WO2009081774A1 - ベンズアントラセン化合物及びそれを用いた有機エレクトロルミネッセンス素子 - Google Patents
ベンズアントラセン化合物及びそれを用いた有機エレクトロルミネッセンス素子 Download PDFInfo
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- WO2009081774A1 WO2009081774A1 PCT/JP2008/072682 JP2008072682W WO2009081774A1 WO 2009081774 A1 WO2009081774 A1 WO 2009081774A1 JP 2008072682 W JP2008072682 W JP 2008072682W WO 2009081774 A1 WO2009081774 A1 WO 2009081774A1
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- 0 *c1c(ccc2ccccc22)c2c(*)c2ccccc12 Chemical compound *c1c(ccc2ccccc22)c2c(*)c2ccccc12 0.000 description 5
- VOPJBEMFGHQJQC-UHFFFAOYSA-N Cc1cc(-c(cc2)cc(C)c2-c2nnc(-c3cccc4c3cccc4)[o]2)ccc1-c1nnc(-c2cccc3ccccc23)[o]1 Chemical compound Cc1cc(-c(cc2)cc(C)c2-c2nnc(-c3cccc4c3cccc4)[o]2)ccc1-c1nnc(-c2cccc3ccccc23)[o]1 VOPJBEMFGHQJQC-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention relates to a novel benzanthracene compound useful as a light-emitting material of an organic electroluminescence device and an organic electroluminescence device using the same.
- An organic electroluminescence (EL) element is a self-luminous element utilizing the principle that a light-emitting material emits light by recombination energy of holes injected from an anode and electrons injected from a cathode when an electric field is applied.
- Organic EL devices have made remarkable progress, and organic EL devices have features such as low-voltage driving, high brightness, diversity of emission wavelengths, high-speed response, and the ability to produce thin and light-emitting devices. Application to applications is expected.
- Luminescent materials used in organic EL elements have been actively studied since they have a great influence on the color of light emitted from the elements and the emission lifetime.
- As the light-emitting material one that emits light by a single substance or one that emits light by adding a small amount of dopant to a host material is known.
- fluorescent materials it has been studied to use phosphorescent compounds as light emitting materials and to use triplet state energy for light emission. With such various light emitting materials, light emission in a visible region from blue to red is obtained.
- Benzanthracene derivatives are disclosed in Patent Documents 1 and 2 as specific light emitting materials.
- organic EL devices using these benzanthracene derivatives have a short device life and poor chromaticity.
- An object of the present invention is to provide a novel benzanthracene compound, a light emitting material using the compound, and an organic EL device using the light emitting material.
- a compound having at least a part of the structure of the following formula. (In the formula, FA and FA ′ are the same or different substituted or unsubstituted condensed aromatic rings, and at least one is a condensed aromatic ring having 4 or more rings.) 2.
- the compound according to 1, wherein the four or more condensed aromatic rings are a pyrenyl group, a chrysenyl group, a benzfluorenyl group, a benzcricenyl group, a dibenzofluorenyl group, or a triphenylenyl group.
- a light emitting material comprising the compound according to 1 or 2. 4).
- An anode and a cathode Having one or more organic thin film layers including a light emitting layer sandwiched between the anode and the cathode,
- the organic electroluminescent element in which at least one layer of the organic thin film layer contains the compound according to 1 or 2. 5).
- the organic electroluminescence device according to 4 wherein the layer containing the compound further contains at least one of a phosphorescent dopant and a fluorescent dopant. 6).
- the fluorescent dopant is at least one of an arylamine compound and a styrylamine compound. 7).
- the novel benzanthracene compound, the luminescent material using the compound, and the organic EL element using the luminescent material can be provided.
- the organic EL element using the light emitting material of the present invention is excellent in chromaticity and lifetime.
- the benzanthracene compound of the present invention is a compound having at least a part of the following structure.
- FA and FA ′ are condensed aromatic groups which may have a substituent, and may be the same or different. At least one of FA and FA ′ is a condensed aromatic ring having 4 or more rings. .
- the benzanthracene compound of the present invention includes the structure of the above formula as a part or all of it.
- the structure shown in the above formula may be further substituted, or the structure shown in the above formula may be used.
- the condensed aromatic ring of FA and FA ′ preferably has 10 to 60 nuclear carbon atoms. (Preferably 10 to 30)
- Examples of the condensed aromatic ring include indenyl group, fluorenyl group, naphthyl group, anthryl group, phenanthryl group, naphthacenyl group, acenaphthylenyl group, biphenylenyl group, chrysenyl group, pyrenyl group, triphenylenyl.
- fluoranthenyl group perylenyl group, benzcricenyl group, benzfluorenyl group, dibenzofluorenyl group, naphthyl group, phenanthryl group, chrycenyl group, pyrenyl group, triphenylenyl group, fluorenyl group, benzcricenyl group, benz A fluorenyl group is preferred.
- the condensed aromatic ring having 4 or more rings preferably has 16 to 60 nuclear carbon atoms. (Preferably 16 to 40.)
- Examples of condensed aromatic rings having 4 or more rings include naphthacenyl group, chrycenyl group, benzcricenyl group, pyrenyl group, triphenylenyl group, fluoranthenyl group, perylenyl group, various tricyclic rings
- Examples include groups in which the condensed ring is benz-type (benzfluorenyl group, dibenzofluorenyl group, benzpyrenyl group, etc.), such as chrysenyl group, pyrenyl group, triphenylenyl group, benzcricenyl group, benzfluorenyl group, dibenzofluorenyl group An oleenyl group is preferred.
- an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, Butyl, sec-butyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (preferably having 2 to 20 carbon atoms, more preferably carbon 2 to 12, particularly preferably 2 to 8 carbon atoms such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably carbon 2 to 12, particularly preferably 2 to 8 carbon atoms, such as propargyl, 3-pentynyl, etc.), an aryl
- a substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, and particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino) , Diphenylamino, dibenzylamino and the like), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy, ethoxy, Butoxy and the like), an aryloxy group (preferably having 6 to 20 carbon atoms, Preferably it has 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy, 2-naphthyloxy, etc.), acyl group (preferably 1 to 20 carbon atoms, more preferably carbon atoms).
- 1 to 16 particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.
- an alkoxycarbonyl group preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms.
- an aryloxycarbonyl group preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably).
- acyloxy groups preferably Has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy.
- An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino, etc.), an alkoxycarbonylamino group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonylamino), aryloxycarbonylamino group (preferably having carbon number) 7 to 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), substituted or unsubstituted sulfonylamino groups (preferably having 1 carbon atom) To 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms.
- substituted or unsubstituted sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms.
- sulfamoyl Methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl etc.
- substituted or unsubstituted carbamoyl groups preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.
- an alkylthio group preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon atoms).
- An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio), substituted or unsubstituted sulfonyl A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), a substituted or unsubstituted sulfinyl group (preferably Has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), a substituted or unsubstituted ureido group (preferably It has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and
- a substituted or unsubstituted phosphoramide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphate amide, phenyl phosphate amide) Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino Group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
- the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
- the above benzanthracene compound can be used as a light emitting material for an organic EL device.
- the organic EL device of the present invention has an anode and a cathode, and one or more organic thin film layers including a light emitting layer sandwiched between the anode and the cathode, and at least one layer of the organic thin film layer is the above compound Containing.
- the layer containing the above compound can further contain at least one of a phosphorescent dopant and a fluorescent dopant. By including such a dopant, it can function as a phosphorescence emission layer and a fluorescence emission layer.
- the compound of the present invention may be used in any of the organic layers described above, but is preferably contained in the light emitting band, and particularly preferably contained in the light emitting layer.
- the content is preferably 30 to 100 wt%.
- Fig. 1 shows the configuration (8).
- the organic EL element includes a cathode 10 and an anode 20 and a hole injection layer 30, a hole transport layer 32, a light emitting layer 34, and an electron injection layer 36 sandwiched therebetween.
- the hole injection layer 30, the hole transport layer 32, the light emitting layer 34, and the electron injection layer 36 correspond to a plurality of organic thin film layers. At least one of these organic thin film layers 30, 32, 34, and 36 contains the benzanthracene compound.
- the organic EL element is usually produced on a substrate, and the substrate supports the organic EL element. It is preferable to use a smooth substrate. When light is extracted through this substrate, it is desirable that the substrate is translucent and that the transmittance of light in the visible region with a wavelength of 400 to 700 nm is 50% or more.
- substrate a glass plate, a synthetic resin board, etc. are used suitably, for example.
- the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
- the synthetic resin plate include plates of polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyethersulfone resin, polysulfone resin, and the like.
- the anode It is effective for the anode to inject holes into the hole injection layer, the hole transport layer, or the light emitting layer and to have a work function of 4.5 eV or more.
- the anode material include indium tin oxide (ITO), a mixture of indium oxide and zinc oxide, a mixture of ITO and cerium oxide (ITCO), a mixture of indium oxide and zinc oxide and cerium oxide (IZCO), an oxidation Examples thereof include a mixture of indium and cerium oxide (ICO), a mixture of zinc oxide and aluminum oxide (AZO), tin oxide (NESA), gold, silver, platinum, and copper.
- the anode can be formed from these electrode materials by vapor deposition or sputtering.
- the transmittance of the anode for light emission is greater than 10%.
- the sheet resistance of the anode is preferably several hundred ⁇ / ⁇ or less.
- the film thickness of the anode depends on the material, it is usually 10 nm to 1 ⁇ m, preferably 10 to 200 nm.
- the light emitting layer has the following functions.
- injection function function capable of injecting holes from the anode or hole injection layer when an electric field is applied, and electron injection from the cathode or electron injection layer
- transport function injected charge (electrons (Iii) light emission function; function to recombine electrons and holes and connect them to light emission
- the light emitting layer is particularly preferably a molecular deposited film.
- the molecular deposited film is a film formed by depositing a material compound in a gas phase state or a film formed by solidifying a material compound in a solution state or a liquid phase state.
- this molecular deposited film is an LB.
- the thin film (molecular accumulation film) formed by the method can be classified by the difference in aggregated structure and higher order structure, and the functional difference resulting therefrom.
- the light emitting layer can also be formed by dissolving a binder such as a resin and a material compound in a solvent to form a solution, and then thinning the solution by a spin coating method or the like.
- Examples of the light emitting material or the doping material that can be used for the light emitting layer include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, Coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine , Merocyanine, imidazole chelating oxinoid compounds, quinacrid
- Ar 001 is a substituted or unsubstituted condensed aromatic group having 10 to 50 nuclear carbon atoms.
- Ar 002 is a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms.
- X 001 to X 003 independently represents a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, a substituted or unsubstituted carbon group having 1 to 50 alkyl groups, substituted or unsubstituted alkoxy groups having 1 to 50 carbon atoms, substituted or unsubstituted aralkyl groups having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups having 5 to 50 carbon atoms, substituted Or an unsubstituted arylthio group having 5 to 50 nucleus atoms, a substituted or unsubstituted alkoxy
- R 001 to R 010 are each independently a hydrogen atom, a substituted or unsubstituted aromatic ring group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, substituted Or an 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, Substituted or unsubstituted aryloxy group having 5 to 50 nucleus atoms, substituted or unsubstituted arylthio group having 5 to 50 nucleus atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, substituted or unsubstituted A silyl group, a
- Ar 005 and Ar 006 are each a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms.
- L 001 and L 002 are 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, respectively.
- m is an integer from 0 to 2
- n is an integer from 1 to 4
- s is an integer from 0 to 2
- t is an integer from 0 to 4.
- L 001 or Ar 005 binds to any of the 1-5 positions of pyrene
- L 002 or Ar 006 binds to any of the 6-10 positions of pyrene.
- n + t is an even number
- Ar 005 , Ar 006 , L 001 , and L 002 satisfy the following (1) or (2).
- a 001 and A 002 are each independently a substituted or unsubstituted condensed aromatic ring group having 10 to 20 nuclear carbon atoms.
- Ar 007 and Ar 008 are each independently a hydrogen atom or a substituted or unsubstituted aromatic ring group having 6 to 50 nuclear carbon atoms.
- R 011 to R 020 are each independently a hydrogen atom, a substituted or unsubstituted aromatic ring group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, a substituted group Or an 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, Substituted or unsubstituted aryloxy group having 5 to 50 nucleus atoms, substituted or unsubstituted arylthio group having 5 to 50 nucleus atoms, substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, substituted or unsubstituted A silyl group
- Ar 007 , Ar 008 , R 019 and R 020 may each be plural, and adjacent ones may form a saturated or unsaturated cyclic structure.
- a group that is symmetrical with respect to the XY axis shown on the anthracene is not bonded to the 9th and 10th positions of the central anthracene.
- R 021 to R 030 are each independently a hydrogen atom, alkyl group, cycloalkyl group, optionally substituted aryl group, alkoxyl group, aryloxy group, alkylamino group, alkenyl group, arylamino group, or substituted.
- a and b each represent an integer of 1 to 5, and when they are 2 or more, R 021s or R 022s may be the same or different from each other In addition, R 021 or R 022 may be bonded to each other to form a ring, or R 023 and R 024 , R 025 and R 026 , R 027 and R 028 , R 029 and R 030 are L 003 may be a single bond, —O—, —S—, —N (R) — (R is an alkyl group or an optionally substituted aryl group). Represents an alkylene group or an arylene group.)
- R 031 to R 040 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxyl group, an aryloxy group, an alkylamino group, an arylamino group, or an optionally substituted multicyclic group
- C, d, e and f each represent an integer of 1 to 5, and when they are 2 or more, R 031s , R 032s , R 036s or R 037s may be the same.
- R 031 may be different from each other, R 032 may be bonded to each other, R 033 may be bonded to each other, or R 037 may be bonded to each other to form a ring, and R 033 and R 034 , R 039 and R 040 are based on each other.
- bonded to ring the optionally formed .L 004 is a single bond, -O -, - S -, - N (R) - (R is an aryl group which may be alkyl or substituted), Al Shows the alkylene group or an arylene group.)
- a 005 to A 008 are each independently a substituted or unsubstituted biphenylyl group or a substituted or unsubstituted naphthyl group.
- a 011 to A 013 are each independently a substituted or unsubstituted arylene group having 6 to 50 nuclear carbon atoms.
- a 014 to A 016 are each independently a hydrogen atom, or a substituted or unsubstituted group.
- a substituted aryl group having 6 to 50 carbon atoms, R 041 to R 043 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or 1 carbon atom; Alkoxy group having 6 to 6 carbon atoms, aryloxy group having 5 to 18 carbon atoms, aralkyloxy group having 7 to 18 carbon atoms, arylamino group having 5 to 16 carbon atoms, nitro group, cyano group, ester group having 1 to 6 carbon atoms Or a halogen atom, and at least one of A 011 to A 016 is a group having three or more condensed aromatic rings.
- Fluorene compound represented by the following formula (ix) is represented by the following formula (ix).
- R 051 and R 052 are 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, or a substituted amino group.
- R 053 and R 054 may be 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 ring.
- R 053 and R 054 representing a group and bonded to different fluorene groups may be the same or different.
- R 053 and R 054 bonded to the same fluorene group may be the same or different, and Ar 011 and Ar 012 are substituted or unsubstituted condensed polycyclic aromatics having a total of 3 or more benzene rings.
- N represents an integer of 1 to 10.
- the host compound when using a phosphorescent dopant include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, aryl Amine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, anthraquinodimethane derivatives , Anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine Derivatives, metal
- the light emitting layer may contain a phosphorescent dopant and / or a fluorescent dopant in addition to the light emitting material of the present invention, if desired. Moreover, you may laminate
- a phosphorescent dopant is a compound that can emit light from triplet excitons. Although it is not particularly limited as long as it emits light from triplet excitons, it 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 ortho Metalated metal complexes are preferred.
- the phosphorescent compounds may be used alone or in combination of two or more.
- the porphyrin metal complex is preferably a porphyrin platinum complex.
- ligands that form orthometalated metal complexes.
- Preferred ligands include compounds having a phenylpyridine skeleton, bipyridyl skeleton or phenanthroline skeleton, or 2-phenylpyridine derivatives, 7,8. -Benzoquinoline derivatives, 2- (2-thienyl) pyridine derivatives, 2- (1-naphthyl) pyridine derivatives, 2-phenylquinoline derivatives and the like.
- These ligands may have a substituent as needed.
- a fluorinated compound or a compound having a trifluoromethyl group introduced is preferable as a blue dopant.
- you may have ligands other than the said ligands, such as an acetylacetonate and picric acid, as an auxiliary ligand.
- metal complexes include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, tris (2- Phenylpyridine) osmium, tris (2-phenylpyridine) rhenium, octaethylplatinum porphyrin, octaphenylplatinum porphyrin, octaethylpalladium porphyrin, octaphenylpalladium porphyrin, etc.
- An appropriate complex is selected depending on the device performance and the host compound to be used.
- content in the light emitting layer of a phosphorescent dopant there is no restriction
- Fluorescent dopants include amine compounds, diamine compounds, aromatic compounds, chelate complexes such as tris (8-quinolinolato) aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives, oxadiazole derivatives, etc.
- the compound is preferably selected in accordance with the required emission color, and a styrylamine compound, a styryldiamine compound, an arylamine compound, and an aryldiamine compound are more preferable.
- the condensed polycyclic aromatic compound which is not an amine compound is also preferable. These fluorescent dopants may be used alone or in combination.
- styrylamine compound and styryldiamine compound those represented by the following formula (A) are preferable.
- Ar 101 is a p-valent group, and a corresponding p-valent group of a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a stilbenyl group, or a distyrylaryl group
- Ar 102 and Ar 103 are Each of them is an aromatic hydrocarbon group having 6 to 20 carbon atoms
- Ar 101 , Ar 102 and Ar 103 may be substituted, and any one of Ar 101 to Ar 103 is substituted with a styryl group.
- At least one of Ar 102 or Ar 103 is substituted with a styryl group, and p is an integer of 1 to 4, and preferably an integer of 1 to 2.
- examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, and a terphenyl group.
- arylamine compound and the aryldiamine compound those represented by the following formula (B) are preferable.
- Ar 111 is a q-valent substituted or unsubstituted aromatic group having 5 to 40 nuclear carbon atoms
- Ar 112 and Ar 113 are each a substituted or unsubstituted aryl group having 5 to 40 nuclear carbon atoms.
- Q is an integer of 1 to 4, preferably an integer of 1 to 2.
- examples of the aryl group having 5 to 40 nuclear carbon atoms include phenyl, naphthyl, anthranyl, phenanthryl, pyrenyl, coronyl, biphenyl, terphenyl, pyrrolyl, furyl, thienyl.
- Preferred substituents substituted on the aryl group include alkyl groups having 1 to 6 carbon atoms (ethyl group, methyl group, i-propyl group, n-propyl group, s-butyl group, t-butyl group, pentyl group).
- the light emitting layer may contain a hole transport material, an electron transport material, and a polymer binder as necessary.
- the thickness of the light emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, and most preferably 10 to 50 nm. If the thickness is less than 5 nm, it is difficult to form a light emitting layer, and it may be difficult to adjust the chromaticity. If the thickness exceeds 50 nm, the driving voltage may increase.
- the hole injection layer and the hole transport layer help to inject holes into the light emitting layer and transport to the light emitting region, and have a high hole mobility and a small ionization energy of usually 5.5 eV or less.
- a material for such a hole injection layer and a hole transport layer a material that transports holes to the light emitting layer with lower electric field strength is preferable, and the hole mobility is, for example, 10 4 to 10 6 V / cm. When applying the electric field of 10 ⁇ 4 cm 2 / V ⁇ sec or more, it is preferable.
- the material for the hole injection layer and the hole transport layer is not particularly limited, and is conventionally used as a charge transport material for holes in optical transmission materials, and the hole injection layer and holes for organic EL devices. An arbitrary thing can be selected and used from the well-known things used for the transport layer.
- Ar 211 to Ar 213 , Ar 221 to Ar 223, and Ar 203 to Ar 208 are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, or a substituted or unsubstituted number of 5 to 50 nuclear atoms.
- a to c and p to r are integers of 0 to 3, respectively.
- Ar 203 and Ar 204 , Ar 205 and Ar 206 , Ar 207 and Ar 208 may be connected to each other to form a saturated or unsaturated ring.
- substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, and 9-anthryl group.
- substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nucleus atoms include 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, and 3-pyridinyl group.
- Ar 231 to Ar 234 are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms.
- L is a linking group, which is a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms.
- x is an integer of 0 to 5.
- Ar 232 and Ar 233 may combine with each other to form a saturated or unsaturated ring. Specific examples of the substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 nuclear carbon atoms and the substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms are the same as those described above. can give.
- the material for the hole injection layer and the hole transport layer include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives. And amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers (particularly thiophene oligomers).
- the above materials can be used for the hole injection layer and the hole transport layer, but porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds, particularly aromatic tertiary amine compounds should be used. Is preferred.
- NPD 4,4′-bis (N- (1-naphthyl) -N-phenylamino) biphenyl
- MTDATA triphenylamine
- R 201 to R 206 each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted heterocyclic group.
- R 201 and R 202 , R 203 and R 204 , R 205 and R 206 , R 201 and R 206 , R 202 and R 203 , or R 204 and R 205 may form a condensed ring.
- R 211 to R 216 are substituents, each preferably an electron-withdrawing group such as a cyano group, a nitro group, a sulfonyl group, a carbonyl group, a trifluoromethyl group, or a halogen.
- inorganic compounds such as p-type Si and p-type SiC can also be used as materials for the hole injection layer and the hole transport layer.
- the hole injection layer and the hole transport layer can be formed by thinning the above-described compound by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method.
- the thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually 5 nm to 5 ⁇ m.
- the hole injection layer and the hole transport layer may be composed of one or more layers made of the above-mentioned materials, or a plurality of hole injection layers and hole transport layers made of different compounds are laminated. There may be.
- the organic semiconductor layer is a layer that assists hole injection or electron injection into the light emitting layer, and preferably has a conductivity of 10 ⁇ 10 S / cm or more.
- a conductive oligomer such as a thiophene-containing oligomer or an arylamine oligomer, a conductive dendrimer such as an arylamine dendrimer, or the like can be used.
- the electron injection layer and the electron transport layer are layers that assist injection of electrons into the light emitting layer and transport them to the light emitting region, and have a high electron mobility.
- the adhesion improving layer is a kind of an electron injecting layer made of a material that particularly adheres well to the cathode.
- the electron transport layer is appropriately selected with a film thickness of 5 nm to 5 ⁇ m. In particular, when the film thickness is large, the electron mobility is 10 ⁇ 5 cm when an electric field of 10 4 to 10 6 V / cm is applied in order to avoid an increase in voltage. It is preferable that it is 2 / Vs or more.
- 8-hydroxyquinoline or a metal complex of its derivative or an oxadiazole derivative is preferable.
- metal complexes of 8-hydroxyquinoline or its derivatives include metal chelate oxinoid compounds containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline), such as tris (8-quinolinolato) aluminum. it can.
- Examples of the oxadiazole derivatives include electron transfer compounds represented by the following formula.
- Ar 301 , Ar 302 , Ar 303 , Ar 305 , Ar 306 , and Ar 309 each represent a substituted or unsubstituted aryl group.
- Ar 304 , Ar 307 , and Ar 308 are each substituted or unsubstituted. Represents an arylene group.
- 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 biphenylene group, an anthranylene group, a peryleneylene group, and a pyrenylene group.
- examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cyano group.
- This electron transfer compound is preferably a thin film-forming compound.
- the electron transfer compound examples include the following. (Me represents a methyl group, and tBu represents a tbutyl group.)
- materials represented by the following formulas (E) to (J) can also be used as materials used for the electron injection layer and the electron transport layer.
- a 311 to A 313 each represent a nitrogen atom or a carbon atom.
- Ar 311 is a substituted or unsubstituted aryl group having 6 to 60 nucleus atoms or a substituted or unsubstituted heteroaryl group having 3 to 60 nucleus atoms
- Ar 311 ′ is a substituted or unsubstituted nucleus atom.
- Ar 312 represents a hydrogen atom, a substituted or unsubstituted aryl group of 6 to 60 nuclear atoms, a substituted or unsubstituted An unsubstituted heteroaryl group having 3 to 60 nucleus 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.
- any one of Ar 311 and Ar 312 is a substituted or unsubstituted condensed ring group having 10 to 60 nucleus atoms, or a substituted or unsubstituted monoheterocondensed ring group having 3 to 60 nucleus atoms.
- L 311 , L 312 and L 313 are each a single bond, a substituted or unsubstituted arylene group having 6 to 60 nucleus atoms, a substituted or unsubstituted heteroarylene group having 3 to 60 nucleus atoms, or a substituted or unsubstituted group. Substituted fluorenylene group.
- R and R 311 are each a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 60 nucleus atoms, a substituted or unsubstituted heteroaryl group having 3 to 60 nucleus atoms, a substituted or unsubstituted carbon atom having 1 to 20 alkyl groups, or substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, n is an integer of 0 to 5, and when n is 2 or more, a plurality of Rs may be the same or different.
- adjacent R groups may be bonded to each other to form a carbocyclic aliphatic ring or a carbocyclic aromatic ring. The nitrogen-containing heterocyclic derivative represented by this.
- HAr is a nitrogen-containing heterocyclic ring having 3 to 40 carbon atoms which may have a substituent
- L 314 has a carbon number of 6 to 60 optionally having a single bond or a substituent.
- Ar 321 may have a substituent
- Ar 322 is an aryl group having 6 to 60 carbon atoms which may have a substituent or a carbon number which may have a substituent.
- X 301 and Y 301 are each 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, a substituted group Or an unsubstituted heterocycle or a structure in which X and Y are combined to form a saturated or unsaturated ring
- R 301 to R 304 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group Perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group,
- R 321 to R 328 and Z 322 are each a hydrogen atom, a saturated or unsaturated hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a substituted amino group, a substituted boryl group, an alkoxy group or an aryl group.
- X 302 , Y 302 and Z 321 each represents a saturated or unsaturated hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, substituted amino group, alkoxy group or aryloxy group; 321 and Z 322 may be bonded to each other to form a condensed ring.
- N represents an integer of 1 to 3, and when n or (3-n) is 2 or more, R 321 to R 328 , X 302 , Y 302 , Z 322 and Z 321 may be the same or different, provided that n is 1, X 302 , Y 302 and R 322 are methyl groups and R 328 is a hydrogen atom or a substituted boryl group. And a compound in which n is 3 and Z 321 is a methyl group).
- Q 301 and Q 302 each represent a ligand represented by the following formula (K), and L 315 represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group , Substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, —OR (where R is a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl Group, a substituted or unsubstituted heterocyclic group) or a ligand represented by —O—Ga—Q 303 (Q 304 ) (Q 303 and Q 304 are the same as Q 301 and Q 302 ). . ] The gallium complex represented by this.
- ring A 301 and A 302 are each a 6-membered aryl ring structure condensed with each other, which may have a substituent. ]
- This metal complex has strong properties as an n-type semiconductor and has a large electron injection capability. Furthermore, since the generation energy at the time of complex formation is also low, the bondability between the metal and the ligand of the formed metal complex is strengthened, and the fluorescence quantum efficiency as a light emitting material is large.
- substituents of the rings A 301 and A 302 that form the ligand of the formula (K) include chlorine, bromine, iodine, halogen atoms of fluorine, methyl group, ethyl group, propyl group, butyl Group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group and other substituted or unsubstituted alkyl groups, phenyl group, naphthyl group, biphenyl group, anthranyl Group, phenanthryl group, fluorenyl group, pyrenyl group, 3-methylphenyl group, 3-methoxyphenyl group, 3-fluorophenyl group, 3-trichloromethylphenyl group, 3-trifluoromethylphenyl group, 3-nitrophenyl group, etc.
- Substituted or unsubstituted aryl group methoxy group, n-butoxy group, t-butoxy group, trichloromethoxy group Trifluoroethoxy group, pentafluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group, 1,1,1,3,3,3-hexafluoro-2-propoxy group, 6- (perfluoroethyl)
- Substituted or unsubstituted alkoxy group such as hexyloxy group, phenoxy group, p-nitrophenoxy group, pt-butylphenoxy group, 3-fluorophenoxy group, pentafluorophenoxy group, 3-trifluoromethylphenoxy group, etc.
- an unsubstituted carbamoyl group, carboxylic acid group, sulfonic acid group, imide group, cyclopentane group, cyclohexyl group and other cycloalkyl groups pyridinyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, triazinyl group, indolinyl group, quinolinyl group Group, acridinyl group, pyrrolidinyl group, dioxanyl group, piperidinyl group, morpholinyl group, piperazinyl group, carbazolyl group, furyl group, thienyl group, oxazolyl group, oxadiazolyl group, benzoxazolyl group, thiazolyl group, thiadiazolyl group, benzothiazolyl group, There are heterocyclic groups such as a triazolyl group, an imidazolyl group, and a benzoimide
- a reducing dopant is contained in a region for transporting electrons or an interface region between the cathode and the organic layer.
- the reducing dopant is defined as a substance capable of reducing the electron transporting compound. Accordingly, various materials can be used as long as they have a certain reducibility, such as alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals.
- preferable reducing dopants include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV) and Cs (work function: 1. 95 eV), at least one alkali metal selected from the group consisting of Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV), and Ba (work function: 2.52 eV) At least one alkaline earth metal selected from the group consisting of: A work function of 2.9 eV or less is particularly preferable.
- a more preferable reducing dopant is at least one alkali metal selected from the group consisting of K, Rb and Cs, more preferably Rb or Cs, and most preferably Cs.
- alkali metals have particularly high reducing ability, and the addition of a relatively small amount to the electron injection region can improve the light emission luminance and extend the life of the organic EL element.
- a reducing dopant having a work function of 2.9 eV or less a combination of these two or more alkali metals is also preferable.
- a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, A combination of Cs, Na and K is preferred.
- An electron injection layer composed of an insulator or a semiconductor may be further provided between the cathode and the organic layer. With such a layer, current leakage can be effectively prevented, and the electron injection property can be improved. If the electron injection layer is an insulating thin film, a more uniform thin film is formed, so that pixel defects such as dark spots can be reduced.
- the insulator it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. It is preferable that the electron injection layer is composed of these alkali metal chalcogenides and the like, since the electron injection property can be further improved.
- preferable alkali metal chalcogenides include, for example, Li 2 O, K 2 O, Na 2 S, Na 2 Se, and Na 2 O
- preferable alkaline earth metal chalcogenides include, for example, CaO, BaO. , SrO, BeO, BaS, and CaSe.
- preferable alkali metal halides include, for example, LiF, NaF, KF, CsF, LiCl, KCl, and NaCl.
- preferable alkaline earth metal halides include fluorides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 and BeF 2 , and halides other than fluorides.
- the inorganic compound constituting the electron injection layer is preferably a microcrystalline or amorphous insulating thin film.
- a material having a work function (for example, 4 eV or less) metal, an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
- electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, cesium, magnesium / silver alloy, aluminum / aluminum oxide, Al / Li 2 O, Al / LiO, Al / LiF, aluminum Examples include lithium alloys, indium, and rare earth metals.
- the cathode can be produced from these electrode materials by vapor deposition or sputtering.
- the transmittance of the cathode for light emission is preferably greater than 10%.
- the sheet resistance as the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually 10 nm to 1 ⁇ m, preferably 50 to 200 nm.
- an insulating thin film layer may be inserted between the pair of electrodes.
- the material used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, Examples include germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide. A mixture or laminate of these may be used.
- the above-described materials and methods may be used to sequentially form the necessary layers from the anode and finally form the cathode.
- an organic EL element can also be produced in the reverse order from the cathode to the anode.
- an example of manufacturing an organic EL element having a structure in which an anode / a hole injection layer / a light emitting layer / an electron injection layer / a cathode are sequentially provided on a translucent substrate will be described.
- a thin film made of an anode material is formed on a translucent substrate by vapor deposition or sputtering to form an anode.
- a hole injection layer is provided on the anode.
- the hole injection layer can be formed by a method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method.
- the deposition conditions vary depending on the compound used (material of the hole injection layer), the structure of the target hole injection layer, etc., but generally the deposition source temperature is 50 to 450. It is preferable to appropriately select at a temperature of 10 ° C., a degree of vacuum of 10 ⁇ 7 to 10 ⁇ 3 Torr, a deposition rate of 0.01 to 50 nm / second, and a substrate temperature of ⁇ 50 to 300 ° C.
- a light emitting layer is provided on the hole injection layer.
- the light emitting layer can also be formed by thinning the light emitting material by a method such as vacuum deposition, sputtering, spin coating, or casting, but it is easy to obtain a uniform film and pinholes are not easily generated. From the point of view, it is preferable to form by vacuum deposition.
- the vapor deposition conditions vary depending on the compound used, but can generally be selected from the same condition range as the formation of the hole injection layer.
- an electron injection layer is provided on the light emitting layer.
- a vacuum evaporation method like the hole injection layer and the light emitting layer, it is preferable to form by a vacuum evaporation method because it is necessary to obtain a homogeneous film.
- Deposition conditions can be selected from the same condition range as the hole injection layer and the light emitting layer.
- a cathode can be laminated
- the cathode can be formed by vapor deposition or sputtering. In order to protect the underlying organic material layer from damage during film formation, vacuum deposition is preferred.
- the above organic EL device is preferably produced from the anode to the cathode consistently by a single vacuum.
- the method for forming each layer of the organic EL element is not particularly limited.
- the organic thin film layer containing the compound of the present invention is prepared by vacuum deposition, molecular beam deposition (MBE method) or dipping method of a solution obtained by dissolving the compound of the present invention in a solvent, spin coating method, casting method, bar coating method, It can be formed by a known method using a coating method such as a roll coating method.
- MBE method molecular beam deposition
- the evaluation of the organic EL element is as follows.
- the following compound A-2 having a thickness of 20 nm was formed as a hole transport layer on the A-1 film. Further, on this A-2 film, the compound H-1 of the present invention and the diamine derivative D-1 were formed in a film thickness ratio of 40: 2 at a film thickness ratio of 40: 2 to obtain a blue light emitting layer. H-1 functions as a host and D-1 functions as a dopant.
- the following compound Alq was deposited as an electron transport layer with a thickness of 20 nm by vapor deposition. Thereafter, LiF was formed to a thickness of 1 nm. On the LiF film, metal Al was deposited to a thickness of 150 nm to form a metal cathode to form an organic EL light emitting device.
- Examples 2 to 36 A device was prepared and evaluated in the same manner as in Example 1 except that H-1 and / or D-1 was changed to the following compounds shown in Table 1 in Example 1. The results are shown in Tables 1 and 2.
- the benzanthracene compound was synthesized according to synthesis routes (2) to (4).
- Example 37 to 42, Comparative Examples 4 to 6 An organic EL device was produced in the same manner as in Example 1 except that the dopant material and host material of the light emitting layer in Example 1 were changed to the compounds shown in Table 3. The results are shown in Table 3.
- the benzanthracene compound of the present invention can be used as a light emitting material for an organic EL device.
- the organic EL device of the present invention can be suitably used for light sources such as flat light emitters and display backlights, display units such as mobile phones, PDAs, car navigation systems, and vehicle instrument panels, and lighting.
- light sources such as flat light emitters and display backlights
- display units such as mobile phones, PDAs, car navigation systems, and vehicle instrument panels, and lighting.
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Abstract
Description
有機EL素子の進歩は目覚しく、また、有機EL素子は、低電圧駆動、高輝度、発光波長の多様性、高速応答性、薄型で軽量な発光デバイスが作製可能等の特徴を有するため、広汎な用途への適用が期待されている。
発光材料は、単独物質で発光するものや、ホスト材料に少量のドーパントを加えて発光するものが知られている。また、蛍光発光材料の他、燐光性化合物を発光材料として用い、三重項状態のエネルギーを発光に用いることが検討されている。このような様々な発光材料により、青色から赤色までの可視領域の発光が得られている。
1.下記式の構造を少なくとも一部として有する化合物。
2.前記4環以上の縮合芳香族環が、ピレニル基、クリセニル基、ベンズフルオレニル基、ベンズクリセニル基、ジベンゾフルオレニル基又はトリフェニレニル基である1に記載の化合物。
3.1又は2記載の化合物からなる発光材料。
4.陽極及び陰極と、
前記陽極及び陰極の間に挟持されている、発光層を含む1以上の有機薄膜層とを有し、
前記有機薄膜層の少なくとも一層が、1又は2記載の化合物を含有する有機エレクトロルミネッセンス素子。
5.前記化合物を含有する層が、さらに、りん光性ドーパント及び蛍光性ドーパントの少なくとも1つを含有する4記載の有機エレクトロルミネッセンス素子。
6.前記蛍光性ドーパントが、アリールアミン化合物及びスチリルアミン化合物の少なくとも1つである5記載の有機エレクトロルミネッセンス素子。
7.前記りん光性ドーパントが、金属錯体である5又は6記載の有機エレクトロルミネッセンス素子。
本発明の発光材料を用いる有機EL素子は、色度と寿命に優れる。
(1)陽極/発光層/陰極
(2)陽極/正孔注入層/発光層/陰極
(3)陽極/発光層/電子注入層/陰極
(4)陽極/正孔注入層/発光層/電子注入層/陰極
(5)陽極/有機半導体層/発光層/陰極
(6)陽極/有機半導体層/電子障壁層/発光層/陰極
(7)陽極/有機半導体層/発光層/付着改善層/陰極
(8)陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極
(9)陽極/絶縁層/発光層/絶縁層/陰極
(10)陽極/無機半導体層/絶縁層/発光層/絶縁層/陰極
(11)陽極/有機半導体層/絶縁層/発光層/絶縁層/陰極
(12)陽極/絶縁層/正孔注入層/正孔輸送層/発光層/絶縁層/陰極
(13)陽極/絶縁層/正孔注入層/正孔輸送層/発光層/電子注入層/陰極
等を挙げることができるが、これらに限定されない。これらの中で通常(8)の構成が好ましく用いられる。
有機EL素子は、通常基板上に作製し、基板は有機EL素子を支持する。平滑な基板を用いるのが好ましい。この基板を通して光を取り出すときは、基板は透光性であり、波長400~700nmの可視領域の光の透過率が50%以上であるものが望ましい。
このような透光性基板としては、例えば、ガラス板、合成樹脂板等が好適に用いられる。ガラス板としては、ソーダ石灰ガラス、バリウム・ストロンチウム含有ガラス、鉛ガラス、アルミノケイ酸ガラス、ホウケイ酸ガラス、バリウムホウケイ酸ガラス、石英等の板が挙げられる。また、合成樹脂板としては、ポリカーボネート樹脂、アクリル樹脂、ポリエチレンテレフタレート樹脂、ポリエーテルスルホン樹脂、ポリスルホン樹脂等の板が挙げられる。
陽極はこれらの電極物質から蒸着法やスパッタリング法等で形成できる。
発光層からの発光を陽極から取り出す場合、陽極の発光に対する透過率を10%より大きくすることが好ましい。また陽極のシート抵抗は、数百Ω/□以下が好ましい。陽極の膜厚は材料にもよるが、通常10nm~1μm、好ましくは10~200nmである。
(i)注入機能;電界印加時に陽極又は正孔注入層より正孔を注入することができ、陰極又は電子注入層より電子を注入することができる機能
(ii)輸送機能;注入した電荷(電子と正孔)を電界の力で移動させる機能
(iii)発光機能;電子と正孔を再結合させ、これを発光につなげる機能
また樹脂等の結着剤と材料化合物とを溶剤に溶かして溶液とした後、これをスピンコート法等により薄膜化することによっても、発光層を形成することができる。
下記式(i)で表される非対称アントラセン。
R001~R010は、それぞれ独立に、水素原子、置換もしくは無置換の核炭素数6~50の芳香族環基、置換もしくは無置換の核原子数5~50の芳香族複素環基、置換もしくは無置換の炭素数1~50のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換の炭素数1~50のアルコキシ基、置換もしくは無置換の炭素数6~50のアラルキル基、置換もしくは無置換の核原子数5~50のアリールオキシ基、置換もしくは無置換の核原子数5~50のアリールチオ基、置換もしくは無置換の炭素数1~50のアルコキシカルボニル基、置換もしくは無置換のシリル基、カルボキシル基、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシ基である。)
mは0~2の整数、nは1~4の整数、sは0~2の整数、tは0~4の整数である。
また、L001又はAr005は、ピレンの1~5位のいずれかに結合し、L002又はAr006は、ピレンの6~10位のいずれかに結合する。ただし、n+tが偶数の時、Ar005,Ar006,L001,L002は下記(1)又は(2)を満たす。
(1) Ar005≠Ar006及び/又はL001≠L002(ここで≠は、異なる構造の基であることを示す。)
(2) Ar005=Ar006かつL001=L002の時
(2-1) m≠s及び/又はn≠t、又は
(2-2) m=sかつn=tの時、
(2-2-1) L001及びL002、又はピレンが、それぞれAr005及びAr006上の異なる結合位置に結合しているか、(2-2-2) L001及びL002、又はピレンが、Ar005及びAr006上の同じ結合位置で結合している場合、L001及びL002又はAr005及びAr006のピレンにおける置換位置が1位と6位、又は2位と7位である場合はない。]
Ar007及びAr008は、それぞれ独立に、水素原子、又は置換もしくは無置換の核炭素数6~50の芳香族環基である。
R011~R020は、それぞれ独立に、水素原子、置換もしくは無置換の核炭素数6~50の芳香族環基、置換もしくは無置換の核原子数5~50の芳香族複素環基、置換もしくは無置換の炭素数1~50のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換の炭素数1~50のアルコキシ基、置換もしくは無置換の炭素数6~50のアラルキル基、置換もしくは無置換の核原子数5~50のアリールオキシ基、置換もしくは無置換の核原子数5~50のアリールチオ基、置換もしくは無置換の炭素数1~50のアルコキシカルボニル基、置換もしくは無置換のシリル基、カルボキシル基、ハロゲン原子、シアノ基、ニトロ基又はヒドロキシ基である。
Ar007、Ar008、R019及びR020は、それぞれ複数であってもよく、隣接するもの同士で飽和もしくは不飽和の環状構造を形成していてもよい。
ただし、式(iv)において、中心のアントラセンの9位及び10位に、該アントラセン上に示すX-Y軸に対して対称型となる基が結合する場合はない。)
具体例としては、以下のような化合物が挙げられる。
オルトメタル化金属錯体を形成する配位子としては種々のものがあるが、好ましい配位子としては、フェニルピリジン骨格、ビピリジル骨格又はフェナントロリン骨格を有する化合物、又は2-フェニルピリジン誘導体、7,8-ベンゾキノリン誘導体、2-(2-チエニル)ピリジン誘導体、2-(1-ナフチル)ピリジン誘導体、2-フェニルキノリン誘導体等が挙げられる。これらの配位子は必要に応じて置換基を有してもよい。特に、フッ素化物、トリフルオロメチル基を導入したものが、青色系ドーパントとしては好ましい。さらに補助配位子としてアセチルアセトナート、ピクリン酸等の上記配位子以外の配位子を有していてもよい。
ここで、炭素数が6~20の芳香族炭化水素基としては、フェニル基、ナフチル基、アントラニル基、フェナンスリル基、ターフェニル基等が挙げられる。
ここで、核炭素数が5~40のアリール基としては、例えば、フェニル基、ナフチル基、アントラニル基、フェナンスリル基、ピレニル基、コロニル基、ビフェニル基、ターフェニル基、ピローリル基、フリル基、チエニル基、ベンゾチエニル基、オキサジアゾリル基、ジフェニルアントラニル基、インドリル基、カルバゾリル基、ピリジル基、ベンゾキノリル基、フルオランテニル基、アセナフトフルオランテニル基、スチルベン基、ペリレニル基、クリセニル基、ピセニル基、トリフェニレニル基、ルビセニル基、ベンゾアントラセニル基、フェニルアントラニル基、ビスアントラセニル基等が挙げられ、ナフチル基、アントラニル基、クリセニル基、ピレニル基が好ましい。
発光層の膜厚は、好ましくは5~50nm、より好ましくは7~50nm、最も好ましくは10~50nmである。5nm未満では発光層形成が困難となり、色度の調整が困難となる恐れがあり、50nmを超えると駆動電圧が上昇する恐れがある。
正孔注入層及び正孔輸送層の材料としては、特に制限はなく、従来、光導伝材料において正孔の電荷輸送材料として慣用されているものや、有機EL素子の正孔注入層及び正孔輸送層に使用されている公知のものの中から任意のものを選択して用いることができる。
正孔注入層及び正孔輸送層は上述した化合物を、真空蒸着法、スピンコート法、キャスト法、LB法等の公知の方法により薄膜化することにより形成することができる。正孔注入層及び正孔輸送層の膜厚は特に制限はないが、通常は5nm~5μmである。正孔注入層及び正孔輸送層は上述した材料の一種又は二種以上からなる一層で構成されてもよいし、異なる化合物からなる複数の正孔注入層及び正孔輸送層を積層したものであってもよい。
電子輸送層は5nm~5μmの膜厚で適宜選ばれるが、特に膜厚が厚いとき、電圧上昇を避けるために、104~106V/cmの電界印加時に電子移動度が10-5cm2/Vs以上であることが好ましい。
Ar311は、置換もしくは無置換の核原子数6~60のアリール基、又は置換もしくは無置換の核原子数3~60のヘテロアリール基であり、Ar311’は、置換もしくは無置換の核原子数6~60のアリーレン基又は置換もしくは無置換の核原子数3~60のヘテロアリーレン基であり、Ar312は、水素原子、置換もしくは無置換の核原子数6~60のアリール基、置換もしくは無置換の核原子数3~60のヘテロアリール基、置換もしくは無置換の炭素数1~20のアルキル基、又は置換もしくは無置換の炭素数1~20のアルコキシ基である。ただし、Ar311及びAr312のいずれか一方は、置換もしくは無置換の核原子数10~60の縮合環基、又は置換もしくは無置換の核原子数3~60のモノヘテロ縮合環基である。
L311、L312及びL313は、それぞれ、単結合、置換もしくは無置換の核原子数6~60のアリーレン基、置換もしくは無置換の核原子数3~60のヘテロアリーレン基、又は置換もしくは無置換のフルオレニレン基である。
R及びR311は、それぞれ水素原子、置換もしくは無置換の核原子数6~60のアリール基、置換もしくは無置換の核原子数3~60のヘテロアリール基、置換もしくは無置換の炭素数1~20のアルキル基、又は置換もしくは無置換の炭素数1~20のアルコキシ基であり、nは0~5の整数であり、nが2以上の場合、複数のRは同一でも異なっていてもよく、また、隣接するR基同士で結合して、炭素環式脂肪族環又は炭素環式芳香族環を形成していてもよい。)で表される含窒素複素環誘導体。
(式中、HArは、置換基を有していてもよい炭素数3~40の含窒素複素環であり、L314は、単結合、置換基を有していてもよい炭素数6~60のアリーレン基、置換基を有していてもよい炭素数3~60のヘテロアリーレン基又は置換基を有していてもよいフルオレニレン基であり、Ar321は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基であり、Ar322は、置換基を有していてもよい炭素数6~60のアリール基又は置換基を有していてもよい炭素数3~60のヘテロアリール基である。)で表される含窒素複素環誘導体。
式(K)の配位子を形成する環A301及びA302の置換基の具体的な例を挙げると、塩素、臭素、ヨウ素、フッ素のハロゲン原子、メチル基、エチル基、プロピル基、ブチル基、s-ブチル基、t-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ステアリル基、トリクロロメチル基等の置換もしくは無置換のアルキル基、フェニル基、ナフチル基、ビフェニル基、アントラニル基、フェナントリル基、フルオレニル基、ピレニル基、3-メチルフェニル基、3-メトキシフェニル基、3-フルオロフェニル基、3-トリクロロメチルフェニル基、3-トリフルオロメチルフェニル基、3-ニトロフェニル基等の置換もしくは無置換のアリール基、メトキシ基、n-ブトキシ基、t-ブトキシ基、トリクロロメトキシ基、トリフルオロエトキシ基、ペンタフルオロプロポキシ基、2,2,3,3-テトラフルオロプロポキシ基、1,1,1,3,3,3-ヘキサフルオロ-2-プロポキシ基、6-(パーフルオロエチル)ヘキシルオキシ基等の置換もしくは無置換のアルコキシ基、フェノキシ基、p-ニトロフェノキシ基、p-t-ブチルフェノキシ基、3-フルオロフェノキシ基、ペンタフルオロフェノキシ基、3-トリフルオロメチルフェノキシ基等の置換もしくは無置換のアリールオキシ基、メチルチオ基、エチルチオ基、t-ブチルチオ基、ヘキシルチオ基、オクチルチオ基、トリフルオロメチルチオ基等の置換もしくは無置換のアルキルチオ基、フェニルチオ基、p-ニトロフェニルチオ基、p-t-ブチルフェニルチオ基、3-フルオロフェニルチオ基、ペンタフルオロフェニルチオ基、3-トリフルオロメチルフェニルチオ基等の置換もしくは無置換のアリールチオ基、シアノ基、ニトロ基、アミノ基、メチルアミノ基、ジメチルアミノ基、エチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジブチルアミノ基、ジフェニルアミノ基等のモノ又はジ置換アミノ基、ビス(アセトキシメチル)アミノ基、ビス(アセトキシエチル)アミノ基、ビス(アセトキシプロピル)アミノ基、ビス(アセトキシブチル)アミノ基等のアシルアミノ基、水酸基、シロキシ基、アシル基、カルバモイル基、メチルカルバモイル基、ジメチルカルバモイル基、エチルカルバモイル基、ジエチルカルバモイル基、プロイピルカルバモイル基、ブチルカルバモイル基、フェニルカルバモイル基等の置換もしくは無置換のカルバモイル基、カルボン酸基、スルフォン酸基、イミド基、シクロペンタン基、シクロヘキシル基等のシクロアルキル基、ピリジニル基、ピラジニル基、ピリミジニル基、ピリダジニル基、トリアジニル基、インドリニル基、キノリニル基、アクリジニル基、ピロリジニル基、ジオキサニル基、ピペリジニル基、モルフォリニル基、ピペラジニル基、カルバゾリル基、フリル基、チエニル基、オキサゾリル基、オキサジアゾリル基、ベンゾオキサゾリル基、チアゾリル基、チアジアゾリル基、ベンゾチアゾリル基、トリアゾリル基、イミダゾリル基、ベンゾイミダゾリル基等の複素環基等がある。また、以上の置換基同士が結合してさらなる6員アリール環もしくは複素環を形成してもよい。
発光層からの発光を陰極から取り出す場合、陰極の発光に対する透過率は10%より大きくすることが好ましい。また、陰極としてのシート抵抗は数百Ω/□以下が好ましく、さらに、膜厚は通常10nm~1μm、好ましくは50~200nmである。
絶縁層に用いる材料としては、例えば、酸化アルミニウム、弗化リチウム、酸化リチウム、弗化セシウム、酸化セシウム、酸化マグネシウム、弗化マグネシウム、酸化カルシウム、弗化カルシウム、窒化アルミニウム、酸化チタン、酸化珪素、酸化ゲルマニウム、窒化珪素、窒化ホウ素、酸化モリブデン、酸化ルテニウム、酸化バナジウム等が挙げられる。これらの混合物や積層物を用いてもよい。
まず、透光性基板上に、陽極材料からなる薄膜を蒸着法あるいはスパッタリング法により形成し、陽極とする。次に、この陽極上に正孔注入層を設ける。正孔注入層の形成は、真空蒸着法、スピンコート法、キャスト法、LB法等の方法により行うことができるが、均質な膜が得られやすく、かつピンホールが発生しにくい等の点から真空蒸着法により形成することが好ましい。真空蒸着法により正孔注入層を形成する場合、その蒸着条件は使用する化合物(正孔注入層の材料)、目的とする正孔注入層の構造等により異なるが、一般に蒸着源温度50~450℃、真空度10-7~10-3Torr、蒸着速度0.01~50nm/秒、基板温度-50~300℃で適宜選択することが好ましい。
そして、最後に陰極を積層して有機EL素子を得ることができる。陰極は蒸着法、スパッタリングにより形成できる。下地の有機物層を製膜時の損傷から守るためには真空蒸着法が好ましい。
以上の有機EL素子の作製は、一回の真空引きで、一貫して陽極から陰極まで作製することが好ましい。
[実施例]
(1)初期性能:輝度計(ミノルタ社製分光輝度放射計CS-1000)で10mA/cm2時の発光輝度値とCIE1931色度座標を測定し発光効率を求めた。
(2)寿命:1000cd/m2の初期輝度で定電流駆動し、輝度の半減期、及び色度の変化で評価した。
次いで、特開2007-77078に記載の方法に準じてハロゲン含有量の低減処理を行った(収量6.85g、HPLC純度99.9%、FD-MS:628.76)。
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、正孔注入層として膜厚60nmの下記の化合物A-1を成膜した。A-1膜の成膜に続けて、このA-1膜上に正孔輸送層として膜厚20nmの下記の化合物A-2を成膜した。
さらに、このA-2膜上に膜厚40nmで本発明の化合物H-1とジアミン誘導体D-1を40:2の膜厚比で成膜し青色系発光層とした。H-1はホスト、D-1はドーパントとして機能する。
この膜上に電子輸送層として膜厚20nmで下記の化合物Alq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発光素子を形成した。
実施例1において、H-1及び/又はD-1を表1に示す下記化合物に変えた他は、実施例1と同様に素子を作製し評価した。結果を表1及び表2に示す。
実施例1において、H-1及びD-1を表2の化合物に変えた他は、実施例1と同様に素子を作製し評価した。結果を表2に示す。
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 (7)
- 前記4環以上の縮合芳香族環が、ピレニル基、クリセニル基、ベンズフルオレニル基、ベンズクリセニル基、ジベンゾフルオレニル基又はトリフェニレニル基である請求項1に記載の化合物。
- 請求項1又は2記載の化合物からなる発光材料。
- 陽極及び陰極と、
前記陽極及び陰極の間に挟持されている、発光層を含む1以上の有機薄膜層とを有し、
前記有機薄膜層の少なくとも一層が、請求項1又は2記載の化合物を含有する有機エレクトロルミネッセンス素子。 - 前記化合物を含有する層が、さらに、りん光性ドーパント及び蛍光性ドーパントの少なくとも1つを含有する請求項4記載の有機エレクトロルミネッセンス素子。
- 前記蛍光性ドーパントが、アリールアミン化合物及びスチリルアミン化合物の少なくとも1つである請求項5記載の有機エレクトロルミネッセンス素子。
- 前記りん光性ドーパントが、金属錯体である請求項5又は6記載の有機エレクトロルミネッセンス素子。
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JP5635775B2 (ja) * | 2007-11-19 | 2014-12-03 | 出光興産株式会社 | モノベンゾクリセン誘導体、及びそれを含む有機エレクトロルミネッセンス素子用材料、並びにそれを用いた有機エレクトロルミネッセンス素子 |
WO2009069602A1 (ja) * | 2007-11-29 | 2009-06-04 | Idemitsu Kosan Co., Ltd. | ベンズアントラセン化合物及びそれを用いた有機エレクトロルミネッセンス素子 |
WO2009081774A1 (ja) * | 2007-12-20 | 2009-07-02 | Idemitsu Kosan Co., Ltd. | ベンズアントラセン化合物及びそれを用いた有機エレクトロルミネッセンス素子 |
PT2271938E (pt) * | 2008-04-11 | 2014-05-09 | Univ Texas | Método e aparelho de amplificação de quimiluminescênci electrogerada por nanopartículas |
KR101603356B1 (ko) * | 2008-05-08 | 2016-03-14 | 보드 오브 리전츠 오브 더 유니버시티 오브 텍사스 시스템 | 전기발생 화학발광에 사용되는 발광 나노구조 물질 |
CN102473857A (zh) | 2010-01-15 | 2012-05-23 | 出光兴产株式会社 | 有机电致发光元件 |
KR101885697B1 (ko) | 2011-06-28 | 2018-08-07 | 삼성디스플레이 주식회사 | 헤테로고리 화합물, 이를 포함한 유기 전계 발광 소자 및 상기 유기 전계 발광 소자를 포함하는 평판 표시 장치 |
US9922818B2 (en) * | 2014-06-16 | 2018-03-20 | Versum Materials Us, Llc | Alkyl-alkoxysilacyclic compounds |
KR101862711B1 (ko) * | 2015-05-29 | 2018-05-30 | 삼성에스디아이 주식회사 | 화합물, 유기막 조성물, 유기막, 및 패턴형성방법 |
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TW200932875A (en) | 2009-08-01 |
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