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Definitions

• the present invention relates to aromatic amine derivatives and an organic electroluminescence (EL) device using any one of them, in particular an organic EL device in which a molecule hardly crystallizes, which is produced with improved yields, and which has a long lifetime and an aromatic amine derivative realizing the organic EL device.
• EL organic electroluminescence
• An organic EL device is a spontaneous light emitting device which utilizes the principle that a fluorescent substance emits light by energy of recombination of holes injected from an anode and electrons injected from a cathode when an electric field is applied. Since an organic EL device of the laminate type driven under a low electric voltage was reported by C. W. Tang et al. of Eastman Kodak Company (C. W. Tang and S. A. Vanslyke, Applied Physics Letters, Volume 51, Pages 913, 1987 or the like) many studies have been conducted on or organic EL devices using organic materials as the constituent materials. Tang et al.
• the laminate structure uses tris(8-quinolinolato)aluminum for a light emitting layer an a triphenyldiamine derivative for a hole transporting layer.
• Advantages of the laminate structure are that the efficiency of hole injection into the light emitting layer can be increased, that the efficiency of forming exciton which are formed by blocking and recombining electrons injected from the cathode can be increased, and that exciton formed within the light emitting layer can be enclosed.
• a two-layered structure having a hole transporting (injecting) layer and an electron-transporting light emitting layer and a three-layered structure having a hole transporting (injecting) layer, a light emitting layer, and an electron-transporting (injecting) layer are well known.
• the structure of the device and the process for forming the device have been studied.
• Patent Document 3 describes an aromatic amine derivative having an asymmetric structure.
• the document has no specific examples and has no description concerning characteristics of an asymmetric compound.
• Patent Document 4 describes an asymmetric aromatic amine derivative having phenanthrene as an example.
• the derivative is treated in the same way as that of asymmetric compound, and the document has no description concerning characteristics of an asymmetric compound.
• none of those patents explicitly describes a method of producing an asymmetric compound in spite of the fact that the asymmetric compound requires a special synthesis method.
• Patent Document 5 describes a method of producing an aromatic amine derivative having an asymmetric structures but has no description concerning characteristics of an asymmetric compound.
• Patent Document 6 describes an asymmetric compound which has a high glass transition temperature and which is thermally stable, but exemplifies only a compound having carbazole.
• the inventors of the present invention have produced a device by using the compound. As a result, they have found that a problem lies in the short lifetime of the device.
• Patent Document 1 U.S. Pat. No. 4,720,432
• the present invention has been made with a view to solving the above-mentioned problems, and an object of the present invention is to provide an organic EL device, in which a molecule hardly crystallizes, which can be produced with improved yields, and which has a long lifetime, and an aromatic amine derivative realizing the organic EL device.
• the inventors of the present invention have made extensive studies with a view to achieving the above-mentioned object. As a results they have found that the use of a novel aromatic amine derivative having an asymmetric structure in which two different amine units are bonded through a linking group as represented by the following general formula (1) as a material for an organic EL device, in particular, a hole transporting material can solve the above-mentioned problems. Thus, they have completed the present invention
• an amino group substituted by an aryl group is suitable as an asymmetric amine unit.
• An interaction between molecules of the amine unit is small because the unit has steric hindrance. Accordingly, the unit has effects such that: crystallization is suppressed; yield in which an organic EL device is produced is improved; decomposition of a molecule is suppressed at the time of vapor deposition because it is possible to deposit at a low sublimation temperature; and an organic EL device having a long lifetime can be provided.
• the asymmetric amine unit can provide an organic EL device having a significantly long lifetime, in particular, when the amine unit is combined with a blue light emitting device.
• the present invention provides an aromatic amine derivative represented by the following general formula (1):
• L represents a linking group composed of a substituted or unsubstituted arylene group having 5 to 50 ring atoms, or a linking group obtained by bonding multiple substituted or unsubstituted arylene groups each having 5 to 50 ring atoms through a single bond, an oxygen atom, a sulfur atom, a nitrogen atom, or a saturated or unsaturated, divalent aliphatic hydrocarbon group having 1 to 20 ring carbon atoms;
• A represents a diarylamino group represented by the following general formula (2).
• B represents a diarylamino group represented by the following general formula (3) provided that A and B are not identical to each other:
• Ar 1 to Ar 4 each independently represent a substituted or unsubstituted aryl group having 5 to 50 ring atoms provided that three or more of Ar 1 to Ar 4 represent aryl groups different from one another.
• the present invention provides an aromatic amine derivative represented by the general formula (1), in which all four of Ar 1 to Ar 4 in the general formulae (2) and (3) represent aryl groups different from one another
• the present invention provides an aromatic amine derivative represented by the general formula (1) in which Ar 3 and Ar 4 in the general formula (3) each independently represent a group represented by the following general formula (4):
• Ar 5 represents a substituted or unsubstituted aryl group having 5 to 50 ring atoms, and m represents an integer of 1 to 5.
• the present invention provides an aromatic amine derivative represented by the general formula (1) in which Ar 3 and Ar 4 in the general formula (3) each independently represent a group represented by the following general formula (5):
• Ar 6 represents a substituted or unsubstituted aryl group having 5 to 50 ring atoms.
• the present invention provides an aromatic amine derivative represented by the general formula (1, in which Ar 1 represents a substituted or unsubstituted naphthyl group, and Ar 3 and Ar 4 each independently represent a group represented by the general formula (5).
• the present invention provides an aromatic amine derivative represented by the general formula (13 in which Ar 2 in the general formula (2) and Ar 4 in the general formula (3) each independently represent a group represented by the following genera formula (4):
• Ar 5 represents a substituted or unsubstituted aryl group having 5 to 50 ring atoms, and m represents an integer of 1 to 5
• the present invention provides an aromatic amine derivative represented by the general formula (1), in which Ar 2 in the general formula (2) and Ar 4 in the general formula (3) each independently represent a group represented by the following general formula (5):
• Ar 6 represents a substituted or unsubstituted aryl group having 5 to 50 ring atoms.
• the present invention provides an aromatic amine derivative represented by the general formula (1), in which Arm represents a substituted or unsubstituted fused ring group having 11 to 50 ring atoms, and Ar 3 and Ar 4 , or Ar 2 and Ar 4 each independently represent a group represented by the above-mentioned general formula (4) or (5).
• the present invention provides an aromatic amine derivative represented by the general formula (1) in which Ar 1 and Ar 3 each independently represent a substituted or unsubstituted fused ring group having 10 to 50 ring atoms.
• the present invention provides an aromatic amine derivative represented by the general formula (1), in which Ar 1 and Ar 2 each independently represent a substituted or unsubstituted fused ring group having 10 to 50 ring atoms
• the present invention provides an aromatic amine derivative represented by the general formula (1), in which Ar 3 and Ar 4 are identical to each other, and Ar 3 and Ar 4 , or Ar 2 and Ar 4 each independently represent a group represented by the above-mentioned general formula (4) or (5), or Ar 1 alone represents, or Ar 1 and Ar 3 each represent, a fused ring.
• the present invention provides an aromatic amine derivative represented by the general formula (1) in which Ar 2 and Ar 3 are identical to each other, and Ar 3 and Ar 4 , or Ar 2 and Ar 4 each independently represent a group represented by the above-mentioned general formula (4) or (5), or Ar 1 alone represents, or Ar 1 and Ar 3 each represent, a fused ring
• the present invention provides an aromatic amine derivative represented by the general formula (X) in which a total number of the ring atoms of the aryl groups represented by Ar 1 to Ar 4 is 41 to 96
• the present invention provides an aromatic amine derivative represented by the general formula (1) in which a total number of the ring atoms of the aryl groups represented by Ar 1 to Ar 4 is 45 to 72.
• the present invention provides any one of the aromatic amine derivative as described above, which is a material for an organic electroluminescence device.
• the present invention provides any one of the aromatic amine derivatives as described above, which is a hole transporting material for an or organic electroluminescence device.
• the present invention provides an organic electroluminescence device including an organic thin film layer composed of one or more layers including at least a light emitting layer the organic thin film layer being interposed between a cathode and an anode in which at least one layer of the organic thin film layer contains any one of the aromatic amine derivatives as described above alone or as a component of a mixture.
• the present invention provides the organic electroluminescence device as described above, in which the organic thin film layer has a hole transporting layer, and the hole transporting layer contains any one of the aromatic amine derivatives alone or as a component of a mixture.
• the present invention provides the organic electroluminescence device as descried above, in which the light emitting layer contains an arylamine compound and/or a styrylamine compound.
• the present invention provides anyone of the organic electroluminescence devices as described above which emits bluish light.
• An aromatic amine and an organic EL device using the aromatic amine derivative of the present inventions which hardly cause the crystallization of a molecule, can improve yields upon production of the organic EL device, and can increase the lifetime of the organic EL device.
• An aromatic amine derivative of the present invention is represented by the following general formula (1).
• L represents (I) a linking group composed of a substituted or unsubstituted arylene group having 5 to 50 ring atoms, or (II) a linking group obtained by bonding multiple substituted or unsubstituted arylene groups each having 5 to 50 ring atoms through (II-7) a single bond, (II-2) an oxygen atom (—O—) (II-3) a sulfur atom (—S—), (II-4) a nitrogen atom (—NH— or —NR— [where R represents a substituent]) or (II-5) a saturated or unsaturated, divalent aliphatic hydrocarbon group having 1 to 20 ring carbon atoms.
• Examples of the arylene group having 5 to 50 ring atoms in each of the above-mentioned items (I) and (II) include a 1,4-phenylene group, a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-naphthylene group, a 2,6-naphthylene group, a 1,5-naphthylene group, a 9,10-anthranylene group, a 9,10-phenanthrenylene group, a 3,6-phenanthrenylene group, a 1,6-pyrenylene groups a 2,7-pyrenylene group, a 6,12-chrysenylene group, a 1,1′-biphenylene group, a 4,4′-b-phenylene group, a 3,3′-biphenylene group, a 2,2′-biphenylene group, a 2,7-fluorenylene group, a 2,5-thiophenylene group, a
• a 1,4-phenylene group a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-naphthylene group, a 9,10-anthranylene group, a 6,12-chrysenylene group, a 4,4′-biphenylene group, a 3,31-biphenylene group, a 2,2′-biphenylene group, and a 2,7-fluorenylene group are preferable.
• the saturated or unsaturated, divalent aliphatic hydrocarbon group having 1 to 20 ring carbon atoms in the above-mentioned item (II-5) may be linear, branched, or cyclic, and examples of the group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an ethylidene group, a cyclohexylidene group, and an adamantylene group.
• L preferably represents a phenylene group, a biphenylene group, a terphenylene group, or a fluorenylene group, more preferably represents a biphenylene group, or particularly preferably represents a 1,1′-biphenylene group.
• A represents a diarylamino group represented by the following general formula (2).
• B represents a diarylamino group represented by the following general formula (3).
• a and B in the general formula (1) are not identical to each other.
• Ar 1 to Ar 4 each independently represent a substituted or unsubstituted aryl group having 5 to 50 ring atoms.
• Examples of the aryl groups of Ar 1 to Ar 4 include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a I-naphthacenyl group, a 2-naphthacenyl group, a 9-naphthacenyl group a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a p-terphenyl-4-yl group, a p-terphenyl-3-yl group, a p
• a phenyl group, a naphthyl group, a biphenyl group, an anthranyl group a phenanthryl group, a pyrenyl group, a chrysenyl group, a fluoranthenyl group, and a fluorenyl group are preferable.
• the aromatic amine derivative of the present invention is preferably such that Ar 1 to Ar 4 in the general formulae (1) to (3) represent groups different from one another.
• the aromatic amine derivative of the present invention is preferably such that at least two of Ar 2 to Ar 4 in the general formulae (1) to (3) each represent an aryl group represented by the following general formula (4), and is more preferably such that at least two of them each represent an aryl group represented by the following general formula (5):
• Ar 5 represents a substituted or unsubstituted aryl group having 5 to 50 ring atoms
• examples of the aryl group include the same examples as those described for the aryl group represented by any one of Ar 1 to Ar 4 and m represents an integer of 1 to 5;
• Ar 6 represents a substituted or unsubstituted aryl group having 5 to 50 ring atoms.
• Examples of a substituent for each of Ar 1 to Ar 6 and L include a substituted or unsubstituted aryl group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 1 to 50 carbon atoms a substituted or unsubstituted aryloxy group having 5 to 50 ring atoms a substituted or unsubstituted arylthio group having 5 to 50 ring atoms a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, an amino group substituted by a substituted or unsubstituted aryl group having 5 to 50 ring atoms a halogen atom a cyano group a nitro group a hydroxyl group and a carboxyl group
• the substituted or unsubstituted aryl group having 5 to 50 ring atoms which is a substituent for each of Ar 1 to Ar 6 and L includes the same examples as those described for the above-mentioned Ar 1 to Ar 6 .
• Examples of the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, which is a substituent for each of Ar 1 to Ar 6 and L include a methyl group, an ethyl group, a propyl group, an isopropyl group, an r-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an r-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 2-hydroxyisobutyl group, a 1,2-dihydroxyethyl group, a 3-dihydroxyisopropyl group, a 1,3-dihydroxy-2-methyl-2-propyl group, a 1,2,3-trihydroxypropyl group, a chloromethyl group, a 1-ch
• the substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, which is a substituent for each of Ar 1 to Ar 6 and L is represented by —OY, and examples of Y include the same examples as those described for the above-mentioned alkyl group.
• Examples of the substituted or unsubstituted aralkyl group having 6 to 50 ring atoms, which is a substituent for each of Ar 1 to Ar 6 and L include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group a 1-phenylisopropyl group, a 2-phenylisopropyl group, a phenyl-t-butyl group, an ⁇ -naphthylmethyl group, a 1- ⁇ -naphthylethyl group, a 2- ⁇ -naphthylethyl group, a 1- ⁇ -naphthylisopropyl group a 2- ⁇ -naphthylisopropyl group, a ⁇ -naphthylmethyl group, a 1- ⁇ -naphthylethyl group, a 2- ⁇ -naphthylethyl group, a 1- ⁇ -n
• the substituted or unsubstituted aryloxy group having 5 to 50 ring atoms as a substituent for each of Ar 1 to Ar 6 and L is represented by —OY′, and examples of Y′ include the same examples as those described for the aryl group represented by any one of Ar 1 to Ar 4 .
• the substituted or unsubstituted arylthio group having 5 to 50 ring atoms as a substituent for each of Ar 1 to Ar 6 and L is represented by —SY′, and examples of Y′ include the same examples as those described for the aryl group represented by any one of Ar 1 to Ar 4 .
• the substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms as a substituent for each of Ar 1 to Ar 6 and L is a group represented by —COOY, and examples of Y include the same examples as those described for the alkyl group.
• Examples of a substituted or unsubstituted aryl group having 5 to 50 ring atoms in the amino group substituted by the aryl group as a substituent for each of Ar 1 to Ar 6 and L include the same examples as those described for the aryl group represented by any one of Ar 1 to Ar 4 .
• halogen atom examples include a fluorine atom a chlorine atom, a bromine atom and an iodine atom.
• the aromatic amine derivative of the present invention is preferably a material for an organic EL device, and more preferably a hole transporting material for an organic EL device.
• organic EL device of the present invention includes one or multiple organic thin film layers including at least a light emitting layer, the one or multiple organic thin film layers being interposed between a cathode and an anode, in which at least one layer of the one or more multiple organic thin film layers contains the aromatic amine derivative alone or as a component of a mixture.
• the one or multiple organic thin film layers have a hole transporting layer; and the hole transporting layer contain the aromatic amine derivative of the present invention alone or as a component of a mixture. It is more preferable that the hole transporting layer contain the aromatic amine derivative of the present invention as a man component.
• the aromatic amine derivative of the present invention is particularly preferably used in an organic EL device that emits blue-based light.
• the light emitting layer preferably contains an aryl amine compound and/or a styrylamine compound.
• Examples of the arylamine compound include compounds each represented by the following general formula (A) and examples of the styrylamine compound include compounds each represented by the following general formula (B).
• Ar 8 represents a group selected from phenyl biphenyl, terphenyl, stilbene, and distyrylaryl groups
• Ar 9 and Ar 10 each represent a hydrogen atom or an aromatic group having 6 to 20 carbon atoms
• each of Ar 9 and Ar 10 may be substituted
• p′ represents an integer of 1 to 4
• Ar 9 and/or Ar 10 are/is more preferably substituted by a styryl group.
• the aromatic group having 6 to 20 carbon atoms is preferably a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a terphenyl group, or the like.
• Ar 11 to Ar 13 each represent an aryl group which has 5 to 40 ring carbon atoms and which may be substituted, and q′ represents an integer of 1 to 4.
• examples of the aryl group having 5 to 40 ring atoms preferably include phenyl, naphthyl, anthranyl phenanthryl, pyrenyl, coronyl, biphenyl, terphenyl, pyrrolyl, furanyl, thiophenyl, benzothiophenyl, oxadiazolyl, diphenylanthranyl, indolyl, carbazolyl, pyridyl, benzoquinolyl, fluoranthenyl, acenaphthofluoranthenyl and stilbene.
• the aryl group having to 40 ring atoms may further be substituted by a substituent
• substituents preferably include: an alkyl group having 1 to 6-carbon atoms such as an ethyl group, a methyl group, an isopropyl group, an n-propyl group, an s-butyl group, a t-butyl group, a pentyl groups a hexyl group, a cyclopentyl group, or a cyclohexyl group; an alkoxy group having 1 to 6 carbon atoms such as an ethoxy groups a methoxy group an isopropoxy group, an n-propoxy group, an s-butoxy group, a t-butoxy group, a pentoxy group, a hexyloxy group, a cyclopentoxy group, or a cyclohexyloxy group; an aryl group having 5 to 40 ring atoms; an amino group substitute
• Typical examples of the structure of the organic EL device of the present invention include the following:
• the structure (8) is preferably used in ordinary cases. However the structure is not limited to the foregoing.
• the aromatic amine derivative of the present invention may be used in any one of the organic thin film layers of the organic EL device.
• the derivative can be used in a light emitting zone or a hole transporting zone.
• the derivative is used preferably in the hole transporting zone, or particularly preferably in a hole transporting layer, thereby making a molecule hardly crystallize and improving yields upon production of the organic EL device.
• the amount of the aromatic amine derivative of the present invention to be incorporated into the organic thin film layers is preferably 30 to 100 mol %.
• the organic EL device of the present invention is prepared on a transparent substrate.
• the transparent substrate is the substrate which supports the organic EL device. It is preferable that the transparent substrate have a transmittance of light of 50% or greater in the visible region of 400 to 700 nm and be flat and smooth.
• the transparent substrate examples include glass plates and polymer plates.
• the glass plate examples include plates made of soda-lime glass, glass containing barium and strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
• Specific examples of the polymer plate include plates made of polycarbonate resins, acrylic resins, polyethylene terephthalate, polyether sulfide, and polysulfone.
• the anode in the organic EL device of the present invention has the function of injecting holes into the hole transporting layer or the light emitting layer. It is effective that the anode has a work function of 4.5 eV or greater.
• Specific examples of the material for the anode used in the present invention include indium tin oxide (ITO) alloys, tin oxide (NESA), indium zinc oxide (ISO) gold, silver, platinum, and copper.
• the anode can be prepared by forming a thin film of the electrode material described above in accordance with a process such as the vapor deposition process and the sputtering process.
• the anode When the light emitted from the light emitting layer is obtained through the anode, it is preferable that the anode have a transmittance of the emitted light greater than 10%. It is also preferable that the sheet resistivity of the anode be several hundred ⁇ / ⁇ or smaller.
• the thickness of the anode is, in general, selected in the range of 10 nm to 1 ⁇ m and preferably in the range of 10 to 200 nm although the preferable range may be different depending on the used material.
• the light emitting layer in the organic EL device has a combination of the following functions (1) to (3).
• the injecting function the function of injecting holes from the anode or the hole injecting layer and injecting electrons from the cathode or the electron injecting layer when an electric field is applied.
• the transporting function the function of transporting injected charges (i.e., electrons and holes) by the force of the electric field.
• the light emitting function the function of providing the field for recombination of electrons and holes and leading to the emission of light.
• the easiness of injection may be different between holes and electrons and the ability of transportation expressed by the mobility may be different between holes and electrons. It is preferable that either one of the charges be transferred.
• the process for forming the light emitting layer a known process such as the vapor deposition process, the spin coating process, and the LB process can be used. It is particularly preferable that the light emitting layer be a molecular deposit film.
• the molecular deposit film is a thin film formed by deposition of a material compound in the gas phase or a film formed by solidification of a material compound in a solution or in the liquid phase.
• the molecular deposit film can be distinguished from the thin film formed in accordance with the LB process (i.e., molecular accumulation film) based on the differences in aggregation structure and higher order structure and functional differences caused by those structural differences.
• the light emitting layer can also be formed by dissolving a binder such as a resin and the material compounds into a solvent to prepare a solution, followed by forming a thin film from the prepared solution by the spin coating process or the like.
• the light emitting layer may include other known light emitting materials other than the light emitting material composed of the aromatic amine derivative of the present invention, or a light emitting layer including other known light emitting material may be laminated to the light emitting layer including the light emitting material composed of the aromatic amine derivative of the present invention as long as the object of the present invention is not adversely affected.
• Examples of a light emitting material or a doping material which can be used in the light emitting layer together with the aromatic amine derivative of the present invention include, but not limited to, anthracene naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluoresceine, perylene, phthaloperylene, naphthaloperylene, perynone, phthaloperynone, naphthaloperynone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complexes, aminoquinoline metal complexes, benzoquinoline metal complexes, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyrane, thiopyr
• a host material that can be used in a light emitting layer together with the aromatic amine derivative of the present invention is preferably a compound represented by any one of the following formulae (i) to (ix).
• Ar represents a substituted or unsubstituted fused aromatic group having 10 to 50 ring carbon atoms
• Ar′ represents a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms
• X represents a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring atoms, a substituted or unsubstituted arylthio group having 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a carboxyl group, a halogen atom, a cyano group, a nitro group, or a hydroxyl group.
• a, b, and c each represent an integer of 0 to 4.
• n an integer of 1 to 3.
• anthracene nuclei in [ ] may be identical to or different from each other.
• Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aromatic ring group having 6 to 50 ring carbon atoms.
• R 1 to R 10 each independently represent a hydrogen atom, a substituted or unsubstituted aromatic ring group having 6 to 50 ring carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group having X to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring atoms, a substituted or unsubstituted arylthio group having 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl
• Ar and Ar′ each represent a substituted or unsubstituted aromatic group having 6 to 50 ring carbon atoms
• L and L′ each represent a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalenylene group, a substituted or unsubstituted fluorenylene group, or a substituted or unsubstituted dibenzosilolylene group;
• n represents an integer of 1 to 4.
• s represents an integer of 0 to 2.
• t represents an integer of 0 to 4;
• Ar, Ar′, L, and L′ satisfy the following item (1) or (2) when n+t represents an even number
• L and L′ or pyrene bind or binds to different binding positions on Ar and Ar′, or
• a 1 and A 2 each independently represent a substituted or unsubstituted fused aromatic ring group having 10 to 20 ring carbon atoms;
• Ar 1 and Ar 2 each independently represent a hydrogen atom, or a substituted or unsubstituted aromatic ring group having 6 to 50 ring carbon atoms;
• R 1 to R 10 each independently represent a hydrogen atom, a substituted or unsubstituted aromatic ring group having 6 to 50 ring carbon atoms a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 50 ring atoms, a substituted or unsubstituted arylthio group having 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a substituted or unsubstituted silyl group,
• each of Ar 1 , Ar 2 , R 9 and R 10 may be two or more, and adjacent groups may form a saturated or unsaturated cyclic structure
• R 11 to R 20 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group an aryl group, an alkoxyl group, an aryloxy group, an alkylamino groups an arylamino group, or a heterocyclic group which may be substituted;
• c, do en and f each represent an integer of 1 to 5, and, when any one of c, do en and f represents 2 or mores R 11 's, R 12 's, R 16 's, or R 17 's may be identical to or different from each other, or R 11 's, R 12 's, R 16 's or R 17 's may be bonded to each other to form a ring;
• R 13 and R 14 , or R 18 and R 19 may be bonded to each other to form a ring;
• L 2 represents a single bonds —O—, —S—, —N(R)— where R represents an alkyl group or an
• a 5 to A 8 each independently represent a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group.
• a 9 to A 14 each have the same meaning as that described above;
• R 21 to R 23 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, an aryloxy group having 5 to 18 carbon atoms, an aralkyloxy group having 7 to 18 carbon atoms, an arylamino group having 5 to 16 carbon atoms, a nitro group, a cyano group, an ester group having 1 to 6 carbon atoms, or a halogen atom, and at least one of A 9 to A 14 represents a group having three or more fused aromatic rings.
• R 1 and R 2 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, a cyano group, or a halogen atom;
• R 1 's or R 2 's bonded to different fluorene groups may be identical to or different from each other, and R 1 and R 2 bonded to the same fluorene group may be identical to or different from each other;
• R 3 and R 4 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;
• an anthracene derivative is preferable, a monoanthracene derivative is more preferable and an asymmetric anthracene is particularly preferable.
• a phosphorescent compound can also be used as a light emitting material for a dopant.
• a compound containing a carbazole ring as a host material is preferable as the phosphorescent compound.
• the dopant is a compound capable of emitting light from a triplet exciton and is not particularly limited as long as light is emitted from a triplet exciton, a metal complex containing at least one metal selected from the group consisting of Ir, Ru, Pd, Pt, Os, and Re is preferable, and a porphyrin metal complex or an orthometalated metal complex is preferable.
• a host composed of a compound containing a carbazole ring and suitable for phosphorescence is a compound having a function of causing a phosphorescent compound to emit light as a result of the occurrence of energy transfer from the excited state of the host to the phosphorescent compound
• a host compound is not particularly limited as long as it is a compound capable of transferring exciton energy to a phosphorescent compound, and can be appropriately selected in accordance with a purpose.
• the host compound may have, for example an arbitrary heterocyclic ring in addition to a carbazole ring.
• Such a host compound include a carbazole derivative, a triazole derivative, an oxazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative, a pyrazolone derivative, a phenylene diamine derivative, an aryl amine derivative, an amino substituted chalcone derivative, a styrylanthracene derivative, a fluorenone derivative, a hydrazone derivative, a stilbene derivative, a silazane derivative, an aromatic tertiary amine compound, a styryl amine compound, an aromatic dimethylidene-based compound, a porphyrin-based compound, an anthraquinodimethane derivative, an anthrone derivative, a diphenylquinone derivative, a thiopyranedioxide derivative, a carbodiimide derivative, a fluorenilidene methane derivative
• a phosphorescent dopant is a compound capable of emitting light from a triplet exciton.
• the dopant which is not particularly limited as long as light is emitted from a triplet exciton, is preferably a metal complex containing at least one metal selected from the group consisting of Ir, Ru, Pd, Pt, Os, and Re, and is preferably a porphyrin metal complex or an orthometalated metal complex.
• a porphyrin platinum complex is preferable as the porphyrin metal complex.
• One kind of a phosphorescent compound may be used alone, or two or more kinds of phosphorescent compounds may be used in combination.
• any one of various ligands can be used for forming an orthometalated metal complex
• a preferable ligand include a 2-phenylpyridine derivative a 7,8-benzoquinoline derivative, a 2-(2-thienyl)pyridine derivative, a 2-(1-naphthyl)pyridine derivative, and a 2-phenylquinoline derivative.
• Each of those derivatives may have a substituent as required.
• a fluoride of any one of those derivatives, or one obtained by introducing a trifluoromethyl group into any one of those derivatives is a particularly preferable blue-based dopant.
• the metal complex may further include a ligand other than the above-mentioned ligands such as acetylacetonate or picric acid as an auxiliary ligand.
• the content of the phosphorescent dopant in the light emitting layer is not particularly limited, and can be appropriately selected in accordance with a purpose.
• the content is, for example, 0.1 to 70 mass %, and is preferably 1 to 30 mass %.
• the content of the phosphorescent compound is less than 0.1 mass %, the intensity of emitted light is weak, and an effect of the incorporation of the compound is not sufficiently exerted.
• the content exceeds 70 mass % a phenomenon referred to as concentration quenching becomes remarkable, and device performance reduces.
• the light emitting layer may contain a hole transporting material, an electron transporting material, or a polymer binder as required.
• the thickness of the light emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, or most preferably 10 to 50 nm.
• the thickness is less than 5 nm it becomes difficult to form the light emitting layer so the adjustment of chromaticity may be difficult.
• the thickness exceeds 50 nm, the voltage at which the device is driven may increase.
• the hole injecting and transporting layer is a layer which helps injection of holes into the light emitting layer and transports the holes to the light emitting region.
• the layer exhibits a great mobility of holes and, in general has an ionization energy as small as 5.5 eV or smaller.
• a material which transports holes to the light emitting layer under an electric field of a smaller strength is preferable.
• a material which exhibits for example, a mobility of holes of at least 10 ⁇ 4 m 2 /V ⁇ sec under application of an electric field of 10 4 to 10 6 V/cm is preferable.
• the aromatic amine derivative of the present invention when used in the hole transporting zone, the aromatic amine derivative of the present invention may be used alone or as a mixture with other materials for forming the hole injecting and transporting layer.
• the material which can be used for forming the hole injecting and transporting layer as a mixture with the aromatic amine derivative of the present invention is not particularly limited as long as the material has a preferable property described above.
• the material can be arbitrarily selected from materials which are conventionally used as the charge transporting material of holes in photo conductive materials and known materials which are used for the hole injecting and transporting layer in organic EL devices.
• a triazole derivative see, for example, U.S. Pat. No. 3,112,197
• an oxadiazole derivative see, for example, U.S. Pat. No. 3,189,447
• an imidazole derivative see, for example, JP-B-37-16096
• a polyarylalkane derivative see, for example, U.S. Pat. No. 3,615,402, U.S. Pat. No. 3,820,989, U.S. Pat. No.
• a porphyrin compound such as, for example, JP-A-63-2956965
• an aromatic tertiary amine compound and a styrylamine compound are preferable, and aromatic tertiary amines are particularly preferable.
• aromatic tertiary amine compounds include compounds having two fused aromatic rings in the molecule such as 4,4′-bis(N-(1-naphthyl)-N-phenylamino)-biphenyl (herein after referred to as NPD) as disclosed in U.S. Pat. No. 5,061,569, and a compound in which three triphenylamine units are bonded together in a star-burst shape, such as 4,4′,4′′-tris(N-(3-methylphenyl)-N-phenylamino)-triphenylamine (herein after referred to as MTDATA) as disclosed in JP-A-4-308688.
• NPD 4,4′-bis(N-(1-naphthyl)-N-phenylamino)-biphenyl
• MTDATA 4,4′,4′′-tris(N-(3-methylphenyl)-N-phenylamino)-triphenylamine
• inorganic compounds such as Si of the p-type and SiC of the p-type can also be used as the material for the hole injecting and transporting layer.
• the hole injecting and transporting layer can be formed by forming a thin layer from the aromatic amine derivative of the present invention in accordance with a known process such as the vacuum vapor deposition process, the spin coating process, the casting process, and the LB process.
• the thickness of the hole injecting and transporting layer is not particularly limited. In general, the thickness is 5 nm to 5 ⁇ m.
• the hole injecting and transporting layer may be constituted of a single layer containing one or more materials described above or may be a laminate constituted of hole injecting and transporting layers containing materials different from the materials of the hole injecting and transporting layer described above as long as the aromatic amine derivative of the present invention is incorporated in the hole injecting and transporting zone.
• an organic semiconductor layer may be disposed as a layer for helping the injection of holes or electrons into the light emitting layer.
• a layer having a conductivity of 10 ⁇ 10 S/cm or greater is preferable.
• oligomers containing thiophene, and conductive oligomers such as oligomers containing arylamine and conductive dendrimers such as dendrimers containing arylamine which are disclosed in JP-A-08-193191 can be used
• the electron injecting and transporting layer is a layer which helps injection of electrons into the light emitting layer transports the electrons to the light emitting region, and exhibits a great mobility of electrons.
• the adhesion improving layer is an electron injecting layer including a material exhibiting particularly improved adhesion with the cathode.
• an electron transporting layer is appropriately selected from the range of several nanometers to several micrometers in order that the interference effect may be effectively utilized.
• an electron mobility is preferably at least 10 ⁇ 5 m 2 /Vs or more upon application of an electric field of 10 4 to 10 6 V/cm in order to avoid an increase in voltage.
• a metal complex of 8-hydroxyquinoline or of a derivative of 8-hydroxyquinoline, or an oxadiazole derivative is suitable as a material to be used in an electron injecting layer.
• Specific examples of the metal complex of 8-hydroxyquinoline or of a derivative of 8-hydroxyqunoline that can be used as an electron injecting material include metal chelate oxynoid compounds each containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline) such as tris/8-quinolinolato)aluminum.
• examples of the oxadiazole derivative include electron transfer compounds represented by the following general formulae:
• Ar 1 , Ar 2 , Ar 3 , Ar 5 , Ar 6 and Ar 9 each represent a substituted or unsubstituted aryl group and may represent the same group or different groups.
• Ar 4 , Ar 7 and Ar 8 each represent a substituted or unsubstituted arylene group and may represent the same group or different groups
• Examples of the aryl group include a phenyl group, a biphenyl group, an anthranyl group, a perylenyl group, and a pyrenyl group.
• Examples of the arylene group include a phenylene group, a naphthylene group, a b-phenylene group, an anthranylene group, a perylenylene group, and a pyrenylene group.
• Examples of the substituent include alkyl groups each having 1 to 10 carbon atoms, alkoxyl groups each having 1 to 10 carbon atoms, and a cyano group.
• the electron transfer compound compounds which can form thin films are preferable
• Examples of the electron transfer compounds described above include the following.
• materials represented by the following general formulae (A) to (E) can be used in an electron injecting layer and an electron transporting layer.
• Nitrogen-containing heterocyclic derivatives represented by the general formulae (A) and (B) are Nitrogen-containing heterocyclic derivatives represented by the general formulae (A) and (B)
• a 1 to A 3 each independently represent a nitrogen atom or a carbon atom
• Ar 1 represents a substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 60 ring carbon atoms
• Ar 2 represents a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 60 ring carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a divalent group of any one of them provided that one of Ar 1 and Ar 2 represents a substituted or unsubstituted fused ring group having 10 to 60 ring carbon atoms or a substituted or unsubstit
• n an integer of 0 to 5, and, when n represents 2 or more, multiple R's may be identical to or different from each other, and multiple R groups adjacent to each other may be bonded to each other to form a carbocyclic aliphatic ring or a carbocyclic aromatic ring.
• HAr represents a nitrogen-containing heterocyclic ring which has 3 to 40 carbon atoms and may have a substituent
• L represents a single bond, an arylene group which has 6 to 60 carbon atoms and may have a substituent, a heteroarylene group which has 3 to 60 carbon atoms and may have a substituent, or a fluorenylene group which may have a substituent
• Ar 1 represents a divalent aromatic hydrocarbon group which has 6 to 60 carbon atoms and may have a substituent
• Ar 2 represents an aryl group which has 6 to 60 carbon atoms and may have a substituent, or a heteroaryl group which has 3 to 0 carbon atoms and may have a substituent
• X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocycle, or X and Y are bonded to each other to form a structure as a saturated or unsaturated ring; and R 1 to R 4 each independently represent hydrogen, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxy group, an aryloxy group, a perfluoroalkyl group, a perfluoroalkoxy group, an amino group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an azo group, an alkylcarbonyloxy group, an aryl
• R 1 to R 8 and Z 2 each independently represent a hydrogen atom, a saturated or unsaturated hydrocarbon group, an aromatic group, a heterocyclic group, a substituted amino group, a substituted boryl group, an alkoxy group, or arm aryloxy group;
• X, Y, and Z 1 each independently represent a saturated or unsaturated hydrocarbon group, an aromatic group, a heterocyclic group, a substituted amino group, an alkoxy group, or an aryloxy group;
• substituents of Z 1 and Z 2 may be bonded to each other to form a fused ring; and n represents an integer of 1 to 3, and, when n represents 2 or more, Z 1 's may be different from each other provided that the case where n represents 1, X, Y, and R 2 each represent a methyl group, R 8 represents a hydrogen atom or a substituted boryl group and the case where n represents 3 and Z 1 's each represent a methyl group are excluded.
• Q 1 and Q 2 each independently represent a ligand represented by the following general formula (G); and L represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, —OR 1 where R 1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or a ligand represented by —O—Ga-Q 3 (Q 4 ) where Q 3 and Q 4 are identical to Q 1 and Q 2 respectively.)
• the rings A 1 and A 2 are six-membered aryl ring structures which are condensed with each other and each of which may have a substituent.
• the metal complex behaves strongly as an n-type semiconductor, and has a large electron injecting ability. Further, generation energy upon formation of the complex is low. As a result, the metal and the ligand of the formed metal complex are bonded to each other so strongly that the fluorescent quantum efficiency of the complex as a light emitting material improves.
• a substituent in the rings A 1 and A 2 which each form a ligand in the general formula (G) include: a halogen atom such as chlorine, bromine, iodine, or fluorine; a substituted or unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a stearyl group, or trichloromethyl group; a substituted or unsubstituted aryl group such as a phenyl group, a naphthyl group, a 3-methylphenyl group, a 3-methoxyphenyl group, a 3-fluorophenyl group, a 3-trichloromethylphenyl group, a 3-trifluor
• a preferable embodiment of the organic EL device of the present invention includes an element including a reducing dopant in the region of electron transport or in the interfacial region of the cathode and the organic thin film layer.
• the reducing dopant is defined as a substance which can reduce a compound having the electron-transporting property.
• Various compounds can be used as the reducing dopant as long as the compounds have a uniform reductive property.
• At least one substance selected from the group consisting of alkali metals alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals can be preferably used.
• the reducing dopant include substances having a work function of 2.9 eV or smaller, specific examples of which include at least one alkali metal selected from the group consisting of Na (the work function: 2.36 eV), K (the work function: 2.28 eV), Rb (the work function: 2.16 eV), and Cs (the work function: 1.95 eV) and at least one alkaline earth metal selected from the group consisting of Ca (the work function: 2.9 eV), Sr (the work function: 2.0 to 2.5 eV), and Ba (the work function: 2.52 eV).
• At least one alkali metal selected from the group consisting of K, Rb, and Cs is more preferable, Rb and Cs are still more preferable, and Cs is most preferable as the reducing dopant.
• Those alkali metals have great reducing ability, and the luminance of the emitted light and the life time of the organic EL device can be increased by addition of a relatively small amount of the alkali metal into the electron injecting zone.
• the reducing dopant having a work function of 2.9 eV or smaller combinations of two or more alkali metals thereof are also preferable.
• Combinations having Cs such as the combinations of Cs and Na, Cs and K, Cs and Rb, and Cs, Na, and K are more preferable.
• the reducing ability can be efficiently exhibited by the combination having Cs.
• the luminance of emitted light and the life time of the organic EL device can be increased by adding the combination having Cs into the electron injecting zone.
• the present invention may further include an electron injecting layer which is composed of an insulating material or a semiconductor and disposed between the cathode and the organic layer. At this time, leak of electric current can be effectively prevented by the electron injecting layer and the electron injecting property can be improved.
• an electron injecting layer which is composed of an insulating material or a semiconductor and disposed between the cathode and the organic layer.
• the electron injecting layer is preferable. It is preferable that the electron injecting layer be composed of the above-mentioned substance such as the alkali metal chalcogenide since the electron injecting property can be further improved.
• Preferable examples of the alkali metal chalcogenide include Li 2 O, K 2 O, Na 2 S, Na 2 Se, and Na 2 O.
• preferable examples of the alkaline earth metal chalcogenide include CaO, BaO, SrO, BeO, BaS and CaSe.
• Preferable examples of the alkali metal halide include LiF, NaF, KF, KCl, and NaCl.
• Preferable examples of the alkaline earth metal halide include fluorides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 , and BeF 2 and halides other than the fluorides.
• Examples of the semiconductor composing the electron-transporting layer include oxides, nitrides, and oxide nitrides of at least one element selected from Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn used alone or in combination of two or more. It is preferable that the inorganic compound composing the electron-transporting layer forms a crystallite or amorphous insulating thin film. When the electron injecting layer is composed of the insulating thin film described above, a more uniform thin film can be formed, and defects of pixels such as dark s-pots can be decreased.
• Examples of the inorganic compound include alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides which are described above.
• the cathode a material such as a metal, an alloy, a conductive compound, or a mixture of those materials which has a small work function (4 eV or smaller) is used because the cathode is used for injecting electrons to the electron injecting and transporting layer or the light emitting layer.
• the electrode material include sodium, sodium-potassium alloys, magnesium, lithium, magnesium-silver alloys, aluminum/aluminum oxide, aluminum lithium alloys, indium, and rare earth metals.
• the cathode can be prepared by forming a thin film of the electrode material described above in accordance with a process such as the vapor deposition process and the sputtering process.
• the cathode When the light-emitted from the light emitting layer is obtained through the cathode, it is preferable that the cathode have a transmittance of the emitted light greater than 10%.
• the sheet resistivity of the cathode be several hundred ⁇ / ⁇ or smaller.
• the thickness of the cathode in the range of 50 to 200 nm
• a layer of a thin film having an insulating property is preferably inserted between the pair of electrodes.
• Examples of the material used for the insulating layer include aluminum oxide, lithium fluorides lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide. Mixtures and laminates of the above-mentioned compounds may also be used.
• the anode and the light emitting layer, and, where necessary, the hole injecting and the transporting layer and the electron injecting and transporting layer are formed in accordance with the illustrated process using the illustrated materials, and the cathode is formed in the last step.
• the organic EL device may also be prepared by forming the above-mentioned layers in the order reverse to that described above, i.e., the cathode being formed in the first step and the anode in the last step.
• a thin film made of a material for the anode is formed in accordance with the vapor deposition process or the sputtering process so that the thickness of the formed thin film is 1 ⁇ m or smaller and preferably in the range of 10 to 200 nm.
• the formed thin film is used as the anode.
• a hole injecting layer is formed on the anode.
• the hole injecting layer can be formed in accordance with the vacuum vapor deposition process, the spin coating process, the casting process, or the LB process, as described above.
• the vacuum vapor deposition process is preferable since a uniform film can be easily obtained and the possibility of formation of pin holes is small.
• the conditions be suitably selected in the following ranges: the temperature of the source of the deposition: 50 to 450° C.; the vacuum: 10 ⁇ 7 to 10 ⁇ 3 Torr; the rate of deposition: 0.01 to 50 nm/second; the temperature of the substrate: ⁇ 50 to 300° C. and the thickness of the film: 5 nm to 5 ⁇ m; although the conditions of the vacuum vapor deposition are different depending on the compound to be used (i.e., the material for the hole injecting layer) and the crystal structure and the recombination structure of the target hole injecting layer.
• a thin film of the organic light emitting material can be formed by using a desired organic light emitting material in accordance with a process such as the vacuum vapor deposition process, the sputtering process, the spin coating process, or the casting process, and the formed thin film is used as the light emitting layer.
• the vacuum vapor deposition process is preferable since a uniform film can be easily obtained and the possibility of formation of pin holes is small.
• the conditions of the vacuum vapor deposition process can be selected in the same ranges as those described for the vacuum vapor deposition of the hole injecting layer, although the conditions are different depending on the used compound.
• an electron injecting layer is formed on the light emitting layer formed above.
• the electron injecting layer be formed in accordance with the vacuum vapor deposition process since a uniform film must be obtained.
• the conditions of the vacuum vapor deposition can be selected in the same ranges as those described for the vacuum vapor deposition of the hole injecting layer and the light emitting layer.
• the aromatic amine derivative of the present invention can be deposited by vapor in combination with other materials, although the situation may be different depending on which layer in the light emitting zone or in the hole transporting zone includes the compound.
• the spin coating process the compound can be incorporated into the formed layer by using a mixture of the compound with other materials.
• a cathode is formed on the electron injecting layer formed above in the last step and an organic EL device can be obtained.
• the cathode is made of a metal and can be formed in accordance with the vacuum vapor deposition process or the sputtering process. It is preferable that the vacuum vapor deposition process be used in order to prevent formation of damages on the lower organic layers during the formation of the film.
• the above-mentioned layers from the anode to the cathode be formed successively while the preparation system is kept in a vacuum after being evacuated once.
• the method of forming the layers in the organic EL device of the present invention is not particularly limited.
• a conventionally known process such as the vacuum vapor deposition process or the spin coating process can be used.
• the organic thin film layer which is used in the organic EL device of the present invention and includes the compound represented by general formula (1) described above can be formed in accordance with a known process such as the vacuum vapor deposition process or the molecular beam epitaxy process (the MBE process) or, using a solution prepared by dissolving the compounds into a solvent, in accordance with a coating process such as the dipping process, the spin coating process, the casting process, the bar coating process, or the roll coating process.
• each layer in the organic thin film layer in the organic EL device of the present invention is not particularly limited.
• an excessively thin layer tends to have defects such as pin holes, and an excessively thick layer requires a high applied voltage to decrease the efficiency. Therefore, a thickness in the range of several nanometers to 1 ⁇ m is preferable.
• the organic EL device which can be prepared as described above emits light when a direct voltage of 5 to 40 V is applied in the condition that the polarity of the anode is positive (+) and the polarity of the cathode is negative ( ⁇ ). When the polarity is reversed, no electric current is observed and no light is emitted at all.
• an alternating voltage is applied to the organic EL devices the uniform light emission is observed only in the condition that the polarity of the anode is positive and the polarity of the cathode is negative.
• an alternating voltage is applied to the
• the flask was set in an oil bath, and was gradually heated to 120° C. while the solution was stirred. At 7 hours after that, the flask was lifted off the oil bath so that the reaction would be completed. The flask was left under an argon atmosphere for 12 hours.
• reaction solution was transferred to a separating funnel, and 600 mL of dichloromethane were added to dissolve the precipitate. After the resultant had been washed with 120 mL of a saturated salt solutions an organic layer was dried with anhydrous potassium carbonate. The solvent of the organic layer obtained by separating potassium carbonate by filtration was removed by distillation. 400 mL of toluene and 80 mL of ethanol were added to the resultant residue. A drying pipe was attached to heat the resultant to 80° C. so that the residue would be completely dissolved. After that the resultant was left for 12 hours, and was slowly cooled to room temperature for recrystallization.
• the precipitated crystal was separated by filtration, and was dried in a vacuum at 60° C., whereby 13.5 g of N,N-di-(4-biphenylyl)benzylamine were obtained
• a stirring rod was placed in the flask.
• a three-way cock mounted with a balloon filled with 2 L of a hydrogen gas was attached to the flask, and the inside of the flask system was replaced with the hydrogen gas ten times by using a vacuum pump.
• the balloon was newly filled with a hydrogen gas in an amount corresponding to the reduced amount so that the volume of the hydrogen gas would be 2 L again.
• the solution was vigorously stirred at room temperature for 30 hours. After that, 100 mL of dichloromethane were added to the resultant, and the catalyst was separated by filtration.
• the resultant solution was transferred to a separating funnel, and was washed with 50 mL of a saturated aqueous solution of sodium hydrogencarbonate. After that, an organic layer was fractionated and dried with anhydrous potassium carbonate. After the resultant had been filtrated, the solvent was removed by distillation, and 50 mL of toluene were added to the resultant residue for recrystallization. The precipitated crystal was separated by filtration, and was dried in a vacuum at 50° C. whereby 0.99 g of di-4-biphenylylamine (Intermediate 1) shown below was obtained.
• the reaction vessel was placed in a water bath, and 44 g of 1,5-dibromopentane (manufactured by HIROSHIMA WAKO CO., LTD.) were added to the mixture while the mixture was stirred.
• the resultant was filtrated and washed with toluene. Further, the resultant was washed with water and methanol. After that the resultant was dried, whereby 15.0 g of a pale yellow powder were obtained.
• the dried product was condensed under reduced pressure, and the resultant crude product was subjected to column purification.
• the purified product was recrystallized with toluene.
• the crystal was taken by filtration, and was then dried, whereby 11.2 g of Intermediate 9 shown below as a white powder were obtained.
• the resultant was filtrated and washed with toluene. Further, the resultant was washed with water and methanol. After that, the resultant was dried whereby 14.0 g of a pale yellow powder were obtained.
• the dried product was condensed under reduced pressure, and the resultant crude product was subjected to column purification.
• the purified product was recrystallized with toluene.
• the crystal was taken by filtration, and was then dried, whereby 9.3 g of Intermediate 13 shown below as a white powder were obtained.
• the resultant was filtrated and washed with toluene. Further, the resultant was washed with water and methanol. After that, the resultant was dried, whereby 27.0 g of a pale yellow powder were obtained.
• the dried product was condensed under reduced pressure, and the resultant crude product was subjected to column purification.
• the purified product was recrystallized with toluene.
• the crystal was taken by filtration, and was then dried, whereby 18.1 g of Intermediate 19 shown below as a white powder were obtained.
• the resultant was slowly heated to room temperature and stirred for 1 hour 80 mL of 10% hydrochloric acid were added to the resultant, and the whole was extracted with ethyl acetate and water. After that, the extract was dried with anhydrous sodium sulfate. The solution was condensed and washed with hexane, whereby 9.7 g of a boric acid compound were obtained.
• the resultant was added with 500 ml of water, and the mixture was subjected to Celite filtration. The filtrate was extracted with toluene and dried with anhydrous magnesium sulfate. The resultant was concentrated under reduced pressure, and the resultant crude product was subjected to column purification. Then, the resultant was recrystallized with toluene, and the recrystallized product was separated by filtration and dried, thereby yielding 4.1 g of pale yellow powder.
• a glass substrate with an ITO transparent electrode measuring 25 mm wide by 75 mm long by 1.1 mm thick (manufactured by GEOMATEC Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes. After that, the substrate was subjected to UV ozone cleaning for 30 minutes.
• the glass substrate with the transparent electrode line after the washing was mounted on a substrate holder of a vacuum deposition device.
• Compound H232 to be described below was formed into the transparent electrode line was formed to cover the transparent electrode.
• the H232 film functions as a hole injecting layer.
• Compound H1 described above, as a hole transporting material was formed into a film having a thickness of 20 nm on the H232 film.
• the film functions as a hole transporting layer.
• Compound EM1 to be described below was deposited from the vapor and formed into a film having a thickness of 40 nm.
• the film functions as a light emitting layer.
• Alq to be described below was formed into a film having a thickness of 10 nm on the resultant film.
• the film functions as an electron injecting layer.
• Li serving as a reducing dopant (Li source: manufactured by SAES Getters) and Alq were subjected to co-deposition.
• an Alq:Li film (having a thickness of 10 nm) was formed as an electron injecting layer (cathode).
• Metal Al was deposited from the vapor onto the Ala:Li film to form a metal cathode.
• an organic EL device was formed.
• the current efficiency of the resultant organic EL device was measured, and the luminescent color of the device was observed.
• a current efficiency at 10 mA/cm 2 was calculated by measuring a luminance by using a CS1000 manufactured by Minolta. Further, the half lifetime of light emission in DC constant current driving at an initial luminance of 5,000 cd/m 2 and room temperature was measured. Table 1 shows the results thereof.
• Organic EL devices were each produced in the same manner as in Example 1 except that any one of the compounds shown in Table was used as a hole transporting material instead of Compound H1.
• An organic EL device was produced in the same manner as in Example 1 except that Comparative Compound 1 was used as a hole transporting material instead of Compound H1.
• the current efficiency of the resultant organic EL device was measured, and the luminescent color of the device was observed. Further, the half lifetime of light emission in DC constant current driving at an initial luminance of 5,000 cd/m 2 and room temperature was measured. Table 1 shows the results thereof.
• An organic EL device was produced in the same manner as in Example 1 except that Arylamine Compound D2 to be described below was used instead of Amine Compound DI having a styryl group.
• Me represents a methyl group.
• the measured current efficiency of the resultant organic EL device was 5.2 cd/A, and the luminescent color of the device was blue. Further, the half lifetime of light emission in DC constant current driving at an initial luminance of 5,000 cd/m 2 and room temperature was measured. The measured half lifetime was 400 hours.
• An organic EL device was produced in the same manner as in Example 27 except that Comparative Compound 1 described above was used instead of Compound H1 as a hole transporting material.
• the measured current efficiency of the resultant organic EL device was 4.9 cd/A, and the luminescent color of the device was blue. Further, the half lifetime of light emission in DC constant current driving at an initial luminance of 5,000 cd/m 2 and room temperature was measured. The measured half life time was 230 hours.
• the use of the aromatic amine derivative of the present invention as a hole transporting material for an organic EL device enables to emit light with luminous efficiency comparable to that of a conventional material, and is extremely effective in lengthening the lifetime.

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