forming method for forming a film [17] [1] A light emitting device using the organic electroluminescent element as described in any one of [11]. [18] [1] A display device using the organic electroluminescent element as described in any one of [11]. [19] [1] An illumination device using the organic electroluminescent element as described in any one of [11].
- the organic electroluminescent device of the present invention has high external quantum efficiency and excellent durability.
- the chromaticity change during high-temperature driving is small, and stable performance can be exhibited even in applications that require driving durability in high-temperature environments such as in-vehicle applications.
- substituent groups A and B are defined as follows.
- An alkyl group preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.
- alkenyl groups preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl , Allyl, 2-butenyl, 3-pentenyl, etc.
- alkynyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as propargyl , 3-pentyn
- pyridyloxy pyrazyloxy, pyrimidyloxy, quinolyloxy and the like
- an acyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms.
- Benzoyl, formyl, pivaloyl, etc. an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxy Carbonyl, etc.), an aryloxycarbonyl group (preferably It has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl.
- an alkoxycarbonyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxy Carbonyl, etc.
- an aryloxycarbonyl group preferably It has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl
- An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy, benzoyloxy, etc.), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino and the like, and alkoxycarbonylamino groups (preferably having 2-2 carbon atoms).
- an aryloxycarbonylamino group preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino).
- an aryloxycarbonylamino group preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino).
- a sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), carbamoyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, etc.), an arylthio group (preferably 6 to 30 carbon atoms).
- Rufinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carb
- Is for example, a nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, selenium atom, tellurium atom, specifically pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, And isoxazolyl, isothiazolyl, quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolyl, benzoimidazolyl, benzothiazolyl, carbazolyl group, azepinyl group, silolyl group and the like.
- a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl).
- a aryloxy group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), phosphoryl group (for example, A diphenylphosphoryl group, a dimethylphosphoryl group, etc.).
- These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.
- alkyl group preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.
- alkenyl groups preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyl , Allyl, 2-butenyl, 3-pentenyl, etc.
- alkynyl group preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as propargyl , 3-pentynyl, etc.
- aryl groups preferably having 6 to 30 carbon
- Hydrogen atoms in the following description of general formulas (1) to (3), general formulas (PQ-1) to (PQ-2), general formulas (C-1) to (C-6) and general formula (IV) Represents an isotope (such as a deuterium atom), and the atoms constituting the substituent further include the isotope.
- the “carbon number” of a substituent such as an alkyl group includes a case where a substituent such as an alkyl group may be substituted by another substituent, and also includes the carbon number of the other substituent. Used to mean.
- a “heteroalkyl” group refers to an alkyl group in which at least one carbon is replaced by O, NR, or S.
- the organic electroluminescent element of the present invention is an organic electroluminescent element having a pair of electrodes on a substrate and a light emitting layer between the electrodes, and the compound represented by the following general formula (1) in the light emitting layer: And a compound represented by the general formula (PQ-1).
- An organic electroluminescent device having high external quantum efficiency and excellent durability by using a compound represented by the general formula (1) and a compound represented by the general formula (PQ-1) in the light emitting layer Can be obtained.
- an organic electroluminescent element having a small change in chromaticity when driven at high temperature can be obtained.
- Cz represents a substituted or unsubstituted arylcarbazolyl group or a substituted or unsubstituted carbazolylaryl group.
- L represents a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted aromatic heterocyclic ring.
- A is a substituted or unsubstituted nitrogen-containing aromatic hetero 6-membered ring, and p and q are each independently an integer of 1 to 6.
- Cz is a substituted or unsubstituted arylcarbazolyl group or a substituted or unsubstituted carbazolylaryl group.
- the aryl group in the arylcarbazolyl group and the carbazolylaryl group preferably has 6 to 30 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a naphthacenyl group, a pyrenyl group, a fluorenyl group, a biphenyl group, A terphenyl group etc.
- a phenyl group, a naphthyl group, a biphenyl group, and a terphenyl group are preferable, and a phenyl group and a biphenyl group are more preferable.
- the substitution position of the aryl group on the carbazole ring (carbazolyl group) in the aryl carbazolyl group and carbazolyl aryl group is not particularly limited, but the aryl group is a carbazole ring from the viewpoint of chemical stability and carrier transportability.
- Cz is an arylcarbazolyl group
- the 2-position, 3-position, 6-position, 7-position or 9-position of the carbazole ring of the arylcarbazolyl group It is preferably linked to L at (N-position), more preferably linked to L at the 3-position, 6-position or 9-position (N-position) of the carbazole ring, and L at 9-position (N-position) of the carbazole ring. Most preferably, they are linked.
- Cz is preferably an alkyl group, a silyl group, an aryl group, a halogen atom, a cyano group, or a carbazolylaryl group optionally substituted with a carbazolyl group, such as an ethyl group, a t-butyl group, or a triphenyl group.
- a carbazolyl aryl group which may be substituted with a silyl group, a phenyl group, a fluorine atom, a cyano group or a carbazolyl group is more preferable.
- A is a substituted or unsubstituted nitrogen-containing aromatic hetero 6-membered ring, preferably a nitrogen-containing aromatic hetero 6-membered ring having 2 to 40 carbon atoms.
- A may have a plurality of substituents, and the substituents may be bonded to each other to form a ring.
- Examples of the nitrogen-containing aromatic heterocycle including a nitrogen-containing aromatic hetero ring or a nitrogen-containing aromatic hetero 6-membered ring include pyridine, pyrimidine, pyrazine, pyridazine, triazine, azaindolizine, indolizine, purine, pteridine, ⁇ -Carboline, naphthyridine, quinoxaline, terpyridine, bipyridine, acridine, phenanthroline, phenazine, imidazopyridine, etc.
- pyridine, pyrimidine, pyrazine, and triazine are more preferable
- pyridine and pyrimidine are more preferable
- pyrimidine is most preferable. .
- L is a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted aromatic heterocycle.
- L is a p + q-valent group obtained by removing p + q-2 arbitrary hydrogen atoms from the arylene group, and p + q-2 arbitrary groups from a cycloalkylene group.
- substituent group A As the substituent that L has, those listed as the substituent group A can be applied, and preferably a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a cyclopentyl group, a phenyl group, a tolyl group, a xylyl group, Pyridyl group, pyrimidyl group, thienyl group, fluorine atom, cyano group, trifluoromethyl group, pentafluorophenyl group, triphenylsilyl group, trimethylsilyl group, more preferably methyl group, ethyl group, butyl group, phenyl group, A pyridyl group, a pyrimidyl group, a fluorine atom, a cyano group, and a trifluoromethyl group are preferable, and a methyl group, a phenyl group, and
- arylene group an arylene group having 6 to 30 carbon atoms is preferable.
- Arylene group etc. are mentioned, Among these, phenylene group, biphenylene group, terphenylene group and perfluoroarylene group are preferable, phenylene group, biphenylene group and terphenylene group are more preferable, and phenylene group and biphenylene group are still more preferable.
- the cycloalkylene group is preferably a cycloalkylene group having 5 to 30 carbon atoms, and examples thereof include a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.
- a cyclopentylene group and a cyclohexylene group are preferable, A hexylene group is more preferred.
- the aromatic heterocycle an aromatic heterocycle having 2 to 30 carbon atoms is preferable.
- L is preferably a single bond, a phenylene group, a biphenylene group, a cyclopentylene group, a cyclohexylene group, a pyridinyl group or a carbazolyl group, more preferably a single bond, a phenylene group or a biphenylene group, and further a single bond or a phenylene group preferable.
- halogen atoms such as fluorine, chlorine, bromine and iodine, carbazolyl groups, hydroxyl groups, substituted or unsubstituted amino groups, nitro groups, cyano groups Group, silyl group, trifluoromethyl group, carbonyl group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted aromatic group, Examples thereof include a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxy group, and a substituted or unsubstituted alkyloxy group.
- fluorine atom methyl group, perfluorophenylene group, phenyl group, naphthyl group, pyridyl group, pyrazyl group, pyrimidyl group, adamantyl group, benzyl group, nitro group, cyano group, silyl group, trifluoromethyl group
- a group consisting of a carbazolyl group and a combination thereof is preferable, and a fluorine atom, a methyl group, a phenyl group, a pyridyl group, a pyrimidyl group, a cyano group, a silyl group, a carbazolyl group, and a group consisting of only these are more preferable.
- a group consisting of a group, a pyridyl group, a pyrimidyl group, a carbazolyl group, and a combination thereof alone is more preferred, and a phenyl group is most preferred.
- this substituent may couple
- P and q are each independently an integer of 1 to 6, preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2.
- the compound represented by the general formula (1) is more preferably a compound represented by the following general formula (2).
- Cz represents a substituted or unsubstituted arylcarbazolyl group or a substituted or unsubstituted carbazolylaryl group.
- L represents a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted aromatic heterocyclic ring, and Ar 1 , Ar 2 , X 1 , X 2 or X 3 To the carbon atom of Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aryl group, or a substituted or unsubstituted aromatic heterocyclic group, and X 1 , X 2 and X 3 each independently represent a nitrogen atom or a hydrogen atom or It represents a carbon atom to which a substituent is bonded.
- p and q each independently represents an integer of 1 to 6.
- the aryl group is preferably a substituted or unsubstituted one having 6 to 30 carbon atoms, for example, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a bienyl group, a chrysenyl group, a fluoranthenyl group, Perfluoroaryl groups and the like.
- a phenyl group, a biphenyl group, a terphenyl group, and a perfluoroaryl group are preferable, a phenyl group, a biphenyl group, and a terphenyl group are more preferable, and a phenyl group and a biphenyl group are still more preferable.
- the arylene group is preferably a substituted or unsubstituted group having 6 to 30 carbon atoms, and specific examples and preferred groups are the same as those described in the description of L in the general formula (1).
- the aromatic heterocyclic group is preferably a substituted or unsubstituted one having 2 to 30 carbon atoms, and specific examples and preferred groups are the same as those described in the description of L in the general formula (1).
- specific examples and preferred groups of the substituent are the same as those exemplified as the substituents for Cz, A and L in the general formula (1).
- Ar 1 and Ar 2 are preferably each independently a phenyl group which may be substituted with a halogen atom or an unsubstituted terphenyl group, and more preferably a phenyl group which may be substituted with a fluorine atom. preferable.
- X 1 , X 2 and X 3 each independently represent a nitrogen atom, a hydrogen atom or a carbon atom to which a substituent is bonded.
- 0 to 2 are preferably nitrogen atoms, more preferably 0 or 1 are nitrogen atoms, and most preferably 1 is a nitrogen atom.
- any of X 1 , X 2 and X 3 contains a nitrogen atom, it is preferable that any one of X 1 and X 3 is a nitrogen atom.
- the ring containing X 1 to X 3 in the general formula (2) preferably represents pyridine or pyrimidine, and more preferably represents pyrimidine.
- the connecting position of L is not particularly limited, but it is preferably connected to the carbon atom of Ar 1 from the viewpoint of chemical stability and carrier transportability.
- the compound represented by the general formula (2) is more preferably a compound represented by the following general formula (3).
- X 4 and X 5 each independently represent a nitrogen atom, a hydrogen atom, or a carbon atom to which a substituent is bonded, and one of X 4 and X 5 is a nitrogen atom, and the other is hydrogen.
- L ′ represents a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted aromatic heterocyclic ring.
- R 1 to R 5 each independently represents a substituent.
- n1 to n5 each independently represents an integer of 0 to 5.
- p ′ and q ′ each independently represents an integer of 1 to 4.
- X 4 and X 5 each independently represent a nitrogen atom, a hydrogen atom, or a carbon atom to which a substituent is bonded. Either one of X 4 and X 5 is preferably a nitrogen atom, and the other is preferably a hydrogen atom or a carbon atom to which a substituent is bonded.
- the ring containing X 4 and X 5 in the general formula (3) preferably represents pyridine or pyrimidine, and more preferably represents pyrimidine. Specific examples and preferred groups of the substituent bonded to the carbon atom are the same as those exemplified as the substituents of Cz, A and L in the general formula (1).
- L ′ is the same as L in General Formula (1) described above, and the preferred group is also the same as L.
- L ′ is linked to the benzene ring in the nitrogen-containing aromatic heterostructure in the general formula (3).
- R 1 to R 5 each independently represents a substituent. Specific examples of the substituent are the same as those mentioned as the substituent for Cz and A in the general formula (1).
- R 1 to R 5 are preferably fluorine atom, methyl group, t-butyl group, phenyl group, pyridyl group, pyrazyl group, pyrimidyl group, adamantyl group, cyano group, trimethylsilyl group, triphenylsilyl group, trifluoromethyl group.
- a carbazolyl group more preferably a fluorine atom, a methyl group, a t-butyl group, a phenyl group, a pyridyl group, a cyano group, a trimethylsilyl group, a triphenylsilyl group, a trifluoromethyl group, and a carbazolyl group, and more preferably Is a fluorine atom, methyl group, t-butyl group, phenyl group, cyano group, silyl group, triphenylsilyl group, trifluoromethyl group, carbazolyl group, more preferably a fluorine atom, t-butyl group, phenyl group, A cyano group, a triphenylsilyl group, and a carbazolyl group.
- R 1 ⁇ R 5 When R 1 ⁇ R 5 are a plurality, it may be different in each of a plurality of R 1 ⁇ R 5 are the same.
- n1 to n5 each independently represents an integer of 0 to 5. Each of them is preferably 0 to 2, more preferably 0 to 1, and still more preferably 0.
- p ′ and q ′ each independently represents an integer of 1 to 4. Each is preferably 1 to 3, more preferably 1 or 2.
- X 4 and X 5 are each independently a carbon atom to which a nitrogen atom or a hydrogen atom is bonded, the ring containing X 4 and X 5 is pyridine or pyrimidine, and L ′ is R 1 to R 5 each independently represents a fluorine atom, a methyl group, a phenyl group, a cyano group, a pyridyl group, a pyrimidyl group, a silyl group, a carbazolyl group, or a tert-butyl group, n1 to n5 each independently represents 0 or 1, and p ′ and q ′ each independently represent 1 or 2.
- L ′ represents a p ′ + q′-valent group obtained by removing any hydrogen atom of p ′ + q′-2 from the phenylene group.
- the compound represented by the general formula (1) is most preferably composed of only carbon, hydrogen and nitrogen atoms.
- the molecular weight of the compound represented by the general formula (1) is preferably 400 or more and 1000 or less, more preferably 450 or more and 800 or less, and further preferably 500 or more and 700 or less.
- the lowest excited triplet (T 1 ) energy in the film state of the compound represented by the general formula (1) is preferably 2.61 eV (62 kcal / mol) or more and 3.51 eV (80 kcal / mol) or less. More preferably, it is not less than .69 eV (63.5 kcal / mol) and not more than 3.51 eV (80 kcal / mol), and still more preferably not less than 2.76 eV (65 kcal / mol) and 3.51 eV (80 kcal / mol).
- the glass transition temperature (Tg) of the compound represented by the general formula (1) is preferably 80 ° C. or higher and 400 ° C. or lower, more preferably 100 ° C. or higher and 400 ° C. or lower, and 120 ° C. or higher and 400 ° C. or lower. More preferably it is.
- an isotope such as deuterium atom
- all hydrogen atoms in the compound may be replaced with isotopes, or a mixture in which a part is a compound containing isotopes may be used.
- Ph represents a phenyl group.
- the compounds exemplified as the compound represented by the above general formula (1) are the methods described in WO03 / 080760, the methods described in WO03 / 078541, and WO05 / 085387. It can be synthesized by various methods such as the method described in the issue pamphlet.
- the above-mentioned No. 4 was prepared by using m-bromobenzaldehyde as a starting material and the method described in paragraph [0074]-[0075] (page 45, line 11 to page 46, line 18) of International Publication No. 05/085387. Can be synthesized. No. above.
- Compound 45 can be synthesized by the method described on page 46, line 9 to page 46, line 12 of WO 03/080760 using 3,5-dibromobenzaldehyde as a starting material.
- the above No. Compound 77 can be synthesized by the method described on page 137, page 10 to page 139, line 9 of WO 05/022962, using N-phenylcarbazole as a starting material.
- the compound represented by the general formula (1) is not limited in its application, and may be contained in any layer in the organic layer other than the light emitting layer in addition to the light emitting layer.
- any of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer Or a plurality of them are preferably contained.
- the compound represented by the general formula (1) may be contained in both the light emitting layer and the layer adjacent to the light emitting layer in order to further suppress the change in chromaticity at the time of high temperature driving.
- the compound represented by the general formula (1) of the present invention should be contained in an amount of 0.1 to 99% by mass with respect to the total mass of the light emitting layer. Preferably, it is contained in an amount of 1 to 95% by mass, more preferably 10 to 95% by mass. In addition, when the compound represented by the general formula (1) is contained in a layer other than the light emitting layer, it is preferably contained in an amount of 10 to 100% by mass, and preferably 30 to 100% by mass with respect to the total mass of the layer other than the light emitting layer. % Is more preferable, and 50 to 100% by mass is more preferable.
- the host material can be used in combination with the compound represented by the general formula (1) and the compound represented by the general formula (PQ-1).
- the host material used in combination may be a hole transporting host material or an electron transporting host material.
- the light emitting layer preferably includes a compound represented by the general formula (1), a compound represented by the general formula (PQ-1), and a host material.
- the host material is preferably a compound represented by the following general formula (4-1) or (4-2).
- the compound represented by the general formula (1) and the compound represented by the general formula (PQ-1), and further represented by the general formula (4-1) or (4-2) are used in the light emitting layer. More preferably, it contains at least one of the compounds to be prepared.
- the compound represented by the general formula (4-1) or (4-2) when the compound represented by the general formula (4-1) or (4-2) is contained in the light emitting layer, the compound represented by the general formula (4-1) or (4-2) is The light emitting layer preferably contains 1 to 90% by mass, more preferably 1 to 70% by mass, and particularly preferably 1 to 40% by mass.
- the compound represented by the general formula (4-1) or (4-2) when it is included together with the compound represented by the general formula (1), In the case where the compound represented by the general formula (1) is not included, it is preferably included in each layer in an amount of 30 to 95% by mass and may be included in an amount of 40 to 95% by mass. More preferably, 60 to 95% by mass is contained.
- the compound represented by the general formula (4-1) or (4-2) may contain only one kind in any organic layer, and a plurality of general formulas (4-1) or (4) The compound represented by -2) may be contained in combination at any ratio.
- R “ 8” represents a substituent, and when d, e, and f are 2 or more, R ′ 8 may be different or the same, and at least one of R ′ 8 is represented by the following general formula (5). Represents a carbazole group.
- R ′ 9 each independently represents a substituent.
- G represents an integer of 0 to 8.
- R ′ 8 independently represents a substituent, specifically, a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, a heterocyclic group, or a substituent represented by the general formula (5) It is.
- R ′ 8 does not represent the general formula (5), it is preferably an alkyl group having 10 or less carbon atoms, a substituted or unsubstituted aryl group having 10 or less carbon atoms, and more preferably an alkyl group having 6 or less carbon atoms. It is.
- R ′ 9 each independently represents a substituent, specifically a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, or a heterocyclic group, preferably an alkyl group having 10 or less carbon atoms, A substituted or unsubstituted aryl group having 10 or less carbon atoms, more preferably an alkyl group having 6 or less carbon atoms.
- g represents an integer of 0 to 8 and is preferably 0 to 4 from the viewpoint of not shielding too much the carbazole skeleton responsible for charge transport. From the viewpoint of ease of synthesis, when carbazole has a substituent, those having a substituent so as to be symmetric with respect to the nitrogen atom are preferable.
- the sum of d and e is preferably 2 or more from the viewpoint of maintaining the charge transport ability.
- R ′ 8 is preferably substituted with meta for the other benzene ring.
- the reason for this is considered to be that the ortho-substitution causes the steric hindrance of adjacent substituents to be large, so that the bond is easily cleaved and the durability is lowered.
- the molecular shape approaches a rigid rod shape and is easily crystallized, so that element degradation is likely to occur under high temperature conditions.
- a compound represented by the following structure is preferable. Note the following R in the compounds '9 and g, R in the formula (5)' is synonymous with 9 and g.
- f is preferably 2 or more from the viewpoint of maintaining the charge transport ability.
- R ′ 8 is substituted with meta from the same viewpoint.
- a compound represented by the following structure is preferable. Note the following R in the compounds '9 and g, R in the formula (5)' is synonymous with 9 and g.
- an isotope of hydrogen such as a deuterium atom
- all hydrogen atoms in the compound may be replaced with hydrogen isotopes, or a mixture in which a part is a compound containing hydrogen isotopes may be used.
- R ′ 9 in the general formula (5) is substituted with deuterium, and the following structures are particularly preferable.
- the atoms constituting the substituents also include their isotopes.
- the compounds represented by the general formulas (4-1) and (4-2) can be synthesized by combining various known synthesis methods.
- carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- the compounds represented by the general formulas (4-1) and (4-2) preferably form a thin layer by a vacuum deposition process, but a wet process such as solution coating is also preferably used. I can do it.
- the molecular weight of the compound is preferably 2000 or less, more preferably 1200 or less, and particularly preferably 800 or less from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred.
- the general formulas (4-1) and (4-2) are preferably compounds represented by the following structures or compounds in which one or more hydrogen atoms are substituted with deuterium atoms. Note the following compounds in the R '8 and R' 9, the general formula (4-1) and (4-2) as well as the same meaning as R '8 and R' 9 in the formula (5).
- R 1 to R 10 each independently represents a hydrogen atom or a substituent.
- the substituents may combine with each other to form a ring, if possible.
- X— Y represents a bidentate monoanionic ligand, and n represents an integer of 1 to 3.
- R 1 to R 10 are preferably a hydrogen atom, an alkyl group (the alkyl group may have a fluorine atom, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms), a cycloalkyl group ( Preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, still more preferably 5 to 10 carbon atoms), an aryl group (preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms), an amino group
- An alkoxy group preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms
- an aryloxy group preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms
- a heterocyclic oxy group preferably 2 to 12 carbon atoms, more preferably 3 to 10 carbon atoms
- a cyano group a heterocyclic group (preferably 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms, a cyan
- An atom more preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an alkoxy group, a cyano group, a heterocyclic group, a silyl group, or a fluorine atom, more preferably a hydrogen atom, an alkyl group,
- An aryl group more preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a neopentyl group, an isobutyl group, a phenyl group, a naphthyl group, a phenanthryl group, a tolyl group, and more preferably a hydrogen atom.
- R 1 to R 10 may be bonded to each other to form a ring, if possible.
- R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 are bonded to each other to form a ring.
- the ring formed together with the benzene ring substituted by R 7 to R 10 is:
- Examples include an aryl ring which may be substituted with an alkyl group, an alkoxy group or the like.
- the formed aryl ring is preferably an aryl ring having 6 to 30 carbon atoms, more preferably an aryl ring having 6 to 15 carbon atoms.
- Examples of the aryl ring to be formed include a naphthalene ring, a phenanthrene ring, and a fluorene ring.
- a naphthalene ring or a fluorene ring is preferable, and a naphthalene ring is more preferable.
- These rings may have a substituent such as an alkyl group or an alkoxy group, and are preferably a naphthalene ring or a fluorene ring which may be substituted with an alkyl group or an alkoxy group.
- R 1 to R 6 each independently represents an alkyl group, a cycloalkyl group, an aryl group, a cyano group, or a fluorine atom
- other R 1 to R 6 it is also preferred but are all hydrogen atom
- 0 or one is alkyl group of R 1 ⁇ R 6, cycloalkyl group, aryl group, with a cyano group or a fluorine atom
- the other R 1 ⁇ R 6 are all
- a hydrogen atom is more preferable, and all of R 1 to R 6 are more preferably hydrogen atoms for the purpose of improving durability.
- R 7 to R 10 each independently represents an alkyl group, an aryl group, a cyano group, a heterocyclic group or a fluorine atom
- the other R 7 to R 10 Are preferably all hydrogen atoms
- 0 to 2 of R 7 to R 10 each independently represents an alkyl group, an aryl group, a cyano group or a fluorine atom
- the other R 7 to R 10 are all hydrogen atoms. More preferably, it is an atom
- R 9 represents an aryl group
- R 7 , R 8 and R 10 are all preferably hydrogen atoms.
- R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 may be bonded to each other to form the aforementioned ring, and when forming a ring, the aforementioned aryl ring is formed. More preferably, it is more preferable to form a benzene ring.
- N is preferably 2 or 3, and more preferably 2.
- XY represents a bidentate monoanionic ligand. These ligands are believed not to contribute directly to the luminescent properties, but to control the luminescent properties of the molecules.
- the bidentate monoanionic ligand used in the luminescent material can be selected from those known in the art. Examples of the bidentate monoanionic ligand include those described in Lamansky et al., PCT application WO 02/15645, pages 89 to 90, but the present invention is not limited thereto.
- Preferred bidentate monoanionic ligands include acetylacetonate (acac) and picolinate (pic), and derivatives thereof.
- the bidentate monoanionic ligand is preferably acetylacetonate from the viewpoint of the stability of the complex and the high emission quantum yield.
- M represents a metal atom.
- R 1 to R 6 are preferably hydrogen atoms.
- R 9 is preferably an aryl group.
- the compound represented by the general formula (PQ-1) is preferably a compound represented by the following general formula (PQ-2).
- R 8 to R 10 each represent a hydrogen atom or a substituent.
- the substituents may be bonded to each other to form a ring, if possible.
- R 8 ⁇ R 10 and X-Y is Formula (PQ-1) have the same meanings as R 8 ⁇ R 10 and X-Y in the preferred ranges are also the same.
- the compounds exemplified as the compound represented by the general formula (PQ-1) can be synthesized by various methods such as the method described in Japanese Patent No. 3929632, for example.
- FR-2 can be synthesized by the method described in Japanese Patent No. 3929632, page 18, lines 2 to 13 using 2-phenylquinoline as a starting material.
- FR-3 can be synthesized by the method described on page 18, line 14 to page 19, line 8 of Japanese Patent No. 3929632 using 2- (2-naphthyl) quinoline as a starting material.
- the content is preferably 0.1 to 30% by mass in the light emitting layer, and 2 to 20% by mass. More preferably, it is more preferably 5 to 15% by mass.
- the compound represented by the general formula (PQ-1) is contained in the light emitting layer, but its use is not limited and may be further contained in any layer in the organic layer. .
- the compound represented by the general formula (1) and the compound represented by the general formula (PQ-1) are contained in the light emitting layer.
- the organic electroluminescent element of the present invention preferably further contains a compound represented by the following general formula (C-1) in the light emitting layer.
- Q 1 , Q 2 , Q 3 and Q 4 each independently represent a ligand coordinated to Pt.
- L 1 , L 2 and L 3 are each independently a single bond. Or represents a divalent linking group.
- Q 1 , Q 2 , Q 3 and Q 4 each independently represent a ligand coordinated to Pt.
- the bond between Q 1 , Q 2 , Q 3 and Q 4 and Pt may be any of a covalent bond, an ionic bond, a coordinate bond, and the like.
- a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are preferable, and in Q ⁇ 1 >, Q ⁇ 2 >, Q ⁇ 3 > and Q ⁇ 4 >
- a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are preferable, and in Q ⁇ 1 >, Q ⁇ 2 >, Q ⁇ 3 > and Q ⁇ 4 >
- at least one is preferably a carbon atom, more preferably two are carbon atoms, particularly preferably two are carbon atoms and two are nitrogen atoms.
- Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt by a carbon atom may be an anionic ligand or a neutral ligand, and the anionic ligand is a vinyl ligand, Aromatic hydrocarbon ring ligand (eg benzene ligand, naphthalene ligand, anthracene ligand, phenanthrene ligand etc.), heterocyclic ligand (eg furan ligand, thiophene ligand, pyridine) Ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, thiazole ligand, oxazole ligand, pyrrole ligand, imidazole ligand, pyrazole ligand, triazole And a condensed ring containing them (for example, quinoline ligand, benzothiazole ligand, etc.).
- a carbene ligand is mentioned as a neutral ligand.
- Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with a nitrogen atom may be neutral ligands or anionic ligands, and as neutral ligands, nitrogen-containing aromatic hetero Ring ligand (pyridine ligand, pyrazine ligand, pyrimidine ligand, pyridazine ligand, triazine ligand, imidazole ligand, pyrazole ligand, triazole ligand, oxazole ligand, Examples include thiazole ligands and condensed rings containing them (for example, quinoline ligands, benzimidazole ligands), amine ligands, nitrile ligands, and imine ligands.
- anionic ligands include amino ligands, imino ligands, nitrogen-containing aromatic heterocyclic ligands (pyrrole ligands, imidazole ligands, triazole ligands and condensed rings containing them) (For example, indole ligand, benzimidazole ligand, etc.)).
- Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with an oxygen atom may be neutral ligands or anionic ligands, and neutral ligands are ether ligands, Examples include ketone ligands, ester ligands, amide ligands, oxygen-containing heterocyclic ligands (furan ligands, oxazole ligands and condensed rings containing them (benzoxazole ligands, etc.)). It is done.
- the anionic ligand include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, and the like.
- Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with a sulfur atom may be neutral ligands or anionic ligands, and neutral ligands include thioether ligands, Examples include thioketone ligands, thioester ligands, thioamide ligands, sulfur-containing heterocyclic ligands (thiophene ligands, thiazole ligands and condensed rings containing them (such as benzothiazole ligands)). It is done.
- the anionic ligand include an alkyl mercapto ligand, an aryl mercapto ligand, and a heteroaryl mercapto ligand.
- Q 1 , Q 2 , Q 3 and Q 4 bonded to Pt with a phosphorus atom may be neutral ligands or anionic ligands, and neutral ligands include phosphine ligands, Examples include phosphate ester ligands, phosphite ester ligands, and phosphorus-containing heterocyclic ligands (phosphinin ligands, etc.).
- Anionic ligands include phosphino ligands and phosphinyl ligands.
- phosphoryl ligands The groups represented by Q 1 , Q 2 , Q 3, and Q 4 may have a substituent, and those listed as the substituent group A can be appropriately applied as the substituent.
- substituents may be connected to each other (when Q 3 and Q 4 are connected, a Pt complex of a cyclic tetradentate ligand is formed).
- the group represented by Q 1 , Q 2 , Q 3 and Q 4 is preferably an aromatic hydrocarbon ring ligand bonded to Pt with a carbon atom, and an aromatic heterocyclic ligand bonded to Pt with a carbon atom.
- L 1 , L 2 and L 3 represent a single bond or a divalent linking group.
- Divalent linking groups represented by L 1 , L 2 and L 3 include alkylene groups (methylene, ethylene, propylene, etc.), arylene groups (phenylene, naphthalenediyl), heteroarylene groups (pyridinediyl, thiophenediyl, etc.) ), Imino group (—NR L —) (such as phenylimino group), oxy group (—O—), thio group (—S—), phosphinidene group (—PR L —) (such as phenylphosphinidene group), silylene (-SiR L R L '-) ( dimethylsilylene group, a diphenylsilylene group), or the like combinations thereof.
- R L and R L ′ each independently represents an alkyl group or an aryl group. These linking groups may further have a substituent.
- L 1 , L 2 and L 3 are preferably a single bond, an alkylene group, an arylene group, a heteroarylene group, an imino group, an oxy group, a thio group or a silylene group. More preferably a single bond, an alkylene group, an arylene group or an imino group, still more preferably a single bond, an alkylene group or an arylene group, still more preferably a single bond, a methylene group or a phenylene group, still more preferably.
- Single bond, disubstituted methylene group more preferably single bond, dimethylmethylene group, diethylmethylene group, diisobutylmethylene group, dibenzylmethylene group, ethylmethylmethylene group, methylpropylmethylene group, isobutylmethylmethylene group, diphenyl Methylene, methylphenylmethylene, cyclohexanediyl, cycl A lopentanediyl group, a fluorenediyl group, and a fluoromethylmethylene group.
- L 1 is particularly preferably a dimethylmethylene group, a diphenylmethylene group, or a cyclohexanediyl group, and most preferably a dimethylmethylene group.
- L 2 and L 3 are most preferably a single bond.
- platinum complexes represented by the general formula (C-1) a platinum complex represented by the following general formula (C-2) is more preferable.
- L 21 represents a single bond or a divalent linking group.
- a 21 and A 22 each independently represent a carbon atom or a nitrogen atom.
- Z 21 and Z 22 each independently represent a nitrogen-containing aromatic heterocyclic ring.
- Z 23 and Z 24 each independently represent a benzene ring or an aromatic heterocycle.
- L 21 has the same meaning as L 1 in formula (C-1), and the preferred range is also the same.
- a 21 and A 22 each independently represent a carbon atom or a nitrogen atom. Of A 21 and A 22, Preferably, at least one is a carbon atom, it A 21 and A 22 are both carbon atoms are preferred from the standpoint of emission quantum yield stability aspects and complexes of the complex .
- Z 21 and Z 22 each independently represent a nitrogen-containing aromatic heterocycle.
- the nitrogen-containing aromatic heterocycle represented by Z 21 and Z 22 include a pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadiazole ring, Examples include thiadiazole rings.
- the ring represented by Z 21 and Z 22 is preferably a pyridine ring, a pyrazine ring, an imidazole ring or a pyrazole ring, more preferably a pyridine ring.
- the nitrogen-containing aromatic heterocycle represented by Z 21 and Z 22 may have a substituent, the substituent group A as a substituent on a carbon atom, and the substituent on a nitrogen atom as The substituent group B can be applied.
- the substituent on the carbon atom is preferably an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, or a halogen atom.
- the substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of shortening the wavelength, an electron donating group, a fluorine atom, and an aromatic ring group are preferable.
- an alkyl group, a dialkylamino group, an alkoxy group, A fluorine atom, an aryl group, an aromatic heterocyclic group and the like are selected.
- an electron withdrawing group is preferable, and for example, a cyano group, a perfluoroalkyl group, or the like is selected.
- the substituent on the nitrogen atom is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex.
- the substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.
- Z 23 and Z 24 each independently represent a benzene ring or an aromatic heterocycle.
- the nitrogen-containing aromatic heterocycle represented by Z 23 and Z 24 include a pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, triazole ring, oxadi Examples include an azole ring, a thiadiazole ring, a thiophene ring, and a furan ring.
- the ring represented by Z 23 and Z 24 is preferably a benzene ring, a pyridine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, or a thiophene ring, More preferred are a benzene ring, a pyridine ring and a pyrazole ring, and still more preferred are a benzene ring and a pyridine ring.
- the benzene ring and nitrogen-containing aromatic heterocycle represented by Z 23 and Z 24 may have a substituent.
- the substituent group A is substituted on the nitrogen atom.
- the substituent group B can be applied as the group.
- the substituent on carbon is preferably an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, or a halogen atom.
- the substituent is appropriately selected for controlling the emission wavelength and potential, but in the case of increasing the wavelength, an electron donating group and an aromatic ring group are preferable, for example, an alkyl group, a dialkylamino group, an alkoxy group, an aryl group, An aromatic heterocyclic group or the like is selected.
- an electron withdrawing group is preferable, and for example, a fluorine group, a cyano group, a perfluoroalkyl group, and the like are selected.
- the substituent on the nitrogen atom is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and an alkyl group or an aryl group is preferable from the viewpoint of the stability of the complex.
- the substituents may be linked to form a condensed ring, and the formed ring includes a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a pyrazole. Ring, thiophene ring, furan ring and the like.
- platinum complexes represented by the general formula (C-2) one of more preferred embodiments is a platinum complex represented by the following general formula (C-3).
- a 301 to A 313 each independently represent C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent.
- L 31 represents a single bond or a divalent linking group.
- L 31 has the same meaning as L 21 in formula (C-2), and the preferred range is also the same.
- a 301 to A 306 each independently represents C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent.
- substituent represented by R those exemplified as the substituent group A can be applied.
- a 301 to A 306 are preferably C—R, and Rs may be connected to each other to form a ring.
- R in A 302 and A 305 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group, or a cyano group. More preferably a hydrogen atom, an amino group, an alkoxy group, an aryloxy group or a fluorine group, and particularly preferably a hydrogen atom or a fluorine group.
- R in A 301 , A 303 , A 304 and A 306 is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group or a cyano group, more preferably a hydrogen atom or an amino group.
- a 307 , A 308 , A 309 and A 310 each independently represent C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent. As the substituent represented by R, those exemplified as the substituent group A can be applied.
- R is preferably a hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, aromatic heterocyclic group, dialkylamino group, diarylamino Group, alkyloxy group, cyano group, halogen atom, more preferably hydrogen atom, alkyl group, perfluoroalkyl group, aryl group, dialkylamino group, cyano group, fluorine atom, more preferably hydrogen atom, alkyl group. , A trifluoromethyl group and a fluorine atom. If possible, the substituents may be linked to form a condensed ring structure.
- a 308 is preferably a nitrogen atom.
- the 6-membered ring formed from two carbon atoms and A 307 , A 308 , A 309 and A 310 includes a benzene ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring.
- a pyridazine ring and a triazine ring more preferably a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring and a pyridazine ring, and particularly preferably a benzene ring and a pyridine ring.
- the 6-membered ring is a pyridine ring, a pyrazine ring, a pyrimidine ring, or a pyridazine ring (particularly preferably a pyridine ring), a hydrogen atom present at a position where a metal-carbon bond is formed as compared with a benzene ring. Since the acidity is improved, it is advantageous in that a metal complex is more easily formed.
- a 311 , A 312 and A 313 each independently represent C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent.
- substituent represented by R those exemplified as the substituent group A can be applied.
- R is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, an aromatic heterocyclic group, a dialkylamino group, a diarylamino group, an alkyl An oxy group, a cyano group, and a halogen atom, more preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, a dialkylamino group, a cyano group, and a fluorine atom, and more preferably a hydrogen atom, an alkyl group, and trifluoro A methyl group and a fluorine atom.
- platinum complexes represented by the general formula (C-2) one of the more preferred embodiments is a platinum complex represented by the following general formula (C-4).
- a 401 to A 414 each independently represents C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent.
- L 41 represents a single bond or a divalent linking group.
- a 401 to A 414 each independently represents C—R or a nitrogen atom.
- R represents a hydrogen atom or a substituent.
- a 401 to A 406 and L 41 have the same meanings as A 301 to A 306 and L 31 in formula (C-3), and preferred ranges thereof are also the same.
- the number of nitrogen atoms is preferably 0 to 2, and more preferably 0 or 1.
- a 408 and A 412 are preferably nitrogen atoms, and both A 408 and A 412 are more preferably nitrogen atoms.
- R of A 408 and A 412 is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group, A cyano group, more preferably a hydrogen atom, a perfluoroalkyl group, an alkyl group, an aryl group, a fluorine group, or a cyano group, and particularly preferably a hydrogen atom, a phenyl group, a perfluoroalkyl group, or a cyano group.
- R in A 407 , A 409 , A 411 and A 413 is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a fluorine group or a cyano group, more preferably A hydrogen atom, a perfluoroalkyl group, a fluorine group and a cyano group are particularly preferred, and a hydrogen atom, a phenyl group and a fluorine group are particularly preferred.
- R in A 410 and A 414 is preferably a hydrogen atom or a fluorine group, and more preferably a hydrogen atom.
- platinum complexes represented by the general formula (C-2) one of the more preferred embodiments is a platinum complex represented by the following general formula (C-5).
- a 501 to A 512 each independently represents C—R or a nitrogen atom, R represents a hydrogen atom or a substituent, and L 51 represents a single bond or a divalent linkage. Represents a group.
- a 501 to A 506 and L 51 have the same meanings as A 301 to A 306 and L 31 in formula (C-3), and preferred ranges thereof are also the same.
- a 507 , A 508, A 509 and A 510 , A 511, and A 512 are each independently the same as A 311 , A 312, and A 313 in formula (C-3), and the preferred ranges are also the same. is there.
- platinum complexes represented by the general formula (C-1) another more preferable embodiment is a platinum complex represented by the following general formula (C-6).
- L 61 represents a single bond or a divalent linking group.
- a 61 independently represents a carbon atom or a nitrogen atom.
- Z 61 and Z 62 each independently represent a nitrogen-containing aromatic heterocyclic ring.
- Z 63 independently represents a benzene ring or an aromatic heterocyclic ring, and Y is an anionic acyclic ligand bonded to Pt.
- L 61 has the same meaning as L 1 in formula (C-1), and the preferred range is also the same.
- a 61 represents a carbon atom or a nitrogen atom. In view of the stability of the complex and the light emission quantum yield of the complex, A 61 is preferably a carbon atom.
- Z 61 and Z 62 have the same meanings as Z 21 and Z 22 in formula (C-2), respectively, and preferred ranges are also the same.
- Z 63 has the same meaning as Z 23 in formula (C-2), and the preferred range is also the same.
- Y is an anionic acyclic ligand that binds to Pt.
- An acyclic ligand is one in which atoms bonded to Pt do not form a ring in the form of a ligand.
- a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable, a nitrogen atom and an oxygen atom are more preferable, and an oxygen atom is the most preferable.
- a vinyl ligand is mentioned as Y couple
- Examples of Y bonded to Pt with an oxygen atom include an alkoxy ligand, an aryloxy ligand, a heteroaryloxy ligand, an acyloxy ligand, a silyloxy ligand, a carboxyl ligand, a phosphate ligand, Examples thereof include sulfonic acid ligands.
- Examples of Y bonded to Pt with a sulfur atom include alkyl mercapto ligands, aryl mercapto ligands, heteroaryl mercapto ligands, and thiocarboxylic acid ligands.
- the ligand represented by Y may have a substituent, and those exemplified as the substituent group A can be appropriately applied as the substituent. Moreover, substituents may be connected to each other.
- the ligand represented by Y is preferably a ligand bonded to Pt with an oxygen atom, more preferably an acyloxy ligand, an alkyloxy ligand, an aryloxy ligand, a heteroaryloxy ligand. , A silyloxy ligand, and more preferably an acyloxy ligand.
- platinum complexes represented by the general formula (C-6) one of more preferred embodiments is a platinum complex represented by the following general formula (C-7).
- a 701 to A 710 each independently represents C—R or a nitrogen atom, R represents a hydrogen atom or a substituent, L 71 represents a single bond or a divalent linking group, Y represents An anionic acyclic ligand that binds to Pt.
- L 71 has the same meaning as L 61 in formula (C-6), and the preferred range is also the same.
- a 701 to A 710 have the same meanings as A 301 to A 310 in formula (C-3), and preferred ranges are also the same.
- Y has the same meaning as that in formula (C-6), and the preferred range is also the same.
- platinum complex represented by the general formula (C-1) are described in JP-A-2005-310733, [0143] to [0152], [0157] to [0158], and [0162] to [0168].
- Examples of the platinum complex compound represented by the general formula (C-1) include Journal of Organic Chemistry 53,786, (1988), G.S. R. Newkome et al. ), Page 789, the method described in left line 53 to right line 7, line 790, the method described in left line 18 to line 38, the method described in page 790, right line 19 to line 30 and The combination, Chemische Berichte 113, 2749 (1980), H.C. Lexy et al.), Page 2752, lines 26 to 35, and the like.
- a ligand or a dissociated product thereof and a metal compound are mixed with a solvent (for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfone solvent,
- a solvent for example, a halogen solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfone solvent
- a base inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.
- a base inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine, potassium carbonate, etc.
- a base inorganic or organic various bases such as sodium methoxide, t-butoxypotassium, triethylamine
- the content thereof when the compound represented by the general formula (C-1) is contained in the light emitting layer, the content thereof is preferably 1 to 30% by mass in the light emitting layer, and 3 to 25% by mass. More preferably, the content is 5 to 20% by mass.
- the present invention also relates to a light emitting layer comprising a compound represented by the general formula (1) and a compound represented by the general formula (PQ-1).
- the light emitting layer of this invention can be used for an organic electroluminescent element.
- the light emitting layer of the present invention preferably further contains a compound represented by the general formula (C-1).
- the external quantum efficiency can be further increased.
- an organic electroluminescent element excellent in driving durability can be obtained.
- the content of the compound represented by formula (C-1) in the light emitting layer of the present invention is preferably 1 to 30% by mass, more preferably 3 to 20% by mass in the light emitting layer.
- the present invention also relates to a composition containing the compound represented by the general formula (1) and the compound represented by the general formula (PQ-1).
- the content of the compound represented by the general formula (1) in the composition of the present invention is preferably 50 to 95% by mass, and more preferably 70 to 90% by mass.
- the content of the compound represented by the general formula (PQ-1) in the composition of the present invention is preferably 1 to 40% by mass, and more preferably 5 to 20% by mass.
- composition of the present invention may be organic or inorganic, and as organic materials, materials described as host materials, fluorescent light-emitting materials, phosphorescent light-emitting materials, and hydrocarbon materials described later can be applied.
- a host material or a hydrocarbon material Preferably a host material or a hydrocarbon material, and more preferably a compound represented by the general formula (VI).
- the composition of the present invention can form an organic layer of an organic electroluminescence device by a dry film forming method such as a vapor deposition method or a sputtering method, a transfer method, a printing method, or the like.
- the composition of the present invention preferably further contains a compound represented by the general formula (C-1).
- the content of the compound represented by the general formula (C-1) in the composition of the present invention is preferably 1 to 30% by mass and more preferably 3 to 20% by mass in the composition.
- the organic electroluminescent element of the present invention is an organic electroluminescent element having a pair of electrodes on a substrate and a light emitting layer between the electrodes, and the compound represented by the following general formula (1) in the light emitting layer: And a compound represented by the general formula (PQ-1). It is preferable to further have a layer containing the compound represented by the general formula (1) between the light emitting layer and the cathode.
- the light-emitting layer and the layer containing the compound represented by the general formula (1) are organic layers, and may further have a plurality of organic layers.
- at least one of the anode and the cathode is preferably transparent or translucent.
- FIG. 1 shows an example of the configuration of an organic electroluminescent device according to the present invention.
- a light emitting layer 6 is sandwiched between an anode 3 and a cathode 9 on a substrate 2.
- a hole injection layer 4, a hole transport layer 5, a light emitting layer 6, a hole block layer 7, and an electron transport layer 8 are laminated in this order between the anode 3 and the cathode 9.
- Anode / hole transport layer / light emitting layer / electron transport layer / cathode Anode / hole transport layer / light emitting layer / second electron transport layer (hole block layer) / first electron transport layer / cathode
- Anode / hole injection layer / hole transport layer (electron block layer) / light emitting layer / second electron transport layer (hole block layer) / first electron transport layer / cathode Anode / hole injection layer / first hole transport layer / second hole transport layer (electron block layer) / light emitting layer / second electron transport layer (hole block layer) / first electron transport layer / cathode
- the element configuration, the substrate, the cathode, and the anode of the organic electroluminescence element are described in detail in, for example, Japanese Patent Application Laid-Open No. 2008-270736, and the matters described in the publication can be applied to the present invention.
- the substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer.
- an organic material it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.
- the anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.
- the anode is usually provided as a transparent anode.
- the cathode usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light-emitting element.
- the electrode material can be selected as appropriate.
- Organic layer in the present invention will be described.
- each organic layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.
- the light emitting material in the present invention is preferably a compound represented by the general formula (PQ-1).
- the light emitting material in the light emitting layer is generally contained in the light emitting layer in an amount of 0.1% by mass to 50% by mass with respect to the total mass of the compound forming the light emitting layer. From the viewpoint of durability and external quantum efficiency.
- the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass.
- the thickness of the light emitting layer is not particularly limited, but is usually preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm, and more preferably 5 nm to 100 nm from the viewpoint of external quantum efficiency. More preferably.
- the light emitting layer in the element of the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material.
- the light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one kind or two or more kinds.
- the host material is preferably a charge transport material.
- the host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed.
- the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
- the light emitting layer in the element of the present invention is preferably a layer using a compound represented by the general formula (1) as a host material and a compound represented by the general formula (PQ-1) as a light emitting material. Further, the light emitting layer may be a single layer or a multilayer of two or more layers. When there are a plurality of light emitting layers, the compound represented by the general formula (1) and the compound represented by (PQ-1) may be contained in two or more light emitting layers. In addition, each light emitting layer may emit light with different emission colors.
- the host material used in the present invention is preferably a compound represented by the general formula (1).
- the compound represented by the general formula (1) is capable of transporting both holes and electrons, and in combination with the compound represented by the general formula (PQ-1), the carrier balance between holes and electrons is good.
- PQ-1 the compound represented by the general formula (PQ-1)
- the host material used in the present invention may further contain the following compounds.
- the triplet lowest excitation energy (T 1 energy) of the host material is higher than the T 1 energy of the phosphorescent light emitting material. It is preferable in terms of purity, luminous efficiency, and driving durability.
- the content of the host compound in the present invention is not particularly limited, but from the viewpoint of light emission efficiency and driving voltage, it is 15% by mass to 95% by mass with respect to the total compound mass forming the light emitting layer. Preferably there is.
- the content is preferably 10% by mass to 100% by mass in the layer, and 30% by mass. More preferably, it is contained in an amount of ⁇ 100% by mass.
- fluorescent material examples include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives.
- Condensed aromatic compounds perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl Complexes of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives and pyromethene derivatives
- complexes represented, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.
- phosphorescent material examples include, in addition to the compound represented by the general formula (1), for example, US6303238B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1, WO02 / 02714A2, WO02 / 15645A1, WO02 / 44189A1, WO05 / 19373A2, JP2001-247859, JP2002-302671, JP2002-117978, JP2003-133074, JP2002-235076, JP2003-200376 123982, JP2002-170684, EP121257, JP2002-226495, JP2002-234894, JP2001-247859, JP2001-29 470, JP 2002-173675, JP 2002-203678, JP 2002-203679, JP 2004-357771, JP 2006-256999,
- the phosphorescent light emitting compounds described in the above patent documents are mentioned.
- more preferable light emitting materials include Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex. Eu complex, Tb complex, Gd complex, Dy complex, and Ce complex.
- an Ir complex, a Pt complex, or a Re complex among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or Re complexes are preferred.
- an Ir complex, a Pt complex, or a Re complex containing a tridentate or higher polydentate ligand is particularly preferable.
- the content of the phosphorescent material is preferably in the range of 0.1% by mass to 50% by mass and preferably in the range of 0.2% by mass to 50% by mass with respect to the total mass of the light emitting layer in the light emitting layer. More preferably, the range of 0.3% by mass or more and 40% by mass or less is further preferable, and the range of 20% by mass or more and 30% by mass or less is most preferable.
- the content of the phosphorescent material (the compound represented by the general formula (PQ-1) and / or the phosphorescent material used in combination) that can be used in the present invention is 0.1 mass relative to the total mass of the light emitting layer. % To 50% by mass, more preferably 1% to 40% by mass, and most preferably 5% to 30% by mass. In particular, in the range of 5% by mass or more and 30% by mass or less, the chromaticity of light emission of the organic electroluminescent element is less dependent on the addition concentration of the phosphorescent light emitting material.
- the organic electroluminescent element of the present invention contains 5 to 30% by mass of at least one of the above-mentioned compounds (PQ-1) (compound represented by the general formula (PQ-1)) based on the total mass of the light emitting layer. Most preferred.
- the organic electroluminescent device preferably further contains a hydrocarbon compound, and more preferably contains a hydrocarbon compound in the light emitting layer.
- the hydrocarbon compound is preferably a compound represented by the following general formula (VI).
- the compound represented by the general formula (VI) used in the organic electroluminescence device is excellent in chemical stability, has little alteration such as decomposition of the material during device driving, and is caused by a decomposition product of the material. It is possible to prevent a decrease in the efficiency of the organic electroluminescence device and a decrease in the device life.
- the compound represented by the general formula (VI) will be described.
- R 4 , R 6 , R 8 , R 10 , and X 4 to X 15 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
- the alkyl group represented by R 4 , R 6 , R 8 , R 10 , X 4 to X 15 in the general formula (VI) may be substituted with an adamantane structure or an aryl structure, and has 1 to 70 carbon atoms. Preferably 1 to 50 carbon atoms, more preferably 1 to 30 carbon atoms, still more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and linear alkyl having 2 to 6 carbon atoms. The group is most preferred.
- Examples of the alkyl group represented by R 4 , R 6 , R 8 , R 10 , X 4 to X 15 in the general formula (VI) include, for example, an nC 50 H 101 group and an nC 30 H 61 group. , 3- (3,5,7-triphenyladamantan-1-yl) propyl group (31 carbon atoms), trityl group (19 carbon atoms), 3- (adamantan-1-yl) propyl group (13 carbon atoms) 9-decalyl group (10 carbon atoms), benzyl group (7 carbon atoms), cyclohexyl group (6 carbon atoms), n-hexyl group (6 carbon atoms), n-pentyl group (5 carbon atoms), n-butyl A group (4 carbon atoms), an n-propyl group (3 carbon atoms), a cyclopropyl group (3 carbon atoms), an ethyl group (2 carbon atoms), a methyl
- the aryl group represented by R 4 , R 6 , R 8 , R 10 , X 4 to X 15 in the general formula (VI) may be substituted with an adamantane structure or an alkyl structure, and has 6 to 30 carbon atoms. Preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 10 carbon atoms, and most preferably 6 carbon atoms.
- Examples of the aryl group represented by R 4 , R 6 , R 8 , R 10 , X 4 to X 15 in the general formula (VI) include, for example, a 1-pyrenyl group (16 carbon atoms), a 9-anthracenyl group ( 14) carbon, 1-naphthyl group (10 carbon atoms), 2-naphthyl group (10 carbon atoms), pt-butylphenyl group (10 carbon atoms), 2-m-xylyl group (8 carbon atoms), 5-m-xylyl group (8 carbon atoms), o-tolyl group (7 carbon atoms), m-tolyl group (7 carbon atoms), p-tolyl group (7 carbon atoms), phenyl group (6 carbon atoms), etc. Is mentioned.
- R 4 , R 6 , R 8 and R 10 in the general formula (VI) may be a hydrogen atom, an alkyl group or an aryl group, but the above-mentioned high glass transition temperature is preferable. From the viewpoint, at least one is preferably an aryl group, more preferably at least two are aryl groups, and particularly preferably 3 to 4 are aryl groups.
- X 4 to X 15 in the general formula (VI) may be a hydrogen atom, an alkyl group, or an aryl group, but are preferably a hydrogen atom or an aryl group, Particularly preferred is an atom.
- the molecular weight of the compound represented by the general formula (VI) in the present invention is 2000 or less from the viewpoint of vapor deposition suitability and solubility since an organic electroluminescent device is prepared using a vacuum vapor deposition process or a solution coating process. Is preferable, 1200 or less is more preferable, and 1000 or less is particularly preferable. Further, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Is more preferable, and 400 or more is particularly preferable.
- the compound represented by the general formula (VI) is preferably solid at room temperature (25 ° C), more preferably solid at room temperature (25 ° C) to 40 ° C, and from room temperature (25 ° C). Particularly preferred is a solid in the range of 60 ° C.
- a solid phase can be formed at room temperature by combining with other materials.
- the use of the compound represented by the general formula (VI) is not limited, and the compound may be contained in any layer in the organic layer.
- a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer described later are used.
- it is contained in any one or more of, and more preferably contained in any one or more of the light emitting layer, hole injection layer, hole transport layer, electron transport layer, and electron injection layer, and light emission. It is particularly preferable that it is contained in any one or more of the layer, the hole injection layer, and the hole transport layer, and most preferably included in the light emitting layer.
- the content of the compound represented by the general formula (VI) needs to be limited to an amount that does not suppress the charge transport property.
- the compound represented by the general formula (VI) is preferably contained in an amount of 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, and 0.1 to 25% by mass. Is particularly preferred.
- the compound represented by the general formula (VI) may contain only one kind in any organic layer, and contains a combination of a plurality of compounds represented by the general formula (VI) in any ratio. You may do it.
- the compound represented by the general formula (VI) can be synthesized by appropriately combining adamantane or a halogenated adamantane with an alkyl halide or an alkylmagnesium halide (Grignard reagent).
- a halogenated adamantane and an alkyl halide can be coupled using indium (Reference 1).
- Alkyl halides can also be converted to alkyl copper reagents and coupled with aromatic Grignard reagents (Reference 2).
- Alkyl halides can also be coupled using an appropriate aryl boric acid and a palladium catalyst (Reference 3).
- Reference 1 Tetrahedron Lett. 39, 1998, 9557-9558.
- Reference 2 Tetrahedron Lett. 39, 1998, 2095-2096.
- Reference 3 J.M. Am. Chem. Soc. 124, 2002, 13662-13663.
- the adamantane skeleton having an aryl group can be synthesized by appropriately combining adamantane or a halogenated adamantane with the corresponding arene or aryl halide.
- the thickness of the light emitting layer is not particularly limited, but is usually preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and further preferably 10 nm to 100 nm.
- the electrode includes an anode, a charge transport layer is provided between the light emitting layer and the anode, and the charge transport layer includes a carbazole compound.
- the charge transport layer refers to a layer in which charge transfer occurs when a voltage is applied to the organic electroluminescent element. Specific examples include a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, and an electron injection layer. A hole injection layer, a hole transport layer, an electron blocking layer, or a light emitting layer is preferable.
- the charge transport layer formed by the coating method is a hole injection layer, a hole transport layer, an electron block layer, or a light emitting layer, it is possible to produce an organic electroluminescent element with low cost and high efficiency.
- the charge transport layer is more preferably a hole injection layer, a hole transport layer, or an electron block layer.
- the hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side.
- the hole injection material and the hole transport material used for these layers may be a low molecular compound or a high molecular compound.
- pyrrole derivatives carbazole derivatives, pyrrole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcones Derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, phthalocyanine compounds, porphyrin compounds, thiophene derivatives, organosilane derivatives, carbon, iridium complexes, etc. It is preferable that it is a layer containing these various metal complexes.
- the hole injection layer and the hole transport layer preferably contain a carbazole compound.
- the carbazole compound is preferably a carbazole compound represented by the following general formula (a).
- R a represents a substituent which substitutes the hydrogen atoms of the backbone, the integer R a is optionally the same or different in the presence of two or more .n a 0-8 To express.
- the compound represented by the general formula (a) is preferably contained in an amount of 50 to 100% by mass, and contained in an amount of 80 to 100% by mass.
- the content is preferably 95 to 100% by mass.
- the compound represented by the general formula (a) may contain only one kind in any organic layer, and contains a combination of a plurality of compounds represented by the general formula (a) in an arbitrary ratio. You may do it.
- the thickness of the hole transport layer containing the compound represented by the general formula (a) is 1 nm to 500 nm. It is preferably 3 nm to 200 nm, more preferably 5 nm to 100 nm.
- the hole transport layer is preferably provided in contact with the light emitting layer.
- the hole transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
- substituent represented by Ra include a halogen atom, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, and an aromatic heterocyclic group.
- An alkyl group having 10 or less carbon atoms and a carbon number of 10 The following substituted or unsubstituted aryl groups are preferable, and an alkyl group having 6 or less carbon atoms is more preferable.
- na is preferably from 0 to 4, more preferably from 0 to 2.
- the hydrogen atoms constituting the general formula (a) include hydrogen isotopes (deuterium atoms and the like). In this case, all hydrogen atoms in the compound may be replaced with hydrogen isotopes, or a mixture in which a part is a compound containing hydrogen isotopes may be used.
- the compound represented by the general formula (a) can be synthesized by combining various known synthesis methods.
- carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- LF Tieze by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo).
- the compound represented by the general formula (a) preferably forms a thin layer by a vacuum deposition process, but a wet process such as solution coating can also be suitably used.
- the molecular weight of the compound is preferably 2000 or less, more preferably 1200 or less, and particularly preferably 800 or less from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred.
- An electron-accepting dopant can be contained in the hole injection layer or the hole transport layer of the organic electroluminescence device of the present invention.
- an inorganic compound or an organic compound can be used as long as it has an electron-accepting property and oxidizes an organic compound.
- examples of the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, and metal oxides such as vanadium pentoxide and molybdenum trioxide.
- a compound having a nitro group, halogen, cyano group, trifluoromethyl group or the like as a substituent a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.
- JP2004-342614, JP2005-72012, JP20051666667 The compounds described in JP-A-2005-209643 and the like can be preferably used.
- electron accepting dopants may be used alone or in combination of two or more.
- the amount of the electron-accepting dopant used varies depending on the type of material, but is preferably 0.01% by mass to 50% by mass with respect to the hole transport layer material, and is 0.05% by mass to 20% by mass. It is more preferable that the content be 0.1% by mass to 10% by mass.
- the thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
- the thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
- the thickness of the hole injection layer is preferably from 0.1 nm to 200 nm, more preferably from 0.5 nm to 100 nm, and even more preferably from 1 nm to 100 nm.
- the hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .
- the electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side.
- the hole injection layer, the hole transport layer, the electron injection layer, and the electron transport layer the matters described in paragraph numbers [0165] to [0167] of JP-A-2008-270736 can be applied to the present invention. .
- the hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side.
- a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
- organic compounds constituting the hole blocking layer include aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4- aluminum complexes such as phenylphenolate (abbreviated as Balq)), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-dimethyl-4,7-diphenyl-1,10-) phenanthroline derivatives such as phenanthroline (abbreviated as BCP)) and the like.
- BCP phenanthroline
- the thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
- the hole blocking layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.
- the electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side.
- an electron blocking layer can be provided as an organic layer adjacent to the light emitting layer on the anode side.
- the thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
- the electron blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
- the entire organic EL element may be protected by a protective layer.
- the protective layer the matters described in JP-A-2008-270736, paragraphs [0169] to [0170] can be applied to the present invention.
- the element of this invention may seal the whole element using a sealing container.
- the sealing container the matters described in paragraph [0171] of JP-A-2008-270736 can be applied to the present invention.
- the present invention also relates to a film forming method for forming a film by sublimation by simultaneously heating the compound represented by the general formula (1) and the compound represented by the general formula (PQ-1).
- the compound represented by the general formula (1) and the compound represented by the general formula (PQ-1) are mixed, and the composition of the present invention may be used.
- the content ratio of the compound represented by the general formula (1) and the compound represented by the general formula (PQ-1) is represented by the general formula (PQ-1) with respect to the compound represented by the general formula (1).
- the compound is preferably 1% to 45%, more preferably 1% to 25%.
- the heating temperature is preferably 200 ° C.
- the heating time is preferably 0.1 hours to 350 hours, more preferably 0.1 hours to 150 hours. According to the film forming method of the present invention, there is an advantage that a light emitting layer film having high efficiency, high durability, and little color change at high temperature driving can be easily formed.
- the organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode.
- a direct current which may include an alternating current component as necessary
- the driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234585, and JP-A-8-2441047.
- the driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6,023,308 can be applied.
- the light emitting element of the present invention can improve the light extraction efficiency by various known devices. For example, by processing the substrate surface shape (for example, forming a fine concavo-convex pattern), controlling the refractive index of the substrate / ITO layer / organic layer, controlling the film thickness of the substrate / ITO layer / organic layer, etc. It is possible to improve light extraction efficiency and external quantum efficiency.
- the external quantum efficiency of the light emitting device of the present invention is preferably 20% or more and 30% or less.
- the value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C., or the value of the external quantum efficiency near 100 to 300 cd / m 2 when the device is driven at 20 ° C. Can do.
- the light-emitting element of the present invention may be a so-called top emission type in which light emission is extracted from the anode side.
- the organic EL element in the present invention may have a resonator structure.
- a multilayer film mirror made of a plurality of laminated films having different refractive indexes, a transparent or translucent electrode, a light emitting layer, and a metal electrode are superimposed on a transparent substrate.
- the light generated in the light emitting layer resonates repeatedly with the multilayer mirror and the metal electrode as a reflection plate.
- a transparent or translucent electrode and a metal electrode each function as a reflecting plate on a transparent substrate, and light generated in the light emitting layer repeats reflection and resonates between them.
- the optical path length determined from the effective refractive index of the two reflectors and the refractive index and thickness of each layer between the reflectors is adjusted to an optimum value to obtain the desired resonant wavelength. Is done.
- the calculation formula in the case of the first embodiment is described in JP-A-9-180883.
- the calculation formula in the case of the second embodiment is described in Japanese Patent Application Laid-Open No. 2004-127795.
- the light-emitting element of the present invention can be suitably used for light-emitting devices, pixels, display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like. .
- it is preferably used for a device driven in a region having a high light emission luminance such as a lighting device and a display device.
- FIG. 2 is a cross-sectional view schematically showing an example of the light emitting device of the present invention.
- the light-emitting device 20 in FIG. 2 includes a transparent substrate (substrate) 2, an organic electroluminescent element 10, a sealing container 16, and the like.
- the organic electroluminescent device 10 is configured by sequentially laminating an anode (first electrode) 3, an organic layer 11, and a cathode (second electrode) 9 on a substrate 2.
- a protective layer 12 is laminated on the cathode 9, and a sealing container 16 is provided on the protective layer 12 with an adhesive layer 14 interposed therebetween.
- a part of each electrode 3 and 9, a partition, an insulating layer, etc. are abbreviate
- the adhesive layer 14 a photocurable adhesive such as an epoxy resin or a thermosetting adhesive can be used, and for example, a thermosetting adhesive sheet can also be used.
- the use of the light-emitting device of the present invention is not particularly limited, and for example, it can be a display device such as a television, a personal computer, a mobile phone, and electronic paper in addition to a lighting device.
- FIG. 3 is a cross-sectional view schematically showing an example of a lighting device according to an embodiment of the present invention.
- the illumination device 40 according to the embodiment of the present invention includes the organic EL element 10 and the light scattering member 30 described above. More specifically, the lighting device 40 is configured such that the substrate 2 of the organic EL element 10 and the light scattering member 30 are in contact with each other.
- the light scattering member 30 is not particularly limited as long as it can scatter light.
- the light scattering member 30 is a member in which fine particles 32 are dispersed on a transparent substrate 31.
- the transparent substrate 31 for example, a glass substrate can be preferably cited.
- transparent resin fine particles can be preferably exemplified.
- the glass substrate and the transparent resin fine particles known ones can be used.
- the incident light is scattered by the light scattering member 30, and the scattered light is emitted from the light emitting surface 30B. It is emitted as illumination light.
- the compounds represented by the general formula (1) used in the examples are WO03 / 080760 pamphlet, WO03 / 078541 pamphlet, WO05 / 085387 pamphlet, WO05 / 022962. No. pamphlet etc. was synthesized as a reference.
- Exemplified Compound 4 uses m-bromobenzaldehyde as a starting material and is a method described in WO05 / 085387 pamphlet [0074]-[0075] (page 45, line 11 to page 46, line 18). Can be synthesized.
- Exemplified compound 77 can be synthesized by the method described on page 137, page 10 to page 139, line 9 of International Publication No.
- FR-1 to FR-3 can be synthesized by various methods such as the method described in Japanese Patent No. 3929632, for example.
- FR-2 can be synthesized by the method described on page 18, line 2 to line 13 of Patent Publication No. 3929632, using 2-phenylquinoline as a starting material.
- FR-3 can be synthesized by the method described on page 18, line 14 to page 19, line 8 of Japanese Patent Publication No. 3929632 using 2- (2-naphthyl) quinoline as a starting material.
- Compound 8-4 can be prepared according to Journal of Organic Chemistry 53,786 (1988), G.I. R. Nekome et al. Of page 789, left column 53 to right column 7, line 790, left column, line 18 to line 38, page 790, right column, line 19 to line 30 and the combination thereof.
- the following compound BBPy can be synthesized by the method described in JP-A 2007-19462, page 52, line 34 to page 53, line 23.
- Example 1 A glass substrate having an indium tin oxide (ITO) film having a thickness of 0.5 mm and a square of 2.5 cm (manufactured by Geomatic Co., Ltd., surface resistance: 10 ⁇ / ⁇ ) was placed in a cleaning container, and ultrasonically cleaned in 2-propanol. UV-ozone treatment was performed for a minute. The following organic layers were sequentially deposited on the transparent anode (ITO film) by vacuum deposition.
- ITO indium tin oxide
- First layer CuPc (copper phthalocyanine): film thickness 10 nm
- Second layer NPD (N, N′-di- ⁇ -naphthyl-N, N′-diphenyl) -benzidine): film thickness 30 nm
- Third layer dopant (Ir (btp) 2 (acac), 5 mass%), host material (CBP, 95 mass%): film thickness 30 nm
- Fifth layer Alq (tris (8-hydroxyquinoline) aluminum complex): film thickness 40 nm
- 0.2 nm of lithium fluoride and 70 nm of metallic aluminum were vapor-deposited in this order to form a cathode.
- a film containing two or more materials was formed by sublimation by simultaneously heating the materials.
- the obtained laminate is placed in a glove box substituted with argon gas without being exposed to the atmosphere, and a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.) are used.
- the device of Comparative Example 1 was obtained.
- Examples 1 to 59 and Comparative Examples 2 to 13 Various elements were fabricated in the same manner as in Comparative Example 1 except that the constituent material of the third layer (host material, dopant) and the constituent material of the fourth layer were changed as shown in Tables 1 to 6 below.
- the third layer of Example 40 shows that 85% by mass of Exemplified Compound 4 as a host material, 5% by mass of FR-1, and 10% by mass of Platinum Complex 2-3 were used.
- Example 60 A glass substrate having an indium tin oxide (ITO) film having a thickness of 0.5 mm and a square of 2.5 cm (manufactured by Geomatic Co., Ltd., surface resistance: 10 ⁇ / ⁇ ) was placed in a cleaning container, and ultrasonically cleaned in 2-propanol. UV-ozone treatment was performed for a minute. The following organic layers were sequentially deposited on the transparent anode (ITO film) by vacuum deposition.
- ITO indium tin oxide
- First layer CuPc (copper phthalocyanine): film thickness 10 nm
- Second layer NPD (N, N′-di- ⁇ -naphthyl-N, N′-diphenyl) -benzidine): film thickness 30 nm
- Third layer Adjacent layer material (V-1): film thickness 3 nm
- Fourth layer dopant (FR-1, 5 mass%), host material (exemplary compound 4, 95 mass%): film thickness 30 nm
- Sixth layer Alq (tris (8-hydroxyquinoline) aluminum complex): film thickness 40 nm
- 0.2 nm of lithium fluoride and 70 nm of metallic aluminum were vapor-deposited in this order to form a cathode.
- the obtained laminate is placed in a glove box substituted with argon gas without being exposed to the atmosphere, and a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.) are used. And the device of Example 60 was obtained.
- Example 60 to 65 Various elements were produced in the same manner as in Example 60 except that the constituent material of the third layer and the constituent material (host material, dopant) of the fourth layer were changed as shown in Table 7 below.
- (C) Change in chromaticity when driven at high temperature
- the luminance is 500 cd / m 2
- the host material containing the compound having a carbazole group represented by the general formula (1) and the specific iridium complex represented by the general formula (PQ-1) are used for the light emitting layer. It can be seen that the device according to the present invention has extremely excellent external quantum efficiency and driving durability as compared with the device of the comparative example, and there is little change in chromaticity after high temperature driving.
- the light emitting element of the present invention is designed to increase the light emission efficiency in such a case. Therefore, it can be used advantageously.
- the element of the present invention is excellent in luminous efficiency and durability even when used in a high temperature environment such as in-vehicle use, and is suitable for a light emitting device, a display device, and a lighting device.
- the organic electroluminescent element of the present invention has high external quantum efficiency and is excellent in durability. Further, since the change in chromaticity at the time of high-temperature driving is small, it can also be applied to applications that require driving durability in high-temperature environments such as in-vehicle applications.
- This application includes Japanese patent applications filed on July 31, 2009 (Japanese Patent Application No. 2009-180223), Japanese patent applications filed on August 31, 2009 (Japanese Patent Application No. 2009-201155), and applications filed on September 25, 2009. Based on Japanese patent application (Japanese Patent Application No. 2009-221663), the contents of which are incorporated herein by reference
- Cathode 10 Organic electroluminescent device (organic EL device) DESCRIPTION OF SYMBOLS 11 ... Organic layer 12 ... Protective layer 14 ... Adhesive layer 16 ... Sealing container 20 ... Light emitting device 30 ... Light scattering member 30A ... Light incident surface 30B ... Light Outgoing surface 31 ... Transparent substrate 32 ... Fine particles 40 ... Illumination device
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Abstract
Description
また、発光材料をホスト材料中にドープした発光層を用いるドープ型素子が広く採用されている。ホスト材料の開発も盛んに行われており、赤色燐光素子用のホスト材料としてはCBP(4,4’-bis(N-carbazolyl)biphenyl)、Balq(Aluminum (III)bis(2-methyl-8-quinolinato)4-phenylphenolate)を用いる例が良く知られている(例えば、特許文献2参照)。
例えば、特許文献2には高効率及び長寿命の素子の作製を目的として、芳香族多環縮環系材料を赤色燐光材料のホスト材料に用いる発明が開示されているが、素子の発光効率、高温駆動時の耐久性は十分ではない。更に、ディスプレイや照明用途を考えた場合、駆動に伴い色度が変化する問題があり、改善が求められている。
従来、素子の耐久性評価において、駆動電圧の上昇や効率の低下と共に駆動に伴う色度の変化が評価項目として挙げられてきた。また、環境温度も室温から(おもに加速試験の意味で)高温での評価もなされてきた。しかしながら、高温駆動時に低温よりも色度の変化量が大きくなることは注目されておらず、80℃以上の高温にもなりうる車載パネル用途などを考えた場合、高温駆動時の色度の変化は重要な問題になることが予想される。
しかしながら、本発明者らは、カルバゾール基を含む本発明のホスト材料を、特定のイリジウム錯体材料と組み合わせた場合に、耐久性向上効果が発現することを見出した。
すなわち、本発明の目的は、優れた発光特性を備え、高温駆動時の色度変化を抑制し、耐久性に優れた有機電界発光素子の提供にある。
また、本発明の別の目的は有機電界発光素子に有用な組成物及び発光層を提供することである。更に、本発明の別の目的は有機電界発光素子に有用な、化合物の成膜方法を提供することである。そして、本発明の別の目的は有機電界発光素子を含む発光装置、表示装置及び照明装置を提供することである。
〔1〕
基板上に、一対の電極と、該電極間に発光層を有する有機電界発光素子であって、前記発光層に以下の一般式(1)で表される化合物と、一般式(PQ-1)で表される化合物とを含有する有機電界発光素子。
〔2〕
前記一般式(PQ-1)において、n=3である、〔1〕に記載の有機電界発光素子。
〔3〕
前記一般式(PQ-1)において、n=2である、〔1〕に記載の有機電界発光素子。
〔4〕
前記一般式(PQ-1)において、R1~R6が水素原子である、〔1〕~〔3〕のいずれか一項に記載の有機電界発光素子。
〔5〕
前記一般式(PQ-1)において、R9がアリール基を表す、〔1〕~〔4〕のいずれか一項に記載の有機電界発光素子。
〔6〕
前記一般式(1)で表される化合物が、以下の一般式(2)で表される化合物である〔1〕~〔5〕のいずれか一項に記載の有機電界発光素子。
〔7〕
前記一般式(2)で表される化合物が、以下の一般式(3)で表される化合物である〔6〕に記載の有機電界発光素子。
〔8〕
前記(X-Y)がアセチルアセトネート(acac)、ピコリネート(pic)、及びこれらの誘導体のいずれかである〔1〕~〔7〕のいずれか一項に記載の有機電界発光素子。
〔9〕
前記発光層に下記一般式(C-1)で表される化合物を更に含有する、〔1〕~〔8〕のいずれか一項に記載の有機電界発光素子。
〔10〕
前記一般式(C-1)で表される化合物が下記一般式(C-2)で表される化合物である、〔9〕に記載の有機電界発光素子。
〔11〕
前記発光層と陰極の間に前記一般式(1)で表される化合物を含有する層を有する、〔1〕~〔10〕のいずれか一項に記載の有機電界発光素子。
〔12〕
〔1〕~〔11〕のいずれか一項に記載の前記一般式(1)で表される化合物と前記一般式(PQ-1)で表される化合物とを含有する組成物。
〔13〕
前記一般式(C-1)で表される化合物を更に含む〔12〕に記載の組成物。
〔14〕
〔1〕~〔11〕のいずれか一項に記載の前記一般式(1)で表される化合物と前記一般式(PQ-1)で表される化合物とを含有する発光層。
〔15〕
前記一般式(C-1)で表される化合物を更に含む〔14〕に記載の発光層。
〔16〕
〔1〕~〔11〕のいずれか一項に記載の前記一般式(1)で表される化合物と前記一般式(PQ-1)で表される化合物とを同時に加熱することにより昇華させて成膜する成膜方法。
〔17〕
〔1〕~〔11〕のいずれか一項に記載の有機電界発光素子を用いた発光装置。
〔18〕
〔1〕~〔11〕のいずれか一項に記載の有機電界発光素子を用いた表示装置。
〔19〕
〔1〕~〔11〕のいずれか一項に記載の有機電界発光素子を用いた照明装置。
(置換基群A)
アルキル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10であり、例えばメチル、エチル、イソプロピル、tert-ブチル、n-オクチル、n-デシル、n-ヘキサデシル、シクロプロピル、シクロペンチル、シクロヘキシルなどが挙げられる。)、アルケニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばビニル、アリル、2-ブテニル、3-ペンテニルなどが挙げられる。)、アルキニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばプロパルギル、3-ペンチニルなどが挙げられる。)、アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニル、p-メチルフェニル、ナフチル、アントラニルなどが挙げられる。)、アミノ基(好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~10であり、例えばアミノ、メチルアミノ、ジメチルアミノ、ジエチルアミノ、ジベンジルアミノ、ジフェニルアミノ、ジトリルアミノなどが挙げられる。)、アルコキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10であり、例えばメトキシ、エトキシ、ブトキシ、2-エチルヘキシロキシなどが挙げられる。)、アリールオキシ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニルオキシ、1-ナフチルオキシ、2-ナフチルオキシなどが挙げられる。)、ヘテロ環オキシ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばピリジルオキシ、ピラジルオキシ、ピリミジルオキシ、キノリルオキシなどが挙げられる。)、アシル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12であり、例えばアセチル、ベンゾイル、ホルミル、ピバロイルなどが挙げられる。)、アルコキシカルボニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12であり、例えばメトキシカルボニル、エトキシカルボニルなどが挙げられる。)、アリールオキシカルボニル基(好ましくは炭素数7~30、より好ましくは炭素数7~20、特に好ましくは炭素数7~12であり、例えばフェニルオキシカルボニルなどが挙げられる。)、アシルオキシ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばアセトキシ、ベンゾイルオキシなどが挙げられる。)、アシルアミノ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばアセチルアミノ、ベンゾイルアミノなどが挙げられる。)、アルコキシカルボニルアミノ基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~12であり、例えばメトキシカルボニルアミノなどが挙げられる。)、アリールオキシカルボニルアミノ基(好ましくは炭素数7~30、より好ましくは炭素数7~20、特に好ましくは炭素数7~12であり、例えばフェニルオキシカルボニルアミノなどが挙げられる。)、スルホニルアミノ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメタンスルホニルアミノ、ベンゼンスルホニルアミノなどが挙げられる。)、スルファモイル基(好ましくは炭素数0~30、より好ましくは炭素数0~20、特に好ましくは炭素数0~12であり、例えばスルファモイル、メチルスルファモイル、ジメチルスルファモイル、フェニルスルファモイルなどが挙げられる。)、カルバモイル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばカルバモイル、メチルカルバモイル、ジエチルカルバモイル、フェニルカルバモイルなどが挙げられる。)、アルキルチオ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメチルチオ、エチルチオなどが挙げられる。)、アリールチオ基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニルチオなどが挙げられる。)、ヘテロ環チオ基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばピリジルチオ、2-ベンズイミゾリルチオ、2-ベンズオキサゾリルチオ、2-ベンズチアゾリルチオなどが挙げられる。)、スルホニル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメシル、トシルなどが挙げられる。)、スルフィニル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばメタンスルフィニル、ベンゼンスルフィニルなどが挙げられる。)、ウレイド基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばウレイド、メチルウレイド、フェニルウレイドなどが挙げられる。)、リン酸アミド基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~12であり、例えばジエチルリン酸アミド、フェニルリン酸アミドなどが挙げられる。)、ヒドロキシ基、メルカプト基、ハロゲン原子(例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子)、シアノ基、スルホ基、カルボキシル基、ニトロ基、ヒドロキサム酸基、スルフィノ基、ヒドラジノ基、イミノ基、ヘテロ環基(芳香族ヘテロ環基も包含し、好ましくは炭素数1~30、より好ましくは炭素数1~12であり、ヘテロ原子としては、例えば窒素原子、酸素原子、硫黄原子、リン原子、ケイ素原子、セレン原子、テルル原子であり、具体的にはピリジル、ピラジニル、ピリミジル、ピリダジニル、ピロリル、ピラゾリル、トリアゾリル、イミダゾリル、オキサゾリル、チアゾリル、イソキサゾリル、イソチアゾリル、キノリル、フリル、チエニル、セレノフェニル、テルロフェニル、ピペリジル、ピペリジノ、モルホリノ、ピロリジル、ピロリジノ、ベンゾオキサゾリル、ベンゾイミダゾリル、ベンゾチアゾリル、カルバゾリル基、アゼピニル基、シロリル基などが挙げられる。)、シリル基(好ましくは炭素数3~40、より好ましくは炭素数3~30、特に好ましくは炭素数3~24であり、例えばトリメチルシリル、トリフェニルシリルなどが挙げられる。)、シリルオキシ基(好ましくは炭素数3~40、より好ましくは炭素数3~30、特に好ましくは炭素数3~24であり、例えばトリメチルシリルオキシ、トリフェニルシリルオキシなどが挙げられる。)、ホスホリル基(例えばジフェニルホスホリル基、ジメチルホスホリル基などが挙げられる。)が挙げられる。これらの置換基は更に置換されてもよく、更なる置換基としては、以上に説明した置換基群Aから選択される基を挙げることができる。
アルキル基(好ましくは炭素数1~30、より好ましくは炭素数1~20、特に好ましくは炭素数1~10であり、例えばメチル、エチル、イソプロピル、tert-ブチル、n-オクチル、n-デシル、n-ヘキサデシル、シクロプロピル、シクロペンチル、シクロヘキシルなどが挙げられる。)、アルケニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばビニル、アリル、2-ブテニル、3-ペンテニルなどが挙げられる。)、アルキニル基(好ましくは炭素数2~30、より好ましくは炭素数2~20、特に好ましくは炭素数2~10であり、例えばプロパルギル、3-ペンチニルなどが挙げられる。)、アリール基(好ましくは炭素数6~30、より好ましくは炭素数6~20、特に好ましくは炭素数6~12であり、例えばフェニル、p-メチルフェニル、ナフチル、アントラニルなどが挙げられる。)、シアノ基、ヘテロ環基(芳香族ヘテロ環基も包含し、好ましくは炭素数1~30、より好ましくは炭素数1~12であり、ヘテロ原子としては、例えば窒素原子、酸素原子、硫黄原子、リン原子、ケイ素原子、セレン原子、テルル原子であり、具体的にはピリジル、ピラジニル、ピリミジル、ピリダジニル、ピロリル、ピラゾリル、トリアゾリル、イミダゾリル、オキサゾリル、チアゾリル、イソキサゾリル、イソチアゾリル、キノリル、フリル、チエニル、セレノフェニル、テルロフェニル、ピペリジル、ピペリジノ、モルホリノ、ピロリジル、ピロリジノ、ベンゾオキサゾリル、ベンゾイミダゾリル、ベンゾチアゾリル、カルバゾリル基、アゼピニル基、シロリル基などが挙げられる。)これらの置換基は更に置換されてもよく、更なる置換基としては、以上に説明した置換基群Bから選択される基を挙げることができる。
本発明において、上記アルキル基等の置換基の「炭素数」とは、アルキル基等の置換基が他の置換基によって置換されてもよい場合も含み、当該他の置換基の炭素数も包含する意味で用いる。
また、「ヘテロアルキル」基とは少なくとも1つの炭素がO、NR、又はSに置き換わったアルキル基をいう。
一般式(1)で表される化合物と、一般式(PQ-1)で表される化合物とを発光層に用いることで、高い外部量子効率を有し、かつ耐久性に優れる有機電界発光素子を得ることができる。また、高温駆動時の色度変化が小さい有機電界発光素子を得ることができる。
〔一般式(1)で表される化合物〕
Czは、置換若しくは無置換のアリールカルバゾリル基又は置換若しくは無置換のカルバゾリルアリール基である。
アリールカルバゾリル基及びカルバゾリルアリール基におけるアリール基は、炭素数6~30が好ましく、例えば、フェニル基、ナフチル基、アントリル基、フェナントリル基、ナフタセニル基、ピレニル基、フルオレニル基、ビフェニル基、ターフェニル基等が挙げられ、これらのうち、フェニル基、ナフチル基、ビフェニル基、ターフェニル基が好ましく、フェニル基、ビフェニル基がより好ましい。
アリールカルバゾリル基及びカルバゾリルアリール基におけるカルバゾール環(カルバゾリル基)上でのアリール基の置換位置は、特に限定されないが、化学的安定性やキャリア輸送性の観点から、アリール基がカルバゾール環の2位、3位、6位、7位又は9位に置換していることが好ましく、カルバゾール環の3位、6位又は9位に置換していることがより好ましく、カルバゾール環の9位(N位)に置換していることが最も好ましい。
Czがアリールカルバゾリル基の場合、特に限定されないが、化学的安定性やキャリア輸送性の観点から、アリールカルバゾリル基のカルバゾール環の2位、3位、6位、7位又は9位(N位)でLと連結することが好ましく、カルバゾール環の3位、6位又は9位(N位)でLと連結することがより好ましく、カルバゾール環の9位(N位)でLと連結することが最も好ましい。
また、Czとしてはアルキル基、シリル基、アリール基、ハロゲン原子、シアノ基又はカルバゾリル基で置換されていてもよいカルバゾリルアリール基であることが好ましく、エチル基、t-ブチル基、トリフェニルシリル基、フェニル基、フッ素原子、シアノ基又はカルバゾリル基で置換されていてもよいカルバゾリルアリール基であることがより好ましい。
窒素含有芳香族ヘテロ6員環又は窒素含有芳香族ヘテロ6員環を含む窒素含有芳香族ヘテロ環としては、ピリジン、ピリミジン、ピラジン、ピリダジン、トリアジン、アザインドリジン、インドリジン、プリン、プテリジン、β-カルボリン、ナフチリジン、キノキサリン、ターピリジン、ビピリジン、アクリジン、フェナントロリン、フェナジン、イミダゾピリジン等が挙げられ、これらのうち、ピリジン、ピリミジン、ピラジン、トリアジンがより好ましく、ピリジン、ピリミジンが更に好ましく、ピリミジンが最も好ましい。
なお、一般式(1)においてp+qが3以上を表す場合、Lは、前記アリーレン基からp+q-2個の任意の水素原子を除したp+q価の基、シクロアルキレン基からp+q-2個の任意の水素原子を除したp+q価の基、又はp+q価の芳香族ヘテロ環基を表す。
Lが有する置換基としては、前記置換基群Aとしてあげたものが適用でき、好ましくはメチル基、エチル基、プロピル基、ブチル基、シクロヘキシル基、シクロペンチル基、フェニル基、トリル基、キシリル基、ピリジル基、ピリミジル基、チエニル基、フッ素原子、シアノ基、トリフルオロメチル基、ペンタフルオロフェニル基、トリフェニルシリル基、トリメチルシリル基であり、より好ましくはメチル基、エチル基、ブチル基、フェニル基、ピリジル基、ピリミジル基、フッ素原子、シアノ基、トリフルオロメチル基であり、更に好ましくはメチル基、フェニル基、フッ素原子である。
アリーレン基としては、炭素数6~30のアリーレン基が好ましく、例えば、フェニレン基、ビフェニレン基、ターフェニレン基、ナフチレン基、アントラニレン基、フェナンスリレン基、ビレニレン基、クリセニレン基、フルオランテニレン基、パーフルオロアリーレン基等が挙げられ、これらのうちフェニレン基、ビフェニレン基、ターフェニレン基、パーフルオロアリーレン基が好ましく、フェニレン基、ビフェニレン基、ターフェニレン基がより好ましく、フェニレン基、ビフェニレン基が更に好ましい。
シクロアルキレン基としては、炭素数5~30のシクロアルキレン基が好ましく、例えばシクロペンチレン基、シクロヘキシレン基、シクロヘプチレン基などが挙げられ、これらのうちシクロペンチレン基、シクロヘキシレン基が好ましく、シクロへキシレン基がより好ましい。
芳香族ヘテロ環としては、炭素数2~30の芳香族ヘテロ環が好ましく、1-ピロリル基、2-ピロリル基、3-ピロリル基、ピラジニル基、2-ピリジニル基、3-ピリジニル基、4-ピリジニル基、1-インドリル基、2-インドリル基、3-インドリル基、4-インドリル基、5-インドリル基、6-インドリル基、7-インドリル基、1-イソインドリル基、2-イソインドリル基、3-イソインドリル基、4-イソインドリル基、5-イソインドリル基、6-イソインドリル基、7-イソインドリル基、2-フリル基、3-フリル基、2-ベンゾフラニル基、3-ベンゾフラニル基、4-ベンゾフラニル基、5-ベンゾフラニル基、6-ベンゾフラニル基、7-ベンゾフラニル基、1-イソベンゾフラニル基、3-イソベンゾフラニル基、4-イソベンゾフラニル基、5-イソベンゾフラニル基、6-イソベンゾフラニル基、7-イソベンゾフラニル基、2-キノリル基、3-キノリル基、4-キノリル基、5-キノリル基、6-キノリル基、7-キノリル基、8-キノリル基、1-イソキノリル基、3-イソキノリル基、4-イソキノリル基、5-イソキノリル基、6-イソキノリル基、7-イソキノリル基、8-イソキノリル基、2-キノキサリニル基、5-キノキサリニル基、6-キノキサリニル基、1-カルバゾリル基、2-カルバゾリル基、3-カルバゾリル基、4-カルバゾリル基、9-カルバゾリル基、1-フェナンスリジニル基、2-フェナンスリジニル基、3-フェナンスリジニル基、4-フェナンスリジニル基、6-フェナンスリジニル基、7-フェナンスリジニル基、8-フェナンスリジニル基、9-フェナンスリジニル基、10-フェナンスリジニル基、1-アクリジニル基、2-アクリジニル基、3-アクリジニル基、4-アクリジニル基、9-アクリジニル基、1,7-フェナンスロリン-2-イル基、1,7-フェナンスロリン-3-イル基、1,7-フェナンスロリン-4-イル基、1,7-フェナンスロリン-5-イル基、1,7-フェナンスロリン-6-イル基、1,7-フェナンスロリン-8-イル基、1,7-フェナンスロリン-9-イル基、1,7-フェナンスロリン-10-イル基、1,8-フェナンスロリン-2-イル基、1,8-フェナンスロリン-3-イル基、1,8-フェナンスロリン-4-イル基、1,8-フェナンスロリン-5-イル基、1,8-フェナンスロリン-6-イル基、1,8-フェナンスロリン-7-イル基、1,8-フェナンスロリン-9-イル基、1,8-フェナンスロリン-10-イル基、1,9-フェナンスロリン-2-イル基、1,9-フェナンスロリン-3-イル基、1,9-フェナンスロリン-4-イル基、1,9-フェナンスロリン-5-イル基、1,9-フェナンスロリン-6-イル基、1,9-フェナンスロリン-7-イル基、1,9-フェナンスロリン-8-イル基、1,9-フェナンスロリン-10-イル基、1,10-フェナンスロリン-2-イル基、1,10-フェナンスロリン-3-イル基、1,10-フェナンスロリン-4-イル基、1,10-フェナンスロリン-5-イル基、2,9-フェナンスロリン-1-イル基、2,9-フェナンスロリン-3-イル基、2,9-フェナンスロリン-4-イル基、2,9-フェナンスロリン-5-イル基、2,9-フェナンスロリン-6-イル基、2,9-フェナンスロリン-7-イル基、2,9-フェナンスロリン-8-イル基、2,9-フェナンスロリン-10-イル基、2,8-フェナンスロリン-1-イル基、2,8-フェナンスロリン-3-イル基、2,8-フェナンスロリン-4-イル基、2,8-フェナンスロリン-5-イル基、2,8-フェナンスロリン-6-イル基、2,8-フェナンスロリン-7-イル基、2,8-フェナンスロリン-9-イル基、2,8-フェナンスロリン-10-イル基、2,7-フェナンスロリン-1-イル基、2,7-フェナンスロリン-3-イル基、2,7-フェナンスロリン-4-イル基、2,7-フェナンスロリン-5-イル基、2,7-フェナンスロリン-6-イル基、2,7-フェナンスロリン-8-イル基、2,7-フェナンスロリン-9-イル基、2,7-フェナンスロリン-10-イル基、1-フェナジニル基、2-フェナジニル基、1-フェノチアジニル基、2-フェノチアジニル基、3-フェノチアジニル基、4-フェノチアジニル基、10-フェノチアジニル基、1-フェノキサジニル基、2-フェノキサジニル基、3-フェノキサジニル基、4-フェノキサジニル基、10-フェノキサジニル基、2-オキサゾリル基、4-オキサゾリル基、5-オキサゾリル基、2-オキサジアゾリル基、5-オキサジアゾリル基、3-フラザニル基、2-チエニル基、3-チエニル基、2-メチルピロール-1-イル基、2-メチルピロール-3-イル基、2-メチルピロール-4-イル基、2-メチルピロール-5-イル基、3-メチルピロール-1-イル基、3-メチルピロール-2-イル基、3-メチルピロール-4-イル基、3-メチルピロール-5-イル基、2-t-ブチルピロール-4-イル基、3-(2-フェニルプロピル)ピロール-1-イル基、2-メチル-1-インドリル基、4-メチル-1-インドリル基、2-メチル-3-インドリル基、4-メチル-3-インドリル基、2-t-ブチル-1-インドリル基、4-t-ブチル-1-インドリル基、2-t-ブチル-3-インドリル基、4-t-ブチル-3-インドリル基等が挙げられ、これらのうち、ピリジニル基、キノリル基、インドリル基、カルバゾリル基が好ましく、ピリジニル基、カルバゾリル基がより好ましい。
Lとしては、単結合、フェニレン基、ビフェニレン基、シクロペンチレン基、シクロへキシレン基、ピリジニル基、カルバゾリル基が好ましく、単結合、フェニレン基、ビフェニレン基がより好ましく、単結合、フェニレン基が更に好ましい。
一般式(2)中、Cz、L、p及びqの定義は、一般式(1)におけるCz、L、p及びqと同様であり、好ましいものも同様である。
Ar1及びAr2はそれぞれ独立に置換若しくは無置換のアリール基、置換若しくは無置換のアリーレン基、又は置換若しくは無置換の芳香族へテロ環基である。
アリール基は置換又は無置換の炭素数6~30のものが好ましく、例えば、フェニル基、ビフェニル基、ターフェニル基、ナフチル基、アントラニル基、フェナンスリル基、ビレニル基、クリセニル基、フルオランテニル基、パーフルオロアリール基等が挙げられ、これらのうちフェニル基、ビフェニル基、ターフェニル基、パーフルオロアリール基が好ましく、フェニル基、ビフェニル基、ターフェニル基がより好ましく、フェニル基、ビフェニル基が更に好ましい。
アリーレン基としては置換又は無置換の炭素数6~30のものが好ましく、具体例や好ましい基は前述の一般式(1)におけるLの説明で挙げたものと同様である。
芳香族へテロ環基としては、置換又は無置換の炭素数2~30のものが好ましく、具体例や好ましい基は前述の一般式(1)におけるLの説明で挙げたものと同様である。これらに置換基が結合する場合、置換基の具体例や好ましい基は前述の一般式(1)におけるCz、A及びLの置換基として挙げたものと同様である。
Ar1及びAr2は、好ましくはそれぞれ独立に、ハロゲン原子で置換されていてもよいフェニル基又は無置換のターフェニル基であり、フッ素原子で置換されていてもよいフェニル基であることがより好ましい。
X1、X2及びX3は、それぞれ独立に、窒素原子又は水素原子若しくは置換基が結合した炭素原子を表す。X1、X2及びX3のうち、0~2個が窒素原子である場合が好ましく、0又は1個が窒素原子である場合がより好ましく、1個が窒素原子である場合が最も好ましい。X1、X2及びX3のいずれかに窒素原子が含まれる場合、X1及びX3のいずれか一方が窒素原子であることが好ましい。一般式(2)におけるX1~X3を含む環がピリジン又はピリミジンを表すことが好ましく、ピリミジンを表すことがより好ましい。炭素原子に結合する置換基の具体例や好ましい基は前述の一般式(1)におけるCz、A及びLの置換基として挙げたものと同様である。また、一般式(2)においてLの連結位置は特に限定されないが、化学的安定性やキャリア輸送性の観点から、Ar1の炭素原子と連結することが好ましい。
X4及びX5はそれぞれ独立に窒素原子又は水素原子若しくは置換基が結合した炭素原子を表す。X4及びX5のいずれか一方は窒素原子であり、他方は水素原子若しくは置換基が結合した炭素原子であることが好ましい。一般式(3)におけるX4及びX5を含む環がピリジン又はピリミジンを表すことが好ましく、ピリミジンを表すことがより好ましい。炭素原子に結合する置換基の具定例や好ましい基は前述の一般式(1)におけるCz、A及びLの置換基として挙げたものと同様である。
L’の定義は、前述の一般式(1)におけるLと同様であり、好ましい基もLと同様である。L’は、一般式(3)中の含窒素芳香族ヘテロ構造においてベンゼン環と連結している。
R1~R5はそれぞれ独立に置換基を表す。置換基の具体例は前述の一般式(1)におけるCz及びAの置換基として挙げたものと同様である。R1~R5として好ましくは、フッ素原子、メチル基、t-ブチル基、フェニル基、ピリジル基、ピラジル基、ピリミジル基、アダマンチル基、シアノ基、トリメチルシリル基、トリフェニルシリル基、トリフルオロメチル基、カルバゾリル基であり、より好ましくは、フッ素原子、メチル基、t-ブチル基、フェニル基、ピリジル基、シアノ基、トリメチルシリル基、トリフェニルシリル基、トリフルオロメチル基、カルバゾリル基であり、更に好ましくはフッ素原子、メチル基、t-ブチル基、フェニル基、シアノ基、シリル基、トリフェニルシリル基、トリフルオロメチル基、カルバゾリル基であり、更に好ましくはフッ素原子、t-ブチル基、フェニル基、シアノ基、トリフェニルシリル基、カルバゾリル基である。R1~R5が複数のとき、複数のR1~R5はそれぞれ同一でも異なっていてもよい。
n1~n5はそれぞれ独立に0~5の整数を表す。それぞれ0~2であることが好ましく、0~1であることがより好ましく、0であることが更に好ましい。
p’及びq’はそれぞれ独立に1~4の整数を表す。それぞれ1~3であることが好ましく、1又は2であることがより好ましい。
なお、一般式(3)においてp’+q’が3以上を表す場合、L’は、前記フェニレン基からp’+q’-2個の任意の水素原子を除したp’+q’価の基を表す。
以下に、一般式(1)で表される化合物の具体例を例示するが、本発明はこれらに限定されるものではない。なお、下記具体例中のPhはフェニル基を表す。
例えば、上記No.4の化合物は、m-ブロモベンゾアルデヒドを出発原料に用い、国際公開第05/085387号パンフレット段落[0074]-[0075](45頁、11行~46頁、18行)に記載の方法で合成することができる。上記No.45の化合物は、3,5-ジブロモベンゾアルデヒドを出発原料に用い、国際公開第03/080760号パンフレットの46頁、9行~46頁、12行に記載の方法で合成することができる。また、上記No.77の化合物は、N-フェニルカルバゾールを出発原料に用い、国際公開第05/022962号パンフレットの137頁、10行~139頁、9行に記載の方法で合成することができる。
本発明では、高温駆動時の色度変化をより抑えるために、一般式(1)で表される化合物を発光層及び発光層に隣接する層の両層に含有させてもよい。
一般式(1)で表される化合物を発光層中含有させる場合、本発明の一般式(1)で表される化合物は発光層の全質量に対して0.1~99質量%含ませることが好ましく、1~95質量%含ませることがより好ましく、10~95質量%含ませることがより好ましい。
また、一般式(1)で表される化合物を発光層以外の層に含有させる場合は、発光層以外の層の全質量に対して10~100質量%含ませることが好ましく、30~100質量%含ませることがより好ましく、50~100質量%含まれせることがより好ましい。
本発明において、前記発光層が、一般式(1)で表される化合物と、一般式(PQ-1)で表される化合物と、ホスト材料とを含むことが好ましい。前記ホスト材料は下記一般式(4-1)又は(4-2)で表される化合物であることが好ましい。
本発明においては、発光層に前記一般式(1)で表される化合物及び一般式(PQ-1)で表される化合物と、更に一般式(4-1)又は(4-2)で表される化合物の少なくとも1つ以上を含むことがより好ましい。
gは0~8の整数を表し、電荷輸送を担うカルバゾール骨格を遮蔽しすぎない観点から0~4が好ましい。また、合成容易さの観点から、カルバゾールが置換基を有する場合、窒素原子に対し、対称になるように置換基を持つものが好ましい。
一般式(PQ-1)で表される化合物について説明する。
置換基同士は可能であれば互いに結合して環を形成しても良い。環を形成する場合、R1~R10の内の隣接する2つが互いに結合して環を形成することが好ましく、R7とR8、R8とR9、又はR9とR10、とが互いに結合して環を形成することがより好ましい。R7とR8、R8とR9、又はR9とR10、とが互いに結合して環を形成する場合に、R7~R10が置換するベンゼン環とともに形成される環としては、アルキル基、アルコキシ基等で置換されていてもよいアリール環等が挙げられる。
形成されるアリール環は、好ましくは炭素数6~30のアリール環であり、より好ましくは炭素数6~15のアリール環である。形成されるアリール環としては、例えばナフタレン環、フェナントレン環、フルオレン環等が挙げられ、ナフタレン環又はフルオレン環が好ましく、ナフタレン環がより好ましい。これら環はアルキル基、アルコキシ基等の置換基を有していてもよく、アルキル基又はアルコキシ基で置換されていてもよいナフタレン環又はフルオレン環であることが好ましい。
一般式(PQ-1)中、R7~R10の内の0~2つがそれぞれ独立にアルキル基、アリール基、シアノ基、ヘテロ環基又はフッ素原子を表すと共に、その他のR7~R10が全て水素原子であることも好ましく、R7~R10の内の0~2つがそれぞれ独立にアルキル基、アリール基、シアノ基又はフッ素原子を表すと共に、その他のR7~R10が全て水素原子であることがより好ましく、R9がアリール基を表すと共に、R7、R8及びR10が全て水素原子であることが更に好ましい。なお、R7とR8、R8とR9、又はR9とR10、は互いに結合して前述の環を形成していてもよく、環を形成する場合、前述のアリール環を形成することがより好ましく、ベンゼン環を形成することが更に好ましい。
R1~R6は水素原子であることが好ましい。また、R9がアリール基であることが好ましい。
本発明では、高温駆動時の色度変化をより抑えるために、一般式(1)で表される化合物と一般式(PQ-1)で表される化合物とが発光層に含有される。
本発明の有機電界発光素子は、発光層に下記一般式(C-1)で表される化合物を更に含有することが好ましい。下記一般式(C-1)で表される化合物を更に含有することで、キャリアバランスを良化し、効率、耐久性を向上することができる。
正孔輸送性のIr錯体と電子輸送性のPt錯体が共存するためと推測される。
炭素原子でPtに結合するQ1、Q2、Q3及びQ4としては、アニオン性の配位子でも中性の配位子でもよく、アニオン性の配位子としてはビニル配位子、芳香族炭化水素環配位子(例えばベンゼン配位子、ナフタレン配位子、アントラセン配位子、フェナントレン配位子など)、ヘテロ環配位子(例えばフラン配位子、チオフェン配位子、ピリジン配位子、ピラジン配位子、ピリミジン配位子、ピリダジン配位子、トリアジン配位子、チアゾール配位子、オキサゾール配位子、ピロール配位子、イミダゾール配位子、ピラゾール配位子、トリアゾール配位子及び、それらを含む縮環体(例えばキノリン配位子、ベンゾチアゾール配位子など))が挙げられる。中性の配位子としてはカルベン配位子が挙げられる。
窒素原子でPtに結合するQ1、Q2、Q3及びQ4としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としては含窒素芳香族ヘテロ環配位子(ピリジン配位子、ピラジン配位子、ピリミジン配位子、ピリダジン配位子、トリアジン配位子、イミダゾール配位子、ピラゾール配位子、トリアゾール配位子、オキサゾール配位子、チアゾール配位子及びそれらを含む縮環体(例えばキノリン配位子、ベンゾイミダゾール配位子など))、アミン配位子、ニトリル配位子、イミン配位子が挙げられる。アニオン性の配位子としては、アミノ配位子、イミノ配位子、含窒素芳香族ヘテロ環配位子(ピロール配位子、イミダゾール配位子、トリアゾール配位子及びそれらを含む縮環体(例えはインドール配位子、ベンゾイミダゾール配位子など))が挙げられる。 酸素原子でPtに結合するQ1、Q2、Q3及びQ4としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としてはエーテル配位子、ケトン配位子、エステル配位子、アミド配位子、含酸素ヘテロ環配位子(フラン配位子、オキサゾール配位子及びそれらを含む縮環体(ベンゾオキサゾール配位子など))が挙げられる。アニオン性の配位子としては、アルコキシ配位子、アリールオキシ配位子、ヘテロアリールオキシ配位子、アシルオキシ配位子、シリルオキシ配位子などが挙げられる。
硫黄原子でPtに結合するQ1、Q2、Q3及びQ4としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としてはチオエーテル配位子、チオケトン配位子、チオエステル配位子、チオアミド配位子、含硫黄ヘテロ環配位子(チオフェン配位子、チアゾール配位子及びそれらを含む縮環体(ベンゾチアゾール配位子など))が挙げられる。アニオン性の配位子としては、アルキルメルカプト配位子、アリールメルカプト配位子、ヘテロアリールメルカプト配位子などが挙げられる。
リン原子でPtに結合するQ1、Q2、Q3及びQ4としては、中性の配位子でもアニオン性の配位子でもよく、中性の配位子としてはホスフィン配位子、リン酸エステル配位子、亜リン酸エステル配位子、含リンヘテロ環配位子(ホスフィニン配位子など)が挙げられ、アニオン性の配位子としては、ホスフィノ配位子、ホスフィニル配位子、ホスホリル配位子などが挙げられる。
Q1、Q2、Q3及びQ4で表される基は、置換基を有していてもよく、置換基としては前記置換基群Aとして挙げたものが適宜適用できる。また置換基同士が連結していても良い(Q3とQ4が連結した場合、環状四座配位子のPt錯体になる)。
錯体の安定性及び発光量子収率の観点から、L1、L2及びL3として好ましくは単結合、アルキレン基、アリーレン基、ヘテロアリーレン基、イミノ基、オキシ基、チオ基、シリレン基であり、より好ましくは単結合、アルキレン基、アリーレン基、イミノ基であり、更に好ましくは単結合、アルキレン基、アリーレン基であり、更に好ましくは、単結合、メチレン基、フェニレン基であり、更に好ましくは単結合、ジ置換のメチレン基であり、更に好ましくは単結合、ジメチルメチレン基、ジエチルメチレン基、ジイソブチルメチレン基、ジベンジルメチレン基、エチルメチルメチレン基、メチルプロピルメチレン基、イソブチルメチルメチレン基、ジフェニルメチレン基、メチルフェニルメチレン基、シクロヘキサンジイル基、シクロペンタンジイル基、フルオレンジイル基、フルオロメチルメチレン基である。
L1は特に好ましくは、ジメチルメチレン基、ジフェニルメチレン基、シクロヘキサンジイル基であり、最も好ましくはジメチルメチレン基である。
L2及びL3として最も好ましくは単結合である。
A301~A306として好ましくはC-Rであり、R同士が互いに連結して環を形成していても良い。A301~A306がC-Rである場合に、A302、A305のRとして好ましくは水素原子、アルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素基、シアノ基であり、より好ましくは水素原子、アミノ基、アルコキシ基、アリールオキシ基、フッ素基であり、特に好ましくは水素原子、フッ素基である。A301、A303、A304、A306のRとして好ましくは水素原子、アルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素基、シアノ基であり、より好ましくは水素原子、アミノ基、アルコキシ基、アリールオキシ基、フッ素基であり、特に好ましく水素原子である。A307、A308、A309及びA310は、それぞれ独立に、C-R又は窒素原子を表す。Rは水素原子又は置換基を表す。Rで表される置換基としては、前記置換基群Aとして挙げたものが適用できる。A307、A308、A309及びA310がC-Rである場合に、Rとして好ましくは水素原子、アルキル基、ペルフルオロアルキル基、アリール基、芳香族へテロ環基、ジアルキルアミノ基、ジアリールアミノ基、アルキルオキシ基、シアノ基、ハロゲン原子であり、より好ましくは、水素原子、アルキル基、ペルフルオロアルキル基、アリール基、ジアルキルアミノ基、シアノ基、フッ素原子、更に好ましくは、水素原子、アルキル基、トリフルオロメチル基、フッ素原子である。また可能な場合は置換基同士が連結して縮環構造を形成してもよい。発光波長を短波長側にシフトさせる場合、A308が窒素原子であることが好ましい。
A401~A414はそれぞれ独立にC-R又は窒素原子を表す。Rは水素原子又は置換基を表す。A401~A406及びL41は、前記一般式(C-3)におけるA301~A306及びL31と同義であり、好ましい範囲も同様である。
A407~A414がC-Rを表す場合に、A408、A412のRとして好ましくは水素原子、アルキル基、ペルフルオロアルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素基、シアノ基であり、より好ましくは水素原子、ペルフルオロアルキル基、アルキル基、アリール基、フッ素基、シアノ基であり、特に好ましくは、水素原子、フェニル基、ペルフルオロアルキル基、シアノ基である。A407、A409、A411、A413のRとして好ましくは水素原子、アルキル基、ペルフルオロアルキル基、アリール基、アミノ基、アルコキシ基、アリールオキシ基、フッ素基、シアノ基であり、より好ましくは水素原子、ペルフルオロアルキル基、フッ素基、シアノ基であり、特に好ましく水素原子、フェニル基、フッ素基である。A410、A414のRとして好ましくは水素原子、フッ素基であり、より好ましくは水素原子である。A407~A409、A411~A413のいずれかがC-Rを表す場合に、R同士が互いに連結して環を形成していても良い。
Yで表される配位子は、置換基を有していてもよく、置換基としては前記置換基群Aとして挙げたものが適宜適用できる。また置換基同士が連結していても良い。
例えば、配位子、又はその解離体と金属化合物を溶媒(例えば、ハロゲン系溶媒、アルコール系溶媒、エーテル系溶媒、エステル系溶媒、ケトン系溶媒、ニトリル系溶媒、アミド系溶媒、スルホン系溶媒、スルホキサイド系溶媒、水などが挙げられる)の存在下、若しくは、溶媒非存在下、塩基の存在下(無機、有機の種々の塩基、例えば、ナトリウムメトキシド、t-ブトキシカリウム、トリエチルアミン、炭酸カリウムなどが挙げられる)、若しくは、塩基非存在下、室温以下、若しくは加熱し(通常の加熱以外にもマイクロウェーブで加熱する手法も有効である)得ることができる。
本発明は一般式(1)で表される化合物と一般式(PQ-1)で表される化合物とを含む発光層にも関する。本発明の発光層は有機電界発光素子に用いることができる。
本発明の発光層は、前記一般式(C-1)で表される化合物を更に含むことが好ましい。
前記一般式(C-1)で表される化合物を、前記一般式(1)で表される化合物及び前記一般式(PQ-1)で表される化合物と併用することで、より外部量子効率及び駆動耐久性に優れた有機電界発光素子を得ることができる。本発明の発光層における一般式(C-1)で表される化合物の含有量は発光層中1~30質量%であることが好ましく、3~20質量%であることがより好ましい。
本発明は前記一般式(1)で表される化合物と前記一般式(PQ-1)で表される化合物とを含有する組成物にも関する。
本発明の組成物における一般式(1)で表される化合物の含有量は50~95質量%であることが好ましく、70~90質量%であることがより好ましい。
本発明の組成物における一般式(PQ-1)で表される化合物の含有量は1~40質量%であることが好ましく、5~20質量%であることがより好ましい。
本発明の組成物における他に含有しても良い成分としては、有機物でも無機物でもよく、有機物としては、後述するホスト材料、蛍光発光材料、燐光発光材料、炭化水素材料として挙げた材料が適用でき、好ましくはホスト材料、炭化水素材料であり、より好ましくは一般式(VI)で表される化合物である。
本発明の組成物は蒸着法やスパッタ法等の乾式製膜法、転写法、印刷法等により有機電界発光素子の有機層を形成することができる。
本発明の組成物における一般式(C-1)で表される化合物の含有量は組成物中、1~30質量%であることが好ましく、3~20質量%であることがより好ましい。
本発明の素子について詳細に説明する。
本発明の有機電界発光素子は、基板上に、一対の電極と、該電極間に発光層を有する有機電界発光素子であって、前記発光層に以下の一般式(1)で表される化合物と、一般式(PQ-1)で表される化合物とを含有する。発光層と陰極の間に一般式(1)で表される化合物を含有する層を更に有することが好ましい。
発光素子の性質上、陽極及び陰極のうち少なくとも一方の電極は、透明若しくは半透明であることが好ましい。
図1は、本発明に係る有機電界発光素子の構成の一例を示している。図1に示される本発明に係る有機電界発光素子10は、基板2上において、陽極3と陰極9との間に発光層6が挟まれている。具体的には、陽極3と陰極9との間に正孔注入層4、正孔輸送層5、発光層6、正孔ブロック層7、及び電子輸送層8がこの順に積層されている。
前記有機層の層構成としては、特に制限はなく、有機電界発光素子の用途、目的に応じて適宜選択することができるが、前記透明電極上に又は前記背面電極上に形成されるのが好ましい。この場合、有機層は、前記透明電極又は前記背面電極上の前面又は一面に形成される。
有機層の形状、大きさ、及び厚み等については、特に制限はなく、目的に応じて適宜選択することができる。
・陽極/正孔輸送層/発光層/電子輸送層/陰極、
・陽極/正孔輸送層/発光層/第二電子輸送層(正孔ブロック層)/第一電子輸送層/陰極、
・陽極/正孔輸送層/発光層/第二電子輸送層(正孔ブロック層)/第一電子輸送層/電子注入層/陰極、
・陽極/正孔注入層/正孔輸送層(電子ブロック層)/発光層/第二電子輸送層(正孔ブロック層)/第一電子輸送層/陰極、
・陽極/正孔注入層/第一正孔輸送層/第二正孔輸送層(電子ブロック層)/発光層/第二電子輸送層(正孔ブロック層)/第一電子輸送層/電子注入層/陰極。
有機電界発光素子の素子構成、基板、陰極及び陽極については、例えば、特開2008-270736号公報に詳述されており、該公報に記載の事項を本発明に適用することができる。
本発明で使用する基板としては、有機層から発せられる光を散乱又は減衰させない基板であることが好ましい。有機材料の場合には、耐熱性、寸法安定性、耐溶剤性、電気絶縁性、及び加工性に優れていることが好ましい。
<陽極>
陽極は、通常、有機層に正孔を供給する電極としての機能を有していればよく、その形状、構造、大きさ等については特に制限はなく、発光素子の用途、目的に応じて、公知の電極材料の中から適宜選択することができる。前述のごとく、陽極は、通常透明陽極として設けられる。
<陰極>
陰極は、通常、有機層に電子を注入する電極としての機能を有していればよく、その形状、構造、大きさ等については特に制限はなく、発光素子の用途、目的に応じて、公知の電極材料の中から適宜選択することができる。
本発明における有機層について説明する。
本発明の有機電界発光素子において、各有機層は、蒸着法やスパッタ法等の乾式製膜法、転写法、印刷法等いずれによっても好適に形成することができる。
<発光材料>
本発明における発光材料は、前記一般式(PQ-1)で表される化合物であることが好ましい。
また、発光層は一層であっても二層以上の多層であってもよい。発光層が複数の場合、一般式(1)で表される化合物及び(PQ-1)で表される化合物を二層以上の発光層に含んでもよい。また、それぞれの発光層が異なる発光色で発光してもよい。
本発明に用いるホスト材料は、前記一般式(1)で表される化合物が好ましい。
一般式(1)で表される化合物は、正孔と電子の両電荷輸送性であり、一般式(PQ-1)で表される化合物と組み合わせることで、正孔と電子のキャリアバランスを良化することができる。これにより、カルバゾール基を有する化合物であるにもかかわらず駆動耐久性を向上させることができる。更に、高温駆動時の色変化を抑制することができる。
本発明に使用できる蛍光発光材料の例としては、例えば、ベンゾオキサゾール誘導体、ベンゾイミダゾール誘導体、ベンゾチアゾール誘導体、スチリルベンゼン誘導体、ポリフェニル誘導体、ジフェニルブタジエン誘導体、テトラフェニルブタジエン誘導体、ナフタルイミド誘導体、クマリン誘導体、縮合芳香族化合物、ペリノン誘導体、オキサジアゾール誘導体、オキサジン誘導体、アルダジン誘導体、ピラリジン誘導体、シクロペンタジエン誘導体、ビススチリルアントラセン誘導体、キナクリドン誘導体、ピロロピリジン誘導体、チアジアゾロピリジン誘導体、シクロペンタジエン誘導体、スチリルアミン誘導体、ジケトピロロピロール誘導体、芳香族ジメチリディン化合物、8-キノリノール誘導体の錯体やピロメテン誘導体の錯体に代表される各種錯体等、ポリチオフェン、ポリフェニレン、ポリフェニレンビニレン等のポリマー化合物、有機シラン誘導体などの化合物等が挙げられる。
本発明に使用できる燐光発光材料としては、一般式(1)で表される化合物の他、例えば、US6303238B1、US6097147、WO00/57676、WO00/70655、WO01/08230、WO01/39234A2、WO01/41512A1、WO02/02714A2、WO02/15645A1、WO02/44189A1、WO05/19373A2、特開2001-247859、特開2002-302671、特開2002-117978、特開2003-133074、特開2002-235076、特開2003-123982、特開2002-170684、EP1211257、特開2002-226495、特開2002-234894、特開2001-247859、特開2001-298470、特開2002-173674、特開2002-203678、特開2002-203679、特開2004-357791、特開2006-256999、特開2007-19462、特開2007-84635、特開2007-96259等の特許文献に記載の燐光発光化合物などが挙げられ、中でも、更に好ましい発光性材料としては、Ir錯体、Pt錯体、Cu錯体、Re錯体、W錯体、Rh錯体、Ru錯体、Pd錯体、Os錯体、Eu錯体、Tb錯体、Gd錯体、Dy錯体、及びCe錯体が挙げられる。特に好ましくは、Ir錯体、Pt錯体、又はRe錯体であり、中でも金属-炭素結合、金属-窒素結合、金属-酸素結合、金属-硫黄結合の少なくとも一つの配位様式を含むIr錯体、Pt錯体、又はRe錯体が好ましい。更に、発光効率、駆動耐久性、色度等の観点で、3座以上の多座配位子を含むIr錯体、Pt錯体、又はRe錯体が特に好ましい。
本発明の有機電界発光素子は、上記化合物(PQ-1)(一般式(PQ-1)で表される化合物)の少なくとも一種を該発光層の総質量に対して5~30質量%含有することが最も好ましい。
また、炭化水素化合物は下記一般式(VI)で表される化合物であることが好ましい。
一般式(VI)で表される化合物を発光材料とともに適切に用いることにより、材料分子間の相互作用を適切に制御し、隣接分子間のエネルギーギャップ相互作用を均一にすることで駆動電圧を更に低下させることが可能となる。
また、有機電界発光素子において用いられる、一般式(VI)で表される化合物は、化学的な安定性に優れ、素子駆動中における材料の分解等の変質が少なく、当該材料の分解物による、有機電界発光素子の効率低下や素子寿命の低下を防ぐことが出来る。
一般式(VI)で表される化合物について説明する。
室温(25℃)において固体を形成しない一般式(VI)で表される化合物を用いる場合は、他の材料と組み合わせることにより、常温で固相を形成させることができる。
また、一般式(VI)で表される化合物を、複数の有機層に用いる場合はそれぞれの層において、上記の範囲で含有することが好ましい。
文献1:Tetrahedron Lett. 39, 1998, 9557-9558.
文献2:Tetrahedron Lett. 39, 1998, 2095-2096.
文献3:J. Am. Chem. Soc. 124, 2002, 13662-13663.
Wiley&Sons Inc.)(1981年)等)等の手段により容易に製造が可能である。また、必要に応じて適宜置換基導入等の反応工程の順序を変化させることも可能である。
(電荷輸送層)
電荷輸送層とは、有機電界発光素子に電圧を印加した際に電荷移動が起こる層をいう。具体的には正孔注入層、正孔輸送層、電子ブロック層、発光層、正孔ブロック層、電子輸送層又は電子注入層が挙げられる。好ましくは、正孔注入層、正孔輸送層、電子ブロック層又は発光層である。塗布法により形成される電荷輸送層が正孔注入層、正孔輸送層、電子ブロック層又は発光層であれば、低コストかつ高効率な有機電界発光素子の製造が可能となる。また、電荷輸送層として、より好ましくは、正孔注入層、正孔輸送層又は電子ブロック層である。
正孔注入層、正孔輸送層は、陽極又は陽極側から正孔を受け取り陰極側に輸送する機能を有する層である。
これらの層に用いる正孔注入材料、正孔輸送材料は、低分子化合物であっても高分子化合物であってもよい。
具体的には、ピロール誘導体、カルバゾール誘導体、ピロール誘導体、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、芳香族第三級アミン化合物、スチリルアミン化合物、フタロシアニン系化合物、ポルフィリン系化合物、チオフェン誘導体、有機シラン誘導体、カーボン、イリジウム錯体等の各種金属錯体等を含有する層であることが好ましい。
本発明において、カルバゾール化合物は下記一般式(a)で表されるカルバゾール化合物であることが好ましい。一般式(a)
また、一般式(a)で表される化合物を、複数の有機層に用いる場合はそれぞれの層において、上記の範囲で含有することが好ましい。
該正孔輸送層は、上述した材料の一種又は二種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
この他にも、特開平6-212153、特開平11-111463、特開平11-251067、特開2000-196140、特開2000-286054、特開2000-315580、特開2001-102175、特開2001-160493、特開2002-252085、特開2002-56985、特開2003-157981、特開2003-217862、特開2003-229278、特開2004-342614、特開2005-72012、特開2005-166637、特開2005-209643等に記載の化合物を好適に用いることが出来る。
正孔輸送層の厚さとしては、1nm~500nmであるのが好ましく、5nm~200nmであるのがより好ましく、10nm~100nmであるのが更に好ましい。また、正孔注入層の厚さとしては、0.1nm~200nmであるのが好ましく、0.5nm~100nmであるのがより好ましく、1nm~100nmであるのが更に好ましい。
正孔注入層、正孔輸送層は、上述した材料の1種又は2種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
電子注入層、電子輸送層は、陰極又は陰極側から電子を受け取り陽極側に輸送する機能を有する層である。
正孔注入層、正孔輸送層、電子注入層、電子輸送層については、特開2008-270736号公報の段落番号〔0165〕~〔0167〕に記載の事項を本発明に適用することができる。
正孔ブロック層は、陽極側から発光層に輸送された正孔が、陰極側に通りぬけることを防止する機能を有する層である。本発明において、発光層と陰極側で隣接する有機層として、正孔ブロック層を設けることができる。
正孔ブロック層を構成する有機化合物の例としては、アルミニウム(III)ビス(2-メチル-8-キノリナト)4-フェニルフェノレート(Aluminum (III)bis(2-methyl-8-quinolinato)4-phenylphenolate(Balqと略記する))等のアルミニウム錯体、トリアゾール誘導体、2,9-ジメチル-4,7-ジフェニル-1,10-フェナントロリン(2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline(BCPと略記する))等のフェナントロリン誘導体、等が挙げられる。
正孔ブロック層の厚さとしては、1nm~500nmであるのが好ましく、5nm~200nmであるのがより好ましく、10nm~100nmであるのが更に好ましい。
正孔ブロック層は、上述した材料の一種又は二種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
電子ブロック層は、陰極側から発光層に輸送された電子が、陽極側に通りぬけることを防止する機能を有する層である。本発明において、発光層と陽極側で隣接する有機層として、電子ブロック層を設けることができる。
電子ブロック層を構成する有機化合物の例としては、例えば前述の正孔輸送材料として挙げたものが適用できる。
電子ブロック層の厚さとしては、1nm~500nmであるのが好ましく、5nm~200nmであるのがより好ましく、10nm~100nmであるのが更に好ましい。
電子ブロック層は、上述した材料の一種又は二種以上からなる単層構造であってもよいし、同一組成又は異種組成の複数層からなる多層構造であってもよい。
本発明において、有機EL素子全体は、保護層によって保護されていてもよい。
保護層については、特開2008-270736号公報の段落番号〔0169〕~〔0170〕に記載の事項を本発明に適用することができる。
本発明の素子は、封止容器を用いて素子全体を封止してもよい。
封止容器については、特開2008-270736号公報の段落番号〔0171〕に記載の事項を本発明に適用することができる。
更に、本発明は一般式(1)で表される化合物と一般式(PQ-1)で表される化合物とを同時に加熱することにより昇華させて成膜する成膜方法にも関する。
成膜に際し、一般式(1)で表される化合物と一般式(PQ-1)で表される化合物とが混合されていることが好ましく、本発明の組成物を用いてもよい。一般式(1)で表される化合物と一般式(PQ-1)で表される化合物の含有割合は一般式(1)で表される化合物に対して一般式(PQ-1)で表される化合物が1%~45%であることが好ましく、1%~25%であることがより好ましい。
加熱の温度は200℃~400℃であることが好ましく、250℃~320℃であることがより好ましい。
加熱の時間は0.1時間~350時間であることが好ましく、0.1時間~150時間であることがより好ましい。
本発明の成膜方法によれば高効率、高耐久性、かつ高温駆動時の色変化の少ない発光層膜を容易に作成できるという利点がある。
本発明の有機電界発光素子は、陽極と陰極との間に直流(必要に応じて交流成分を含んでもよい)電圧(通常2ボルト~15ボルト)、又は直流電流を印加することにより、発光を得ることができる。
本発明の有機電界発光素子の駆動方法については、特開平2-148687号、同6-301355号、同5-29080号、同7-134558号、同8-234685号、同8-241047号の各公報、特許第2784615号、米国特許5828429号、同6023308号の各明細書等に記載の駆動方法を適用することができる。
別の好ましい態様では、透明基板上に、透明又は半透明電極と金属電極がそれぞれ反射板として機能して、発光層で生じた光はその間で反射を繰り返し共振する。
共振構造を形成するためには、2つの反射板の有効屈折率、反射板間の各層の屈折率と厚みから決定される光路長を所望の共振波長の得るのに最適な値となるよう調整される。第一の態様の場合の計算式は特開平9-180883号明細書に記載されている。第2の態様の場合の計算式は特開2004-127795号明細書に記載されている。
本発明の発光素子は、発光装置、ピクセル、表示素子、ディスプレイ、バックライト、電子写真、照明光源、記録光源、露光光源、読み取り光源、標識、看板、インテリア、又は光通信等に好適に利用できる。特に、照明装置、表示装置等の発光輝度が高い領域で駆動されるデバイスに好ましく用いられる。
本発明の発光装置は、前記有機電界発光素子を用いてなる。
図2は、本発明の発光装置の一例を概略的に示した断面図である。
図2の発光装置20は、透明基板(基板)2、有機電界発光素子10、封止容器16等により構成されている。
ここで、接着層14としては、エポキシ樹脂等の光硬化型接着剤や熱硬化型接着剤を用いることができ、例えば熱硬化性の接着シートを用いることもできる。
図3は、本発明の実施形態に係る照明装置の一例を概略的に示した断面図である。
本発明の実施形態に係る照明装置40は、図3に示すように、前述した有機EL素子10と、光散乱部材30とを備えている。より具体的には、照明装置40は、有機EL素子10の基板2と光散乱部材30とが接触するように構成されている。
光散乱部材30は、光を散乱できるものであれば特に制限されないが、図3においては、透明基板31に微粒子32が分散した部材とされている。透明基板31としては、例えば、ガラス基板を好適に挙げることができる。微粒子32としては、透明樹脂微粒子を好適に挙げることができる。ガラス基板及び透明樹脂微粒子としては、いずれも、公知のものを使用できる。このような照明装置40は、有機電界発光素子10からの発光が散乱部材30の光入射面30Aに入射されると、入射光を光散乱部材30により散乱させ、散乱光を光出射面30Bから照明光として出射するものである。
0.5mm厚み、2.5cm角の酸化インジウム錫(ITO)膜を有するガラス基板(ジオマテック社製、表面抵抗10Ω/□)を洗浄容器に入れ、2-プロパノール中で超音波洗浄した後、30分間UV-オゾン処理を行った。この透明陽極(ITO膜)上に真空蒸着法にて以下の有機層を順次蒸着した。
第1層:CuPc(銅フタロシアニン):膜厚10nm
第2層:NPD(N,N’-ジ-α-ナフチル-N,N’-ジフェニル)-ベンジジン):膜厚30nm
第3層:ドーパント(Ir(btp)2(acac)、5質量%)、ホスト材料(CBP、95質量%):膜厚30nm
第4層:Balq:膜厚10nm
第5層:Alq(トリス(8-ヒドロキシキノリン)アルミニウム錯体):膜厚40nm
この上に、フッ化リチウム0.2nm及び金属アルミニウム70nmをこの順に蒸着し陰極とした。上記第3層のように、二種以上の材料を含有する膜は、該材料を同時に加熱することにより昇華させて成膜した。
得られた積層体を、大気に触れさせること無く、アルゴンガスで置換したグローブボックス内に入れ、ステンレス製の封止缶及び紫外線硬化型の接着剤(XNR5516HV、長瀬チバ(株)製)を用いて封止し、比較例1の素子を得た。
第3層の構成材料(ホスト材料、ドーパント)、第4層の構成材料を、下記表1~6に示すように変更する以外は比較例1と同様にして各種素子を作製した。
例えば、実施例40の第3層はホスト材料として例示化合物4を85質量%、FR-1を5質量%、白金錯体2-3を10質量%を用いたことを示す。
0.5mm厚み、2.5cm角の酸化インジウム錫(ITO)膜を有するガラス基板(ジオマテック社製、表面抵抗10Ω/□)を洗浄容器に入れ、2-プロパノール中で超音波洗浄した後、30分間UV-オゾン処理を行った。この透明陽極(ITO膜)上に真空蒸着法にて以下の有機層を順次蒸着した。
第1層:CuPc(銅フタロシアニン):膜厚10nm
第2層:NPD(N,N’-ジ-α-ナフチル-N,N’-ジフェニル)-ベンジジン):膜厚30nm
第3層:隣接層材料(V-1):膜厚3nm
第4層:ドーパント(FR-1、5質量%)、ホスト材料(例示化合物4、95質量%):膜厚30nm
第5層:Balq:膜厚10nm
第6層:Alq(トリス(8-ヒドロキシキノリン)アルミニウム錯体):膜厚40nm
この上に、フッ化リチウム0.2nm及び金属アルミニウム70nmをこの順に蒸着し陰極とした。
得られた積層体を、大気に触れさせること無く、アルゴンガスで置換したグローブボックス内に入れ、ステンレス製の封止缶及び紫外線硬化型の接着剤(XNR5516HV、長瀬チバ(株)製)を用いて封止し、実施例60の素子を得た。
第3層の構成材料、第4層の構成材料(ホスト材料、ドーパント)を、下記表7に示すように変更する以外は実施例60と同様にして各種素子を作製した。
得られた各種素子の性能を評価した。
(a) 外部量子効率
東陽テクニカ製ソースメジャーユニット2400を用いて、直流電圧を各素子に印加し発光させ、その輝度をトプコン社製輝度計BM-8を用いて測定した。発光スペクトルと発光波長は浜松ホトニクス製スペクトルアナライザーPMA-11を用いて測定した。これらを元に輝度が1000cd/m2付近の外部量子効率を輝度換算法により算出した。
各素子を輝度が1000cd/m2になるように直流電圧を印加して発光させ続け、輝度が500cd/m2になるまでに要した時間を駆動耐久性の指標とし、比較例1の値を100として相対値で示した。
各素子を輝度が1000cd/m2になるように直流電圧を印加して発光させた時の色度と、80℃の恒温槽中で輝度が1000cd/m2になるように直流電圧を印加して発光させ続け、輝度が500cd/m2になった時の色度のx値、y値の差(Δx,Δy)を高温駆動時の色度変化の指標とした。
また、本発明の素子は車載用途などの高温環境で使用する際においても発光効率や耐久性にも優れ、発光装置、表示装置、照明装置に好適である。
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
本出願は、2009年7月31日出願の日本特許出願(特願2009-180223)、2009年8月31日出願の日本特許出願(特願2009-201155)及び2009年9月25日出願の日本特許出願(特願2009-221663)に基づくものであり、それらの内容はここに参照して組み込まれる
3・・・陽極
4・・・正孔注入層
5・・・正孔輸送層
6・・・発光層
7・・・正孔ブロック層
8・・・電子輸送層
9・・・陰極
10・・・有機電界発光素子(有機EL素子)
11・・・有機層
12・・・保護層
14・・・接着層
16・・・封止容器
20・・・発光装置
30・・・光散乱部材
30A・・・光入射面
30B・・・光出射面
31・・・透明基板
32・・・微粒子
40・・・照明装置
Claims (19)
- 基板上に、一対の電極と、該電極間に発光層を有する有機電界発光素子であって、前記発光層に以下の一般式(1)で表される化合物と、一般式(PQ-1)で表される化合物とを含有する有機電界発光素子。
- 前記一般式(PQ-1)において、n=3である、請求項1に記載の有機電界発光素子。
- 前記一般式(PQ-1)において、n=2である、請求項1に記載の有機電界発光素子。
- 前記一般式(PQ-1)において、R1~R6が水素原子である、請求項1~3のいずれか一項に記載の有機電界発光素子。
- 前記一般式(PQ-1)において、R9がアリール基を表す、請求項1~4のいずれか一項に記載の有機電界発光素子。
- 前記一般式(1)で表される化合物が、以下の一般式(2)で表される化合物である請求項1~5のいずれか一項に記載の有機電界発光素子。
- 前記(X-Y)がアセチルアセトネート(acac)、ピコリネート(pic)、及びこれらの誘導体のいずれかである請求項1~7のいずれか一項に記載の有機電界発光素子。
- 前記発光層と陰極の間に前記一般式(1)で表される化合物を含有する層を有する、請求項1~10のいずれか一項に記載の有機電界発光素子。
- 請求項1~11のいずれか一項に記載の前記一般式(1)で表される化合物と前記一般式(PQ-1)で表される化合物とを含有する組成物。
- 前記一般式(C-1)で表される化合物を更に含む請求項12に記載の組成物。
- 請求項1~11のいずれか一項に記載の前記一般式(1)で表される化合物と前記一般式(PQ-1)で表される化合物とを含有する発光層。
- 前記一般式(C-1)で表される化合物を更に含む請求項14に記載の発光層。
- 請求項1~11のいずれか一項に記載の前記一般式(1)で表される化合物と前記一般式(PQ-1)で表される化合物とを同時に加熱することにより昇華させて成膜する成膜方法。
- 請求項1~11のいずれか一項に記載の有機電界発光素子を用いた発光装置。
- 請求項1~11のいずれか一項に記載の有機電界発光素子を用いた表示装置。
- 請求項1~11のいずれか一項に記載の有機電界発光素子を用いた照明装置。
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JP2015006995A (ja) * | 2012-06-18 | 2015-01-15 | 東ソー株式会社 | 環状アジン化合物、その製造方法、及びそれを含有する有機電界発光素子 |
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JP2017518281A (ja) * | 2014-05-14 | 2017-07-06 | プレジデント アンド フェローズ オブ ハーバード カレッジ | 有機発光ダイオード材料 |
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CN107406415A (zh) * | 2015-01-20 | 2017-11-28 | 保土谷化学工业株式会社 | 嘧啶衍生物和有机电致发光器件 |
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JP2015167239A (ja) | 2015-09-24 |
KR101789708B1 (ko) | 2017-10-25 |
JP5735229B2 (ja) | 2015-06-17 |
KR102007594B1 (ko) | 2019-08-05 |
US9340728B2 (en) | 2016-05-17 |
TW201619351A (zh) | 2016-06-01 |
US20120126690A1 (en) | 2012-05-24 |
TWI555823B (zh) | 2016-11-01 |
JP2011091366A (ja) | 2011-05-06 |
TW201109421A (en) | 2011-03-16 |
KR20170120193A (ko) | 2017-10-30 |
TWI529237B (zh) | 2016-04-11 |
KR20120042877A (ko) | 2012-05-03 |
JP6286386B2 (ja) | 2018-02-28 |
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