WO2011074254A1 - 有機発光媒体 - Google Patents
有機発光媒体 Download PDFInfo
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- WO2011074254A1 WO2011074254A1 PCT/JP2010/007271 JP2010007271W WO2011074254A1 WO 2011074254 A1 WO2011074254 A1 WO 2011074254A1 JP 2010007271 W JP2010007271 W JP 2010007271W WO 2011074254 A1 WO2011074254 A1 WO 2011074254A1
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- 0 C*N(*)*C=CC Chemical compound C*N(*)*C=CC 0.000 description 23
- AFJOBNSWSNOIBB-UHFFFAOYSA-N CCC(C)[Si+](C)c(cc1)ccc1N(C(C1)c(cc2)c3c4c2c(C(C)C)cc(NC(Cc(cc2)ccc2[Si](C)(C)C)c(cc2)ccc2F)c4C=CC3C1C(C)C)c(cc1)ccc1F Chemical compound CCC(C)[Si+](C)c(cc1)ccc1N(C(C1)c(cc2)c3c4c2c(C(C)C)cc(NC(Cc(cc2)ccc2[Si](C)(C)C)c(cc2)ccc2F)c4C=CC3C1C(C)C)c(cc1)ccc1F AFJOBNSWSNOIBB-UHFFFAOYSA-N 0.000 description 1
- BNUSVIDVSKMBJX-UHFFFAOYSA-N Cc(cc1)ccc1N(c1ccccc1)c1c(ccc(cc2)c3c(cc4)c2N(c2ccccc2)c(cc2)ccc2C#N)c3c4cc1 Chemical compound Cc(cc1)ccc1N(c1ccccc1)c1c(ccc(cc2)c3c(cc4)c2N(c2ccccc2)c(cc2)ccc2C#N)c3c4cc1 BNUSVIDVSKMBJX-UHFFFAOYSA-N 0.000 description 1
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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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Definitions
- the present invention relates to an organic light emitting medium and an organic electroluminescence element.
- Organic electroluminescence (EL) devices using organic substances are promising for use as solid-state, inexpensive, large-area full-color display devices, and many developments have been made.
- an organic EL element is composed of a light emitting layer and a pair of counter electrodes sandwiching the layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side. Further, the electrons recombine with holes in the light emitting layer to generate an excited state, and energy is emitted as light when the excited state returns to the ground state.
- Patent Documents 1-3 describe a doping material in which an electron withdrawing group is substituted. Although organic EL elements using these doping materials have a feature of pure blue, further improvement in life characteristics has been demanded.
- Patent Documents 4 and 5 disclose some compounds having a substituent at the ortho position as host materials. However, organic EL devices using these host materials have been required to further improve the life characteristics.
- An object of the present invention is to provide an organic light-emitting medium that can obtain blue light emission with high color purity and a long emission lifetime.
- organic light emitting media According to the present invention, the following organic light emitting media and the like are provided. 1.
- R 1 to R 8 and R 11 to R 14 are a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted ring forming carbon number of 3 to 10 cycloalkyl groups, substituted or unsubstituted alkylsilyl groups having 3 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 8 to 30 ring carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms A substituted or unsubstituted aryloxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.
- Ar 1 and Ar 2 each represent a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.
- Ar 11 represents a substituted or unsubstituted anthracene-containing group, a substituted or unsubstituted pyrene-containing group, a substituted or unsubstituted chrysene-containing group, a substituted or unsubstituted benzofluoranthene-containing group, or a substituted or unsubstituted group.
- a substituted styryl-containing group is shown.
- Ar 12 and Ar 13 each represent a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.
- G represents an electron-withdrawing group.
- Ar 21 to Ar 24 , Ar 31 to Ar 34 , Ar 41 to Ar 46 , Ar 51 to Ar 54 , Ar 61 to Ar 66 , and Ar 71 to Ar 73 each have 6 to 30 ring carbon atoms that are substituted or unsubstituted.
- G represents an electron-withdrawing group.
- r 11 , r 12 , r 21 , r 22 , r 31 , r 32 , r 41 , r 42 , r 51 , r 52 , r 71 represent an integer of 1 to 5, respectively. When there are two or more G, they may be the same or different.
- R 101 to R 105 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group.
- the organic light-emitting medium according to 6, wherein the anthracene derivative represented by the formula (1) is represented by the following formula (11).
- R 15 to R 19 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group.
- R 101 to R 105 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms;
- An organic thin film comprising the organic light-emitting medium according to any one of 1 to 8.
- 10. 10 An organic electroluminescence device in which one or more organic thin film layers including at least a light emitting layer are sandwiched between a cathode and an anode, wherein at least one layer of the organic thin film layer is the organic thin film according to 9.
- an organic light emitting medium having a blue light emission with high color purity and a long light emission lifetime.
- the organic light-emitting medium of the present invention contains an anthracene derivative represented by the following formula (1) and a compound containing at least one electron-withdrawing group in the molecular structure.
- each of R 1 to R 8 and R 11 to R 14 represents a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted ring forming carbon number of 3 to 10 Cycloalkyl group, substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 8 to 30 ring carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms Substituted or unsubstituted aryloxy group having 6 to 20 ring carbon atoms, substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms Indicates a group.
- Ar 1 and Ar 2 each represent a substituted or unsubstitute
- the material of the present invention can improve the light emission lifetime by using a combination of the anthracene derivative represented by the above formula (1) and a compound containing at least one electron-withdrawing group in the molecular structure.
- Ar 1 is preferably a condensed aromatic ring group having 10 to 30 ring carbon atoms. Moreover, the anthracene derivative represented by following formula (10) is preferable.
- R 1 to R 8 , R 11 to R 14 , and Ar 2 are the same as those in the formula (1).
- R 101 to R 105 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group.
- an anthracene derivative represented by the following formula (11) is preferable.
- R 1 to R 8 , R 11 to R 14 , and R 101 to R 105 are the same as those in the formula (10).
- R 15 to R 19 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted group.
- any one of R 101 to R 105 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, It is preferable that all other groups of 101 to R 105 are hydrogen atoms.
- ring-forming carbon means a carbon atom constituting a saturated ring, an unsaturated ring, or an aromatic ring.
- Ring-forming atom means a carbon atom and a hetero atom constituting a hetero ring (including a saturated ring, an unsaturated ring, and an aromatic ring).
- substituents in “substituted or unsubstituted” include an alkyl group, an alkylsilyl group, a halogenated alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, a heterocyclic group, and an aralkyl group as described later.
- the hydrogen atom of the compound of the present specification includes light hydrogen and deuterium.
- aryl group having 6 to 30 ring carbon atoms examples include phenyl, naphthyl, anthryl, phenanthryl, naphthacenyl, pyrenyl, chrysenyl, benzo [c] phenanthryl, benzo [g] chrysenyl, triphenylenyl Group, fluorenyl group, 9,9-dimethylfluoren-2-yl group, benzofluorenyl group, dibenzofluorenyl group, biphenylyl group, terphenylyl group, tolyl group, pt-butylphenyl group, p- ( 2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenylyl group, 4 ′′ -t-butyl- and p-terphenyl-4-yl
- the aryl group having 6 to 30 ring carbon atoms is preferably an unsubstituted phenyl group, a substituted phenyl group, a substituted or unsubstituted aryl group having 10 to 14 ring carbon atoms (for example, a 1-naphthyl group, 2 -Naphthyl group, 9-phenanthryl group), substituted or unsubstituted fluorenyl group (2-fluorenyl group) and substituted or unsubstituted pyrenyl group (1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group).
- the aryl group having 6 to 30 ring carbon atoms is preferably an aryl group having 6 to 20 ring carbon atoms, more preferably an aryl group having 6 to 14 ring carbon atoms, and particularly preferably 6 to 10 ring carbon atoms.
- the aryl group having 6 to 30 ring carbon atoms may be substituted with a substituent such as an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and the substituents that may be substituted are described above. The same group as a substituent is mentioned.
- the substituent which may be substituted is preferably an aryl group or a heterocyclic group.
- heterocyclic group having 5 to 30 ring atoms examples include pyrrolyl group, pyrazinyl group, pyridinyl group, indolyl group, isoindolyl group, furyl group, benzofuranyl group, isobenzofuranyl group, dibenzofuranyl group, dibenzothiophenyl group Quinolyl group, isoquinolyl group, quinoxalinyl group, carbazolyl group, phenanthridinyl group, acridinyl group, phenanthronyl group, phenothiazinyl group, phenoxazinyl group, oxazolyl group, oxadiazolyl group, flazanyl group, thienyl group, 2-methylpyrrolyl group, 3 -Methylpyrrolyl group, 2-t-butylpyrrolyl group, 3- (2-phenylpropyl) pyrrolyl group and the like.
- a dibenzofuranyl group, a dibenzothiophenyl group, and a carbazolyl group are preferable.
- the heterocyclic group having 5 to 30 ring atoms is preferably a heterocyclic group having 5 to 20 ring atoms, and more preferably a heterocyclic group having 5 to 14 ring atoms.
- the heterocyclic group having 5 to 30 ring atoms may be substituted with a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. And the same groups as those described above.
- the substituent which may be substituted is preferably an aryl group or a heterocyclic group.
- alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, and n-hexyl group.
- the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
- the alkyl group having 1 to 10 carbon atoms is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group or t-butyl group.
- the alkyl group having 1 to 10 carbon atoms may be substituted with a substituent such as an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and the substituents that may be substituted are the substituents described above. The same group is mentioned.
- the substituent which may be substituted is preferably an aryl group or a heterocyclic group.
- Examples of the cycloalkyl group having 3 to 10 ring carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 1-adamantyl group, 2-adamantyl group, 1-norbornyl group, 2- And norbornyl group. Preferably, they are a cyclopentyl group and a cyclohexyl group.
- the cycloalkyl group having 3 to 10 ring carbon atoms is preferably a cycloalkyl group having 3 to 8 ring carbon atoms, and more preferably a cycloalkyl group having 3 to 6 ring carbon atoms.
- the cycloalkyl group having 3 to 10 ring carbon atoms may be substituted with a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. And the same groups as those described above.
- the substituent which may be substituted is preferably an aryl group or a heterocyclic group.
- alkylsilyl group and arylsilyl group examples include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, and a triphenylsilyl group.
- the silyl group may be substituted with a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and examples of the substituent that may be substituted include the same groups as those described above. It is done.
- the substituent which may be substituted is preferably an aryl group or a heterocyclic group.
- the alkoxy group having 1 to 20 carbon atoms is a group represented by —OZ, and Z is selected from the substituted or unsubstituted alkyl group.
- the alkyl group may be substituted with a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. Examples of the substituent that may be substituted include the same groups as the above-described substituents. It is done.
- the substituent which may be substituted is preferably an aryl group or a heterocyclic group.
- the aryloxy group having 6 to 20 carbon atoms is a group represented by —OZ, and Z is selected from the substituted or unsubstituted aryl group.
- the aryl group may be substituted with a substituent such as an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and examples of the substituent that may be substituted include the same groups as the above-described substituents. .
- the substituent which may be substituted is preferably an aryl group or a heterocyclic group.
- anthracene derivative represented by the formula (1) include the following.
- Ar 11 represents a substituted or unsubstituted anthracene-containing group, a substituted or unsubstituted pyrene-containing group, a substituted or unsubstituted chrysene-containing group, a substituted or unsubstituted benzofluoranthene-containing group, or a substituted or unsubstituted group.
- Ar 12 and Ar 13 each represent a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.
- G represents an electron-withdrawing group.
- p and q are integers of 0 or 1
- r is an integer of 1 to 5
- s is an integer of 1 to 6.
- the substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms and the substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms of Ar 12 are respectively corresponding 1 + r-valent residues. .
- the electron withdrawing group is a group having a function of decreasing the electron density, and examples thereof include a cyano group, fluorine, a halogenated alkyl group, a halogenated alkyl-substituted alkyl group, a nitro group, and a carbonyl group.
- a cyano group, fluorine, a halogenated alkyl group, and a halogenated alkyl-substituted alkyl group are preferable, and a cyano group is particularly preferable. It is presumed that the lifetime can be extended by trapping excess electrons with these electron-withdrawing groups to suppress the entry of electrons into the hole transport material and preventing the deterioration of the hole transport material.
- the anthracene-containing group is a group having an anthracene skeleton in the molecule.
- the pyrene-containing group is a group having a pyrene skeleton in the molecule.
- the chrysene-containing group is a group having a chrysene skeleton in the molecule.
- the benzofluoranthene-containing group is a group having a benzofluoranthene skeleton in the molecule.
- the styryl-containing group is a group having a styryl skeleton in the molecule.
- the compound of the formula (2) is preferably represented by the following formulas (3) to (8).
- R 21 to R 28 , R 31 to R 38 , R 41 to R 46 , R 51 to R 60 , and R 71 to R 79 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted carbon number of 1
- Ar 21 to Ar 24 , Ar 31 to Ar 34 , Ar 41 to Ar 46 , Ar 51 to Ar 54 , Ar 61 to Ar 66 , and Ar 71 to Ar 73 each have 6 to 30 ring carbon atoms that are substituted or unsubstituted.
- G represents an electron-withdrawing group.
- r 11 , r 12 , r 21 , r 22 , r 31 , r 32 , r 41 , r 42 , r 51 , r 52 , r 71 represent an integer of 1 to 5, respectively. When there are two or more G, they may be the same or different.
- the substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms and the substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms of Ar 21 are each a corresponding 1 + r 11- valent residue. is there.
- the aryl group and heterocyclic group of Ar 24 are the corresponding 1 + r 12- valent residue
- the aryl group and heterocyclic group of Ar 31 are the corresponding 1 + r 21- valent residue
- Ar 34 The aryl group and heterocyclic group are the corresponding 1 + r 22 valent residues
- the aryl group and heterocyclic group of Ar 43 are the corresponding 1 + r 31 valent residues
- the aryl group and heterocyclic group of Ar 46 Are the corresponding 1 + r 32 valent residues
- the aryl group and heterocyclic group of Ar 51 are the corresponding 1 + r 41 valent residues
- the aryl group and heterocyclic group of Ar 54 are the corresponding 1 + r 42
- the aryl group and heterocyclic group of Ar 63 are the corresponding 1 + r 51 valent residue
- the aryl group and heterocyclic group of Ar 66 are the corresponding 1 + r 52 valent residue.
- the ru group and heterocyclic group are the corresponding 1 + r 71 valent residues.
- a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms of Ar 61 and Ar 62 are each a corresponding divalent residue. It is. Specific examples of groups and substituents of formulas (2) to (8) are given below.
- alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, An n-octyl group and the like can be mentioned.
- the carbon number is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 6.
- methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl and n-hexyl are preferred.
- the alkylsilyl group is represented as —SiY 3, and examples of Y include the above alkyl examples.
- aryl group for example, phenyl group, naphthyl group, anthryl group, phenanthryl group, naphthacenyl group, pyrenyl group, chrysenyl group, benzo [c] phenanthryl group, benzo [g] chrycenyl group, triphenylenyl group, fluorenyl group, benzofuryl group
- aryl group for example, phenyl group, naphthyl group, anthryl group, phenanthryl group, naphthacenyl group, pyrenyl group, chrysenyl group, benzo [c] phenanthryl group, benzo [g] chrycenyl group, triphenylenyl group, fluorenyl group, benzofuryl group
- Examples include oleenyl group, dibenzofluorenyl group, biphenylyl group, and terphenylyl group.
- Examples of the substituted or unsubstituted heterocyclic group include pyrrolyl group, pyrazinyl group, pyridinyl group, indolyl group, isoindolyl group, furyl group, benzofuranyl group, isobenzofuranyl group, dibenzofuranyl group, dibenzothiophenyl group, Quinolyl group, isoquinolyl group, quinoxalinyl group, carbazolyl group, phenanthridinyl group, acridinyl group, phenanthronyl group, phenazinyl group, phenothiazinyl group, phenoxazinyl group, oxazolyl group, oxadiazolyl group, furazanyl group, thienyl group, 2-methylpyrrolyl group , 3-methylpyrrolyl group, 2-t-butylpyrrolyl group, 3- (2-phenylpropyl) pyrrolyl group, and
- the number of ring-forming atoms of the substituted or unsubstituted heterocyclic group is preferably 5 to 20, and more preferably 5 to 14.
- a dibenzofuranyl group, a dibenzothiophenyl group, and a carbazolyl group are preferable.
- the arylsilyl group is represented as —SiZ 3, and examples of Z include the above examples of aryl.
- the alkoxy group is represented as -OY, and examples of Y include the above examples of alkyl or aryl.
- cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, and a 2-norbornyl group.
- the number of ring-forming carbon atoms is preferably 3 to 10, more preferably 3 to 8, and further preferably 3 to 6. Examples of compounds having at least one electron-withdrawing group in a specific molecular structure are shown below.
- a compound containing at least one electron withdrawing group in the molecular structure is included as a doping material (dopant).
- the content of the compound is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass.
- the anthracene derivative and the electron-withdrawing group-containing compound of the present invention can be used for a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer in addition to the light emitting layer.
- organic EL elements having a plurality of organic compound layers include (anode / hole injection layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer / cathode), Examples of such layers include (anode / hole injection layer / light emitting layer / electron injection layer / cathode) and (anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode).
- the organic EL element can prevent luminance and lifetime from being reduced due to quenching by forming the organic thin film layer into a multi-layer structure.
- a light emitting material, a doping material, a hole injection material, and an electron injection material can be used in combination.
- the hole injection layer, the light emitting layer, and the electron injection layer may each be formed of two or more layers. In that case, in the case of a hole injection layer, the layer that injects holes from the electrode is a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call.
- an electron injection layer a layer for injecting electrons from an electrode is called an electron injection layer, and a layer for receiving electrons from the electron injection layer and transporting electrons to a light emitting layer is called an electron transport layer.
- an electron injection layer a layer for injecting electrons from an electrode
- an electron transport layer a layer for receiving electrons from the electron injection layer and transporting electrons to a light emitting layer.
- Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic layer or metal electrode.
- Examples of materials other than the anthracene derivative of the present invention that can be used in the light emitting layer together with the electron-withdrawing group-containing compound of the present invention include, for example, naphthalene, phenanthrene, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenyl Condensed polycyclic aromatic compounds such as cyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene and their derivatives, organometallic complexes such as tris (8-quinolinolato) aluminum, triarylamine derivatives, styrylamine derivatives, stilbene derivatives, Coumarin derivatives, pyran derivatives, oxazone derivatives, benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives
- a hole injection material a compound having the ability to transport holes, the hole injection effect from the anode, the hole injection effect excellent for the light emitting layer or the light emitting material, and the thin film forming ability Is preferred.
- phthalocyanine derivatives naphthalocyanine derivatives, porphyrin derivatives, benzidine-type triphenylamine, diamine-type triphenylamine, hexacyanohexaazatriphenylene, and derivatives thereof, and polyvinylcarbazole, polysilane, conductive polymers, etc. Examples include, but are not limited to, polymer materials.
- a more effective hole injection material is a phthalocyanine derivative.
- phthalocyanine (Pc) derivatives examples include H2Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl2SiPc, (HO) AlPc, (HO) GaPc, VOPc, and OPP Examples include, but are not limited to, phthalocyanine derivatives and naphthalocyanine derivatives such as MoOPc and GaPc-O-GaPc.
- carriers can be sensitized by adding an electron acceptor such as a TCNQ derivative to the hole injection material.
- a preferred hole transport material that can be used in the organic EL device of the present invention is an aromatic tertiary amine derivative.
- the aromatic tertiary amine derivative include N, N′-diphenyl-N, N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N, N, N ′, N′-tetra Biphenyl-1,1′-biphenyl-4,4′-diamine or the like, or an oligomer or polymer having an aromatic tertiary amine skeleton is not limited thereto.
- the electron injecting material a compound having an ability to transport electrons, an electron injecting effect from the cathode, an excellent electron injecting effect for the light emitting layer or the light emitting material, and an excellent thin film forming ability is preferable.
- more effective electron injection materials are metal complex compounds and nitrogen-containing heterocyclic derivatives.
- the metal complex compound include 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinato) zinc, tris (8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis. (10-Hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, and the like are exemplified, but not limited thereto.
- these electron injection materials further contain a dopant, and more preferably, a dopant typified by an alkali metal is doped in the vicinity of the cathode interface of the second organic layer in order to facilitate the reception of electrons from the cathode.
- the dopant include a donor metal, a donor metal compound, and a donor metal complex. These reducing dopants may be used alone or in combination of two or more.
- the organic EL device of the present invention in the light emitting layer, in addition to at least one selected from the pyrene derivative represented by the formula (1), a light emitting material, a doping material, a hole injecting material, a hole transporting material, and an electron At least one of the injection materials may be contained in the same layer.
- a protective layer is provided on the surface of the device, or the entire device is protected by silicon oil, resin, etc. Is also possible.
- a material having a work function larger than 4 eV is suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum Palladium, etc. and their alloys, metal oxides such as tin oxide and indium oxide used for ITO substrates and NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used.
- Suitable conductive materials for the cathode are those having a work function smaller than 4 eV, such as magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, lithium fluoride, and the like.
- alloys include magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto.
- the ratio of the alloy is controlled by the temperature of the vapor deposition source, the atmosphere, the degree of vacuum, etc., and is selected to an appropriate ratio. If necessary, the anode and the cathode may be formed of two or more layers.
- the organic EL device of the present invention in order to emit light efficiently, it is desirable that at least one surface be sufficiently transparent in the light emission wavelength region of the device.
- the substrate is also preferably transparent.
- the transparent electrode is set using the above-described conductive material so that predetermined translucency is ensured by a method such as vapor deposition or sputtering.
- the electrode on the light emitting surface preferably has a light transmittance of 10% or more.
- the substrate is not limited as long as it has mechanical and thermal strength and has transparency, and includes a glass substrate and a transparent resin film.
- Each layer of the organic EL device of the present invention can be formed by applying any one of dry deposition methods such as vacuum deposition, sputtering, plasma and ion plating, and wet deposition methods such as spin coating, dipping and flow coating. Can do.
- the film thickness is not particularly limited, but must be set to an appropriate film thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied.
- the normal film thickness is suitably in the range of 5 nm to 10 ⁇ m, but more preferably in the range of 10 nm to 0.2 ⁇ m.
- the material for forming each layer is dissolved or dispersed in an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, dioxane or the like to form a thin film, and any solvent may be used.
- an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, dioxane or the like
- any solvent may be used.
- an organic EL material-containing solution containing the electron-withdrawing group-containing compound of the present invention and a solvent can be used as the organic EL material.
- the organic EL material preferably includes a host material and a dopant material, the dopant material is the electron-withdrawing group-containing compound of the present invention, and the host material is the anthracene derivative of the present invention.
- an appropriate resin or additive may be used for improving the film formability and preventing pinholes in the film.
- the organic EL device of the present invention can be used for a flat light emitter such as a flat panel display of a wall-mounted television, a copying machine, a printer, a light source such as a backlight of a liquid crystal display or instruments, a display board, a marker lamp, and the like.
- the compound of this invention can be used not only in an organic EL element but in fields, such as an electrophotographic photoreceptor, a photoelectric conversion element, a solar cell, an image sensor.
- Example 1 A 25 mm ⁇ 75 mm ⁇ 1.1 mm thick glass substrate with ITO transparent electrode (anode) (manufactured by Geomatic) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes.
- a glass substrate with a transparent electrode line after washing is mounted on a substrate holder of a vacuum deposition apparatus, and first, a compound A-1 having a film thickness of 50 nm is formed so as to cover the transparent electrode on the surface on which the transparent electrode line is formed. Was deposited. Subsequent to the formation of the A-1 film, A-2 having a film thickness of 45 nm was formed on the A-1 film.
- the compound EM-1 and the compound DM-1 were formed in a film thickness ratio of 20: 1 with a film thickness of 20 nm to form a blue light emitting layer.
- an ET-1 having a thickness of 30 nm as an electron transport layer was formed by vapor deposition.
- LiF was formed to a thickness of 1 nm.
- metal Al was deposited to a thickness of 150 nm to form a metal cathode, thereby producing an organic EL light emitting device.
- Example 2-48, Comparative Example 1-7 An organic EL device was produced in the same manner as in Example 1 except that the host material and the doping material were changed as shown in Tables 1 and 2. The materials used in each example are shown below.
- a current density of 10 mA / cm 2 was passed through the organic EL elements produced in the above examples and comparative examples, and the emission spectrum was measured with a spectral radiance meter (CS1000: manufactured by Minolta). The quantum yield was calculated. The lifetime was evaluated by a half-life at an initial luminance of 500 cd / m 2 . The results are shown in Tables 1 and 2.
- N P Number of photons
- N E Number of electrons
- ⁇ Emission intensity (W / sr ⁇ m 2 ⁇ nm)
- J Current density (mA / cm 2 )
- the ortho-position aryl or heteroaryl substituent of the phenyl group that substitutes the position has a high anti-association effect.
- the emission chromaticity is significantly pure blue.
- the dopant characterized by the present invention has an electron-withdrawing group, it has an effect of trapping excess electrons.
- anthracene derivatives and dopants which are the characteristics of the present invention, are used in combination, pure blue coloration and long life by suppressing the entry of electrons into the hole transport material are achieved.
- Comparative Examples 1 to 7 and Comparative Example 8 it can be seen that the color purity is enhanced by the compound having an electron-withdrawing group, but the anthracene of the present invention is bulky and has a high anti-association effect due to Ar 2. It can be seen that when combined with the derivative (1), further shorter wavelength light emission is possible.
- the combination of the present invention is a combination that can maintain a pure blue color and achieve a long life. As a result, it is possible to realize a display device having a long life and high color reproducibility.
- the organic EL device of the present invention can be used for a flat light emitter such as a flat panel display of a wall-mounted television, a copying machine, a printer, a light source such as a backlight of a liquid crystal display or instruments, a display board, a marker lamp, and the like.
- a flat light emitter such as a flat panel display of a wall-mounted television, a copying machine, a printer, a light source such as a backlight of a liquid crystal display or instruments, a display board, a marker lamp, and the like.
Abstract
Description
発光層に使用される材料の例として、特許文献1-3には電子吸引性基が置換されたドーピング材料が記載されている。これらのドーピング材料を用いた有機EL素子は、純青色化するという特徴があったが、寿命特性はさらなる改善が求められていた。また、特許文献4、5にはオルト位に置換基を持つ化合物がホスト材料としていくつか開示されている。しかしながら、これらのホスト材料を用いた有機EL素子は、さらなる寿命特性の改善が求められていた。
1.下記式(1)で表されるアントラセン誘導体と、分子構造中に電子吸引性基を少なくとも1つ含有する化合物とを、含有する有機発光媒体。
Ar1、Ar2は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール基、置換もしくは無置換の環形成原子数5~30の複素環基を示す。)
2.前記電子吸引性基を少なくとも1つ含有する化合物が、下記式(2)で表される化合物である1に記載の有機発光媒体。
Ar12及びAr13は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示す。
Gは電子吸引性基を示す。
p及びqは、それぞれ0又は1の整数であり、rは1~5の整数であり、sは1~6の整数を示す。p=q=0の場合、r=1であり、p=1の場合、q=1である。)
3.前記式(2)で表される化合物が、下記式(3)~(8)で表される化合物である2に記載の有機発光媒体。
Ar21~Ar24、Ar31~Ar34、Ar41~Ar46、Ar51~Ar54、Ar61~Ar66、Ar71~Ar73は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール基、置換もしくは無置換の環形成原子数5~30の複素環基を示す。
Gは電子吸引性基を示す。
r11、r12、r21、r22、r31、r32、r41、r42、r51、r52、r71、は、それぞれ、1~5の整数を示す。Gが2つ以上ある場合は、それぞれ同一でも異なっていてもよい。)
4.前記電子吸引性置換基がシアノ基である1~3のいずれかに記載の有機発光媒体。
5.前記式(1)で表されるアントラセン誘導体のAr1が環形成炭素数10~30の縮合芳香族環基である1~4のいずれかに記載の有機発光媒体。
6.前記式(1)で表されるアントラセン誘導体が、下記式(10)で表される1~4のいずれかに記載の有機発光媒体。
R101~R105は、それぞれ水素原子、フッ素原子、置換もしくは無置換の炭素数1~10のアルキル基、置換もしくは無置換の環形成炭素数3~10のシクロアルキル基、置換もしくは無置換の炭素数3~30のアルキルシリル基、置換もしくは無置換の環形成炭素数8~30のアリールシリル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~20のアリールオキシ基、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示す。
7.前記式(1)で表されるアントラセン誘導体が、下記式(11)で表される6に記載の有機発光媒体。
R15~R19は、それぞれ水素原子、フッ素原子、置換もしくは無置換の炭素数1~10のアルキル基、置換もしくは無置換の環形成炭素数3~10のシクロアルキル基、置換もしくは無置換の炭素数3~30のアルキルシリル基、置換もしくは無置換の環形成炭素数8~30のアリールシリル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~20のアリールオキシ基、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示す。)
8.前記R101~R105のいずれか一つが、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基であり、前記R101~R105の他の基が全て水素原子である、6又は7に記載の有機発光媒体。
9.1~8のいずれかに記載の有機発光媒体からなる有機薄膜。
10.陰極と陽極の間に少なくとも発光層を含む1以上の有機薄膜層が挟持されている有機エレクトロルミネッセンス素子において、該有機薄膜層の少なくとも一層が、9に記載の有機薄膜である有機エレクトロルミネッセンス素子。
Ar1、Ar2は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール基、置換もしくは無置換の環形成原子数5~30の複素環基を示す。
R101~R105は、それぞれ水素原子、フッ素原子、置換もしくは無置換の炭素数1~10のアルキル基、置換もしくは無置換の環形成炭素数3~10のシクロアルキル基、置換もしくは無置換の炭素数3~30のアルキルシリル基、置換もしくは無置換の環形成炭素数8~30のアリールシリル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~20のアリールオキシ基、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示す。
R15~R19は、それぞれ水素原子、フッ素原子、置換もしくは無置換の炭素数1~10のアルキル基、置換もしくは無置換の環形成炭素数3~10のシクロアルキル基、置換もしくは無置換の炭素数3~30のアルキルシリル基、置換もしくは無置換の環形成炭素数8~30のアリールシリル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~20のアリールオキシ基、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示す。
また、「置換もしくは無置換の・・・」における置換基としては、後述するようなアルキル基、アルキルシリル基、ハロゲン化アルキル基、アリール基、シクロアルキル基、アルコキシ基、複素環基、アラルキル基、アリールオキシ基、アリールチオ基、アルコキシカルボニル基、ハロゲン原子、ヒドロキシル基、ニトロ基、シアノ基、カルボキシ基、ジベンゾフラニル基、フルオレニル基等が挙げられる。
本明細書の化合物の水素原子には、軽水素、重水素が含まれる。
以下、上記各式の基の例及び置換基の例を示す。
上記環形成炭素数6~30のアリール基は、好ましくは環形成炭素数6~20のアリール基、より好ましくは環形成炭素数6~14のアリール基、特に好ましくは環形成炭素数6~10のアリール基である。
前記環形成炭素数6~30のアリール基は、アルキル基、シクロアルキル基、アリール基、複素環基等の置換基により置換されていてもよく、これら置換してもよい置換基は、上述した置換基と同様の基が挙げられる。なお置換してもよい置換基は、アリール基、複素環基が好ましい。
上記炭素数1~10のアルキル基としては、好ましくは、炭素数1~8のアルキル基であり、より好ましくは炭素数1~6のアルキル基である。
上記炭素数1~10のアルキル基としては、好ましくは、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、s-ブチル基、イソブチル基、t-ブチル基である。前記炭素数1~10のアルキル基は、アルキル基、シクロアルキル基、アリール基、複素環基等の置換基により置換されていてもよく、これら置換してもよい置換基は、上述した置換基と同様の基が挙げられる。なお置換してもよい置換基は、アリール基、複素環基が好ましい。
Ar12及びAr13は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示す。
Gは電子吸引性基を示す。
p,qは0又は1の整数であり、rは1~5の整数であり、sは1~6の整数を示す。p=q=0の場合、r=1であり、p=1の場合、q=1である。
尚、Ar12の置換もしくは無置換の環形成炭素数6~30のアリール基、及び置換もしくは無置換の環形成原子数5~30の複素環基は、それぞれ対応する1+r価の残基である。
前記ピレン含有基は、分子内にピレン骨格を有する基である。
前記クリセン含有基は、分子内にクリセン骨格を有する基である。
前記ベンゾフルオランテン含有基は、分子内にベンゾフルオランテン骨格を有する基である。
前記スチリル含有基は、分子内にスチリル骨格を有する基である。
Ar21~Ar24、Ar31~Ar34、Ar41~Ar46、Ar51~Ar54、Ar61~Ar66、Ar71~Ar73は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール基、置換もしくは無置換の環形成原子数5~30の複素環基を示す。
Gは電子吸引性基を示す。
r11、r12、r21、r22、r31、r32、r41、r42、r51、r52、r71、は、それぞれ、1~5の整数を示す。Gが2つ以上ある場合は、それぞれ同一でも異なっていてもよい。
尚、Ar21の置換もしくは無置換の環形成炭素数6~30のアリール基、及び置換もしくは無置換の環形成原子数5~30の複素環基は、それぞれ対応する1+r11価の残基である。同様に、Ar24のアリール基及び複素環基は、対応する1+r12価の残基であり、Ar31のアリール基及び複素環基は、対応する1+r21価の残基であり、Ar34のアリール基及び複素環基は、対応する1+r22価の残基であり、Ar43のアリール基及び複素環基は、対応する1+r31価の残基であり、Ar46のアリール基及び複素環基は、対応する1+r32価の残基であり、Ar51のアリール基及び複素環基は、対応する1+r41価の残基であり、Ar54のアリール基及び複素環基は、対応する1+r42価の残基であり、Ar63のアリール基及び複素環基は、対応する1+r51価の残基であり、Ar66のアリール基及び複素環基は、対応する1+r52価の残基であり、Ar71のアリール基及び複素環基は、対応する1+r71価の残基である。
また、Ar61及びAr62の置換もしくは無置換の環形成炭素数6~30のアリール基、置換もしくは無置換の環形成原子数5~30の複素環基は、それぞれ対応する2価の残基である。
以下に、式(2)~(8)の各基、及び、置換基の具体例を挙げる。
上記炭素数は、1~10が好ましく、1~8がより好ましく、1~6がさらに好ましい。中でもメチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、s-ブチル基、イソブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基が好ましい。
前記アリール基の環形成炭素数は、6~20が好ましく、6~14がより好ましく、6~10がさらに好ましい。好ましくは、フェニル基、ナフチル基である。
好ましくは、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基である。
具体的な分子構造中に電子吸引性基を少なくとも1つ含有する化合物であるの例を以下に示す。
また、正孔注入材料にTCNQ誘導体等の電子受容物質を添加することによりキャリアを増感させることもできる。
芳香族三級アミン誘導体としては、例えば、N,N’-ジフェニル-N,N’-ジナフチル-1,1’-ビフェニル-4,4’-ジアミン、N,N,N’,N’-テトラビフェニル-1,1’-ビフェニル-4,4’-ジアミン等、又はこれらの芳香族三級アミン骨格を有したオリゴマー若しくはポリマーであるが、これらに限定されるものではない。
前記金属錯体化合物としては、例えば、8-ヒドロキシキノリナートリチウム、ビス(8-ヒドロキシキノリナート)亜鉛、トリス(8-ヒドロキシキノリナート)アルミニウム、トリス(8-ヒドロキシキノリナート)ガリウム、ビス(10-ヒドロキシベンゾ[h]キノリナート)ベリリウム、ビス(10-ヒドロキシベンゾ[h]キノリナート)亜鉛等が挙げられるが、これらに限定されるものではない。
好ましい形態として、これらの電子注入材料にさらにドーパントを含有し、陰極からの電子の受け取りを容易にするため、より好ましくは第2有機層の陰極界面近傍にアルカリ金属で代表されるドーパントをドープする。
ドーパントとしては、ドナー性金属、ドナー性金属化合物及びドナー性金属錯体が挙げられ、これら還元性ドーパントは1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
このような湿式成膜法に適した溶液として、有機EL材料として本発明の電子吸引性基含有化合物と溶媒とを含有する有機EL材料含有溶液を用いることができる。
25mm×75mm×1.1mm厚のITO透明電極(陽極)付きガラス基板(ジオマティック社製)をイソプロピルアルコール中で超音波洗浄を5分間行なった後、UVオゾン洗浄を30分間行なった。洗浄後の透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まず透明電極ラインが形成されている側の面上に前記透明電極を覆うようにして膜厚50nmの化合物A-1を成膜した。A-1膜の成膜に続けて、このA-1膜上に膜厚45nmのA-2を成膜した。
さらに、このA-2膜上に膜厚20nmで化合物EM-1と化合物DM-1を20:1の膜厚比で成膜し青色系発光層とした。
この膜上に電子輸送層として膜厚30nmで下記構造のET-1を蒸着により成膜した。この後、LiFを膜厚1nmで成膜した。このLiF膜上に金属Alを150nm蒸着させ金属陰極を形成し有機EL発光素子を作製した。
また、寿命は、初期輝度500cd/m2における半減寿命で評価した。結果を表1,2に示す。
NE: 電子数
π: 円周率 = 3.1416
λ: 波長 (nm)
φ: 発光強度 (W/sr ・m2 ・nm)
h: プランク定数 = 6.63 x 10-34 (J ・s)
c: 光速度 = 3 x 108 (m/s)
J: 電流密度 (mA/cm2)
e: 電荷 = 1.6 x 10-19 (C)
また、比較例1~7、比較例8を比べると、電子吸引性基を有する化合物により色純度を高められていることが分かるが、Ar2により嵩高くなり会合防止効果が高い本発明のアントラセン誘導体(1)と組み合わせると、さらなる短波長発光を可能とすることが分かる。
本願発明の組合せは、純青色化を維持し、長寿命化を実現できる組合せである。
このことにより、長寿命で色再現性の高いディスプレイデバイスを実現することが可能となる。
この明細書に記載の文献の内容を全てここに援用する。
Claims (10)
- 下記式(1)で表されるアントラセン誘導体と、分子構造中に電子吸引性基を少なくとも1つ含有する化合物とを、含有する有機発光媒体。
Ar1、Ar2は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール基、置換もしくは無置換の環形成原子数5~30の複素環基を示す。) - 前記電子吸引性基を少なくとも1つ含有する化合物が、下記式(2)で表される化合物である請求項1に記載の有機発光媒体。
Ar12及びAr13は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示す。
Gは電子吸引性基を示す。
p及びqは、それぞれ0又は1の整数であり、rは1~5の整数であり、sは1~6の整数を示す。p=q=0の場合、r=1であり、p=1の場合、q=1である。) - 前記式(2)で表される化合物が、下記式(3)~(8)で表される化合物である請求項2に記載の有機発光媒体。
Ar21~Ar24、Ar31~Ar34、Ar41~Ar46、Ar51~Ar54、Ar61~Ar66、Ar71~Ar73は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール基、置換もしくは無置換の環形成原子数5~30の複素環基を示す。
Gは電子吸引性基を示す。
r11、r12、r21、r22、r31、r32、r41、r42、r51、r52、r71、は、それぞれ、1~5の整数を示す。Gが2つ以上ある場合は、それぞれ同一でも異なっていてもよい。) - 前記電子吸引性置換基がシアノ基である請求項1~3のいずれかに記載の有機発光媒体。
- 前記式(1)で表されるアントラセン誘導体のAr1が環形成炭素数10~30の縮合芳香族環基である請求項1~4のいずれかに記載の有機発光媒体。
- 前記式(1)で表されるアントラセン誘導体が、下記式(10)で表される請求項1~4のいずれかに記載の有機発光媒体。
R101~R105は、それぞれ水素原子、フッ素原子、置換もしくは無置換の炭素数1~10のアルキル基、置換もしくは無置換の環形成炭素数3~10のシクロアルキル基、置換もしくは無置換の炭素数3~30のアルキルシリル基、置換もしくは無置換の環形成炭素数8~30のアリールシリル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~20のアリールオキシ基、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示す。 - 前記式(1)で表されるアントラセン誘導体が、下記式(11)で表される請求項6に記載の有機発光媒体。
R15~R19は、それぞれ水素原子、フッ素原子、置換もしくは無置換の炭素数1~10のアルキル基、置換もしくは無置換の環形成炭素数3~10のシクロアルキル基、置換もしくは無置換の炭素数3~30のアルキルシリル基、置換もしくは無置換の環形成炭素数8~30のアリールシリル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~20のアリールオキシ基、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基を示す。) - 前記R101~R105のいずれか一つが、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基であり、前記R101~R105の他の基が全て水素原子である、請求項6又は7に記載の有機発光媒体。
- 請求項1~8のいずれかに記載の有機発光媒体からなる有機薄膜。
- 陰極と陽極の間に少なくとも発光層を含む1以上の有機薄膜層が挟持されている有機エレクトロルミネッセンス素子において、該有機薄膜層の少なくとも一層が、請求項9に記載の有機薄膜である有機エレクトロルミネッセンス素子。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013135237A (ja) * | 2011-12-26 | 2013-07-08 | Samsung Display Co Ltd | 寿命が向上した有機発光素子およびその製造方法 |
US9947879B2 (en) | 2013-03-15 | 2018-04-17 | Idemitsu Kosan Co., Ltd. | Anthracene derivative and organic electroluminescence element using same |
WO2020039708A1 (ja) | 2018-08-23 | 2020-02-27 | 国立大学法人九州大学 | 有機エレクトロルミネッセンス素子 |
Families Citing this family (3)
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KR101566578B1 (ko) | 2012-02-27 | 2015-11-05 | 주식회사 엘지화학 | 유기 발광 소자 |
US9312500B2 (en) | 2012-08-31 | 2016-04-12 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device |
TWI681037B (zh) * | 2018-08-10 | 2020-01-01 | 元智大學 | 含蒽基團之有機電激發光材料以及有機發光二極體元件 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000351965A (ja) * | 1999-03-31 | 2000-12-19 | Fuji Photo Film Co Ltd | 発光素子材料、アミン化合物、およびそれを用いた発光素子 |
WO2002038524A1 (fr) * | 2000-11-08 | 2002-05-16 | Idemitsu Kosan Co., Ltd. | Element electroluminescent organique |
WO2004018587A1 (ja) | 2002-08-23 | 2004-03-04 | Idemitsu Kosan Co., Ltd. | 有機エレクトロルミネッセンス素子及びアントラセン誘導体 |
WO2005054162A1 (ja) | 2003-12-01 | 2005-06-16 | Idemitsu Kosan Co., Ltd. | 非対称モノアントラセン誘導体、有機エレクトロルミネッセンス素子用材料及びそれを利用した有機エレクトロルミネッセンス素子 |
KR20070115588A (ko) | 2006-06-01 | 2007-12-06 | 에스에프씨 주식회사 | 청색발광화합물 및 이를 이용한 유기전계발광소자 |
WO2008102740A1 (ja) | 2007-02-19 | 2008-08-28 | Idemitsu Kosan Co., Ltd. | 有機エレクトロルミネッセンス素子 |
KR20080079956A (ko) | 2007-02-28 | 2008-09-02 | 에스에프씨 주식회사 | 청색발광화합물 및 이를 이용한 유기전계발광소자 |
WO2008150942A1 (en) * | 2007-06-01 | 2008-12-11 | E.I. Du Pont De Nemours And Company | Blue luminescent materials |
WO2008150940A1 (en) * | 2007-06-01 | 2008-12-11 | E. I. Du Pont De Nemours And Company | Chrysenes for green luminescent applications |
JP2010111621A (ja) * | 2008-11-06 | 2010-05-20 | Sony Corp | 芳香族アミン化合物及びこれを用いた有機電界発光素子、並びに有機電界発光素子を用いた表示装置 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1437395B2 (en) * | 2002-12-24 | 2015-08-26 | LG Display Co., Ltd. | Organic electroluminescent device |
WO2005042668A1 (en) * | 2003-10-24 | 2005-05-12 | Eastman Kodak Company | Electroluminescent device with anthracene derivative host |
US7887931B2 (en) * | 2003-10-24 | 2011-02-15 | Global Oled Technology Llc | Electroluminescent device with anthracene derivative host |
US9214636B2 (en) * | 2006-02-28 | 2015-12-15 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device |
CN101595080B (zh) * | 2006-11-15 | 2013-12-18 | 出光兴产株式会社 | 荧蒽化合物和使用该荧蒽化合物的有机电致发光元件以及含有机电致发光材料的溶液 |
US8512878B2 (en) * | 2007-05-08 | 2013-08-20 | Idemitsu Kosan Co., Ltd. | Diaminopyrene derivative and organic EL device using the same |
JP2009249551A (ja) * | 2008-04-09 | 2009-10-29 | Toyo Ink Mfg Co Ltd | 有機エレクトロルミネッセンス素子用材料および素子 |
KR101359701B1 (ko) * | 2008-12-05 | 2014-02-11 | 엘지디스플레이 주식회사 | 청색 형광 물질 및 이를 이용한 유기전계발광소자 |
-
2010
- 2010-12-15 WO PCT/JP2010/007271 patent/WO2011074254A1/ja active Application Filing
- 2010-12-15 JP JP2011512332A patent/JP5478615B2/ja active Active
- 2010-12-15 EP EP10837285.5A patent/EP2390938A4/en not_active Withdrawn
- 2010-12-15 KR KR1020117008987A patent/KR101379114B1/ko active IP Right Grant
- 2010-12-15 CN CN201080003273.1A patent/CN102224614B/zh active Active
- 2010-12-15 US US13/138,776 patent/US20120013244A1/en not_active Abandoned
- 2010-12-16 TW TW099144169A patent/TW201129672A/zh unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000351965A (ja) * | 1999-03-31 | 2000-12-19 | Fuji Photo Film Co Ltd | 発光素子材料、アミン化合物、およびそれを用いた発光素子 |
WO2002038524A1 (fr) * | 2000-11-08 | 2002-05-16 | Idemitsu Kosan Co., Ltd. | Element electroluminescent organique |
WO2004018587A1 (ja) | 2002-08-23 | 2004-03-04 | Idemitsu Kosan Co., Ltd. | 有機エレクトロルミネッセンス素子及びアントラセン誘導体 |
WO2005054162A1 (ja) | 2003-12-01 | 2005-06-16 | Idemitsu Kosan Co., Ltd. | 非対称モノアントラセン誘導体、有機エレクトロルミネッセンス素子用材料及びそれを利用した有機エレクトロルミネッセンス素子 |
KR20070115588A (ko) | 2006-06-01 | 2007-12-06 | 에스에프씨 주식회사 | 청색발광화합물 및 이를 이용한 유기전계발광소자 |
WO2008102740A1 (ja) | 2007-02-19 | 2008-08-28 | Idemitsu Kosan Co., Ltd. | 有機エレクトロルミネッセンス素子 |
KR20080079956A (ko) | 2007-02-28 | 2008-09-02 | 에스에프씨 주식회사 | 청색발광화합물 및 이를 이용한 유기전계발광소자 |
WO2008150942A1 (en) * | 2007-06-01 | 2008-12-11 | E.I. Du Pont De Nemours And Company | Blue luminescent materials |
WO2008150940A1 (en) * | 2007-06-01 | 2008-12-11 | E. I. Du Pont De Nemours And Company | Chrysenes for green luminescent applications |
JP2010111621A (ja) * | 2008-11-06 | 2010-05-20 | Sony Corp | 芳香族アミン化合物及びこれを用いた有機電界発光素子、並びに有機電界発光素子を用いた表示装置 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2390938A4 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013135237A (ja) * | 2011-12-26 | 2013-07-08 | Samsung Display Co Ltd | 寿命が向上した有機発光素子およびその製造方法 |
US9515280B2 (en) | 2011-12-26 | 2016-12-06 | Samsung Display Co., Ltd. | Organic light emitting device with enhanced lifespan |
US9947879B2 (en) | 2013-03-15 | 2018-04-17 | Idemitsu Kosan Co., Ltd. | Anthracene derivative and organic electroluminescence element using same |
WO2020039708A1 (ja) | 2018-08-23 | 2020-02-27 | 国立大学法人九州大学 | 有機エレクトロルミネッセンス素子 |
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JPWO2011074254A1 (ja) | 2013-04-25 |
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EP2390938A1 (en) | 2011-11-30 |
TW201129672A (en) | 2011-09-01 |
KR20110099086A (ko) | 2011-09-06 |
CN102224614A (zh) | 2011-10-19 |
EP2390938A4 (en) | 2013-07-17 |
US20120013244A1 (en) | 2012-01-19 |
KR101379114B1 (ko) | 2014-03-31 |
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