WO2010084729A1 - ピリジル基が連結したトリアゾール環構造を有する化合物および有機エレクトロルミネッセンス素子 - Google Patents
ピリジル基が連結したトリアゾール環構造を有する化合物および有機エレクトロルミネッセンス素子 Download PDFInfo
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- WO2010084729A1 WO2010084729A1 PCT/JP2010/000243 JP2010000243W WO2010084729A1 WO 2010084729 A1 WO2010084729 A1 WO 2010084729A1 JP 2010000243 W JP2010000243 W JP 2010000243W WO 2010084729 A1 WO2010084729 A1 WO 2010084729A1
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- 0 *c(c(*)c1*)c(*)c(*)c1-c1nc(-c2nnc(-c3cccc(-[n]4c(cccc5)c5c5c4cccc5)n3)[n]2-c2ccccc2)ccc1 Chemical compound *c(c(*)c1*)c(*)c(*)c1-c1nc(-c2nnc(-c3cccc(-[n]4c(cccc5)c5c5c4cccc5)n3)[n]2-c2ccccc2)ccc1 0.000 description 1
- IPCFOMILXCTVMT-UHFFFAOYSA-N Cc(cc1)cc2c1c(cccc1)c1[n]2-c1cc(-c2nnc(-c3nc(-c4ccccc4)ccc3)[n]2-c2ccccc2)nc(-c2cc(cc(C)cc3)c3cc2)c1 Chemical compound Cc(cc1)cc2c1c(cccc1)c1[n]2-c1cc(-c2nnc(-c3nc(-c4ccccc4)ccc3)[n]2-c2ccccc2)nc(-c2cc(cc(C)cc3)c3cc2)c1 IPCFOMILXCTVMT-UHFFFAOYSA-N 0.000 description 1
- YLAXVGKFEZTQTI-UHFFFAOYSA-N Cc(cc1C)cc(C)c1-[n]1c(-c2cc(-[n]3c4ccccc4c4c3cccc4)ncc2)nnc1-c1cc(-[n]2c3ccccc3c3c2cccc3)ncc1 Chemical compound Cc(cc1C)cc(C)c1-[n]1c(-c2cc(-[n]3c4ccccc4c4c3cccc4)ncc2)nnc1-c1cc(-[n]2c3ccccc3c3c2cccc3)ncc1 YLAXVGKFEZTQTI-UHFFFAOYSA-N 0.000 description 1
- KKOWGMXGLZJYLQ-UHFFFAOYSA-N Cc(cc1C)cc(C)c1-[n]1c(-c2cccc(-[n]3c(cccc4)c4c4c3cccc4)n2)nnc1-c1cc(-c2ccccc2)ccc1 Chemical compound Cc(cc1C)cc(C)c1-[n]1c(-c2cccc(-[n]3c(cccc4)c4c4c3cccc4)n2)nnc1-c1cc(-c2ccccc2)ccc1 KKOWGMXGLZJYLQ-UHFFFAOYSA-N 0.000 description 1
- CXAPXQZSFSJVEL-UHFFFAOYSA-N c(cc1)ccc1-c1cc(-c2nnc(-c3cccc(-[n]4c(cccc5)c5c5c4cccc5)n3)[n]2-c2ccccc2)ncc1 Chemical compound c(cc1)ccc1-c1cc(-c2nnc(-c3cccc(-[n]4c(cccc5)c5c5c4cccc5)n3)[n]2-c2ccccc2)ncc1 CXAPXQZSFSJVEL-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K50/00—Organic light-emitting devices
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- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/18—Carrier blocking layers
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H10K2101/10—Triplet emission
Definitions
- the present invention relates to a compound suitable for an organic electroluminescence element which is a self-luminous element suitable for various display devices and the element, and more specifically, has a triazole ring structure in which a pyridyl group substituted with a carbazolyl group is linked.
- the present invention relates to a compound and an organic electroluminescence device using the compound.
- the organic electroluminescence element is a self-luminous element, it has been actively researched because it is brighter and more visible than a liquid crystal element and has a clear display.
- the phosphorescent emitter Since the phosphorescent emitter causes concentration quenching, it is supported by doping the phosphorescent emitter with a charge transporting compound generally called a host compound.
- the supported phosphorescent emitter is called a guest compound.
- a host compound 4,4′-di (N-carbazolyl) biphenyl (hereinafter abbreviated as CBP) represented by the following formula has been generally used (for example, see Non-patent Document 1).
- TCTA N-carbazolyl triphenylamine
- TCBI which is a hole transporting host compound
- High-efficiency and low-voltage driving is achieved by using the TCTA as an electron blocking layer for confining triplet excitons as a light-emitting layer doped with a mixed host compound mixed with.
- TCTA as an electron blocking layer for confining triplet excitons as a light-emitting layer doped with a mixed host compound mixed with.
- blue phosphorescent emitter FIrpic represented by the following formula
- the external quantum efficiency of the phosphorescent light emitting device doped with CBP as a host compound of the light emitting layer is only 6%.
- the reason is that the triplet level of FIrpic is 2.62 eV, whereas the triplet level of CBP is as low as 2.56 eV, so that the trapping of triplet excitons by FIrpic is insufficient. it was thought.
- the excited triplet level of TCTA used as the electron blocking layer of the green phosphorescent light emitting device is 2.60 eV, which is still considered insufficient for confining FIrpic triplet excitons.
- a host compound of the light emitting layer that completely confines the triplet excitons of the phosphorescent light emitter is required.
- An object of the present invention is to provide a hole-blocking compound and a light emitting material having high excitation triplet levels and capable of completely confining triplet excitons of phosphorescent emitters as materials for highly efficient organic electroluminescence devices. It is an object of the present invention to provide a layer host compound, and to provide a high-efficiency, high-brightness organic electroluminescence device using this compound.
- the physical properties that the organic compound to be provided by the present invention should have include (1) high excitation triplet level, (2) bipolar transportability, and (3) stable thin film state. And can be used as a constituent material of an electron transport layer, a hole blocking layer, or a light emitting layer.
- the physical characteristics that the organic electroluminescence device to be provided by the present invention should have include (1) high luminous efficiency, (2) high emission luminance, and (3) low practical driving voltage. I can give you something.
- the present inventors say that the triazole ring structure linked to the pyridyl group has an electron transporting ability and that the carbazole structure has a hole transporting ability. Focusing on this, the compound is designed and chemically synthesized using the excited triplet level as an index, and is actually substituted with a novel carbazolyl group having characteristics suitable for phosphorescent devices by measuring the excited triplet level. In addition, a compound having a triazole ring structure in which pyridyl groups are linked was found. Then, various organic electroluminescence devices were prototyped using the compound, and the characteristics of the devices were intensively evaluated. As a result, the present invention was completed.
- the present invention is a compound having a triazole ring structure in which a pyridyl group substituted with a carbazolyl group represented by the following general formula (1) is connected, and comprising at least one organic layer sandwiched between a pair of electrodes.
- a compound having a triazole ring structure in which a pyridyl group substituted with a carbazolyl group represented by the following general formula (1) is connected is used as a constituent material of at least one organic layer It is an organic electroluminescent element characterized by these.
- Ar represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group
- R1 represents a substituted or unsubstituted aromatic group
- Substituted or unsubstituted aromatic hydrocarbon group "substituted or unsubstituted aromatic heterocyclic group” or “substituted or unsubstituted condensed polycyclic aromatic represented by Ar in the general formula (1)”
- aromatic hydrocarbon group “aromatic heterocyclic group”, or “fused polycyclic aromatic group” in the “group” include the following groups.
- substituted aromatic hydrocarbon group “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group” represented by Ar in the general formula (1), specifically Is a deuterium atom, fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, linear or branched alkyl group having 1 to 6 carbon atoms, alkoxy group, amino group, trifluoromethyl group, phenyl group , Biphenylyl group, terphenylyl group, naphthyl group, phenanthryl group, aralkyl group, fluorenyl group, indenyl group, pyridyl group, pyrimidyl group, furanyl group, pyronyl group, thiophenyl group, quinolyl group, benzofuranyl group, benzothiophenyl group, indolyl group , Carbazolyl group
- substituted or unsubstituted aromatic hydrocarbon group “substituted or unsubstituted aromatic heterocyclic group” or “substituted or Specific examples of the “aromatic hydrocarbon group”, “aromatic heterocyclic group” or “fused polycyclic aromatic group” in the “unsubstituted fused polycyclic aromatic group” include the following groups: it can.
- substituted aromatic hydrocarbon group “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group”
- substituted aromatic hydrocarbon group “substituted aromatic heterocyclic group” or “substituted condensed polycyclic aromatic group”
- substituents of the triazole group represented by R1 in the general formula (1) include a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, a nitro group, a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group, and an amino group.
- Trifluoromethyl group Trifluoromethyl group, phenyl group, biphenylyl group, terphenylyl group, naphthyl group, phenanthryl group, aralkyl group, fluorenyl group, indenyl group, pyridyl group, pyrimidyl group, furanyl group, pyronyl group, thiophenyl group, quinolyl group, benzofuranyl group , Benzothiophenyl group, indolyl group, carbazolyl group, carbolyl group, benzoxazolyl group, quinoxalyl group, ben Imidazolyl group, a pyrazolyl group, a dibenzofuranyl group, can be mentioned groups such as dibenzothiophenyl group, it may be further substituted.
- substituted or unsubstituted aromatic hydrocarbon group substituted or unsubstituted aromatic heterocyclic group
- aromatic hydrocarbon group substituted or unsubstituted aromatic heterocyclic group
- fused polycyclic aromatic group fused polycyclic aromatic group in the “substituted or unsubstituted condensed polycyclic aromatic group” include the following groups: be able to.
- substituted aromatic hydrocarbon group substituted aromatic heterocyclic group
- substituted condensed polycyclic aromatic group substituted condensed polycyclic aromatic group
- substituted or unsubstituted aromatic hydrocarbon group substituted or unsubstituted aromatic heterocyclic group
- aromatic hydrocarbon group substituted or unsubstituted aromatic heterocyclic group
- fused polycyclic aromatic group fused polycyclic aromatic group in the “substituted or unsubstituted condensed polycyclic aromatic group” include the following groups: be able to.
- substituted aromatic hydrocarbon group substituted aromatic heterocyclic group
- substituted condensed polycyclic aromatic group substituted condensed polycyclic aromatic group
- deuterium atom fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, linear or branched alkyl group having 1 to 6 carbon atoms, alkoxy group, Amino group, trifluoromethyl group, phenyl group, biphenylyl group, terphenylyl group, naphthyl group, phenanthryl group, aralkyl group, fluorenyl group, indenyl group, pyridyl group, pyrimidyl group, furanyl group, pyronyl group, thiophenyl group, quinolyl group, Benzofuranyl group, benzothiophen
- a compound having a triazole ring structure in which a pyridyl group substituted with a carbazolyl group, represented by the general formula (1) of the present invention is a novel compound, is an excited triplet level more than a conventional hole blocking layer material. Is high, has the ability to confine excellent triplet excitons, and is stable in a thin film state.
- a compound having a triazole ring structure represented by the general formula (1) of the present invention and having a pyridyl group substituted with a carbazolyl group linked to each other is transported by an electron in an organic electroluminescence device (hereinafter abbreviated as an organic EL device). It can be used as a constituent material of a layer, a hole blocking layer or a light emitting layer.
- an organic EL device organic electroluminescence device
- the compound having a triazole ring structure in which a pyridyl group substituted with a carbazolyl group of the present invention is linked is useful as a compound for an electron transport layer, a hole blocking compound, or a host compound for a light emitting layer of an organic EL device, By producing an organic EL element using the compound, an organic EL element having high efficiency, high luminance, and low driving voltage can be obtained.
- FIG. 1 is a 1H-NMR chart of the compound of Example 1 of the present invention (Compound 8).
- FIG. 6 is a diagram showing EL element configurations of Example 5 and Comparative Example 1.
- the compound having a triazole ring structure in which a pyridyl group substituted with a carbazolyl group of the present invention is linked is a novel compound.
- a halogenopyridyltriazole intermediate was synthesized by cyclization reaction of the corresponding acyl hydrazine with an arylamine in the presence of phosphorus trichloride, and further an Ullmann reaction with the corresponding carbazole or a palladium catalyst was used.
- a compound having a triazole ring structure in which a pyridyl group substituted with a carbazolyl group is linked by an amination reaction or the like can be synthesized.
- the melting point and glass transition point were measured using a powder and a high-sensitivity differential scanning calorimeter DSC3100S manufactured by Bruker AXS.
- the work function was measured using an atmospheric photoelectron spectrometer AC-3 manufactured by Riken Keiki Co., Ltd., by forming a 100 nm thin film on the ITO substrate.
- the work function is an index of hole transport ability and hole blocking ability.
- the excited triplet energy level of the compound of the present invention can be calculated from the measured phosphorescence spectrum.
- the phosphorescence spectrum can be measured using a commercially available spectrophotometer.
- As a general phosphorescence spectrum measurement method it is dissolved in a solvent and irradiated with excitation light at a low temperature (for example, see Non-Patent Document 6), or vapor deposited on a silicon substrate to form a thin film at a low temperature.
- a method of irradiating excitation light and measuring a phosphorescence spectrum see, for example, Patent Document 1).
- the excited triplet level can be calculated by reading the wavelength of the first peak on the short wavelength side of the phosphorescence spectrum or the wavelength of the rising position on the short wavelength side and converting it to the light energy value according to the following equation.
- the excited triplet level is an indicator of the confinement of triplet excitons in the phosphorescent emitter.
- E is the value of light energy
- h Planck's constant (6.63 ⁇ 10 ⁇ 34 Js)
- c is the speed of light (3.00 ⁇ 10 8 m / s)
- ⁇ is the short wavelength of the phosphorescence spectrum. It represents the wavelength (nm) where the side rises.
- 1 eV becomes 1.60 ⁇ 10 ⁇ 19 J.
- an anode As the structure of the organic EL device of the present invention, on the substrate sequentially, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, a cathode, Further, there may be mentioned those having an electron injection layer between the electron transport layer and the cathode.
- an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode can be sequentially formed on the substrate.
- the light emitting layer, the hole transport layer, and the electron transport layer may have a structure in which two or more layers are stacked.
- the material usually used for the layer is further doped with trisbromophenylamine hexachloroantimony, or N, N′-diphenyl-N, N ′
- TPD trisbromophenylamine hexachloroantimony
- a material usually used for the layer and further doped with a metal such as cesium can be used.
- an electrode material having a large work function such as ITO or gold is used.
- a material such as a naphthalene diamine derivative or a starburst type triphenylamine derivative or a coating type material can be used for the hole injection layer.
- TPD in addition to a compound containing m-carbazolylphenyl group, TPD, N, N′-diphenyl-N, N′-di ( ⁇ -naphthyl) benzidine (abbreviated as NPD) Bis [N, N-di (p-tolyl) -4-aminophenyl] cyclohexane (abbreviated as TPAC) can be used.
- NPD N, N′-diphenyl-N, N′-di ( ⁇ -naphthyl) benzidine
- TPAC Bis [N, N-di (p-tolyl) -4-aminophenyl] cyclohexane
- TCTA 9,9-bis [4- (carbazol-9-yl) phenyl] fluorene, 1,3-bis (carbazol-9-yl) benzene
- a carbazole derivative such as 9- [4- (carbazol-9-yl) phenyl] -9- [4- (triphenylsilyl) phenyl] -9H-fluorene
- a compound having an electron blocking action such as a compound having a triarylamine structure can be used.
- the light emitting layer of the organic EL device of the present invention is produced by doping a hole injecting / transporting host material with a light emitter called a guest material.
- a compound having a triazole ring structure in which a pyridyl group substituted with a carbazolyl group represented by the general formula (1) of the present invention is connected, and TPBI exhibiting electron transporting properties can be used as a host material of the light emitting layer.
- the guest material used for the light emitting layer of the organic EL device of the present invention may be a fluorescent light emitter or a phosphorescent light emitter.
- a fluorescent light emitter such as a rubrene derivative, anthracene derivative, or coumarin derivative can be used.
- a green phosphorescent body such as an iridium complex Ir (ppy) 3 of phenylpyridine, a blue phosphorescent body such as FIrpic or FIr6, or a red phosphorescent body such as Btp2Ir (acac) should be used. Can do.
- the guest material which is a phosphorescent material causes concentration quenching, it is preferably doped by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light emitting layer.
- an element having a structure in which a light-emitting layer manufactured using a compound having a different work function as a host material is stacked adjacent to a light-emitting layer manufactured using the compound of the present invention can be manufactured (for example, non-patented). Reference 7).
- compounds having a hole blocking action such as aluminum (III) bis (2-methyl-8-quinolinate) -4-phenylphenolate (hereinafter abbreviated as BAlq), oxazole derivatives and triazole derivatives are used.
- a compound having a triazole ring structure in which a pyridyl group substituted with a carbazolyl group represented by the general formula (1) of the present invention is connected, an oxadiazole derivative, a triazole derivative Tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq) and BAlq, which are aluminum complexes of quinoline, are used.
- the electron injection layer of the organic EL device of the present invention includes, for example, lithium fluoride, but this can be omitted in the preferred selection of the electron transport layer and the cathode.
- an electrode material having a low work function such as aluminum or an alloy of magnesium and silver is used.
- the reaction vessel purged with argon was charged with 2.9 g of 3,5-bis (6-bromopyridin-2-yl) -4-phenyl- [1,2,4] triazole, 2.3 g of carbazole, and 0.2 g of copper powder. Then, 2.6 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide and 25 ml of 1,2-dichlorobenzene were added and heated, followed by stirring at 150 ° C. for 7 hours. The mixture was cooled to room temperature, 200 ml of chloroform was added, insoluble matters were removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product.
- the compound of the present invention exhibits a glass transition point of 100 ° C. or higher and is stable in a thin film state.
- the compound of the present invention has a suitable energy level as compared with CBP generally used as a host compound in the light emitting layer.
- a 1.0 ⁇ 10 ⁇ 5 mol / L 2-methyltetrahydrofuran solution was prepared for the compound of the present invention.
- the prepared solution was put into a dedicated quartz tube, pure oxygen was passed through to remove oxygen, and a septum rubber stopper was used to prevent further oxygen contamination.
- a phosphorescence spectrum was measured by irradiating excitation light using a fluorescent phosphorescence spectrophotometer (manufactured by Horiba, Ltd., FluoroMax-4 type). The wavelength at the rising position on the short wavelength side of the phosphorescence spectrum was read, and the excited triplet level was calculated by converting the wavelength value into light energy.
- Excited triplet level Compound of Example 1 of the invention 3.02 eV CBP 2.56eV FIrpic 2.62eV
- the compound of the present invention has a value larger than the triplet energy of commonly used blue phosphorescent materials such as FIrpic and CBP, and sufficiently confines the triplet energy excited in the light emitting layer. Has the ability.
- the organic EL element has a hole transport layer 3, an electron blocking layer 4, a light emitting layer 5, and an electron transport layer 6 on a glass substrate 1 on which an ITO electrode is previously formed as a transparent electrode 2.
- the electron injection layer 7 and the cathode (aluminum electrode) 8 were deposited in this order.
- the glass substrate 1 having a 150 nm-thick ITO film formed thereon was washed with an organic solvent, the surface was washed by oxygen plasma treatment. Then, this glass substrate with an ITO electrode was mounted in a vacuum vapor deposition machine and the pressure was reduced to 0.001 Pa or less.
- NPD was formed as a hole transport layer 3 so as to cover the transparent electrode 2 so as to have a film thickness of 40 nm at a deposition rate of 1.0 cm / sec.
- mCP was formed as an electron blocking layer 4 so as to have a film thickness of 10 nm at a deposition rate of 1.0 cm / sec.
- the TPBI was formed as the electron transport layer 6 so as to have a film thickness of 45 nm at a deposition rate of 1.0 ⁇ / sec.
- lithium fluoride was formed as the electron injection layer 7 so as to have a film thickness of 0.5 nm at a deposition rate of 0.1 ⁇ / sec. Finally, aluminum was deposited to a thickness of 150 nm to form the cathode 8. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
- Table 1 summarizes the measurement results of the light emission characteristics when a DC voltage was applied to the organic EL device produced using the compound of Example 1 (Compound 8) of the present invention.
- An organic EL element was produced under the same conditions as in Example 5 except that the above was formed. About the produced organic EL element, the characteristic measurement was performed at normal temperature in air
- the compound of the present invention has a high excited triplet level, transfers energy well to the phosphorescent emitter, completely confines the triplet excitons of the phosphorescent emitter, and the host compound of the emitting layer It can be said that it is excellent as.
- the compound having a triazole ring structure in which a pyridyl group substituted with a carbazolyl group of the present invention is linked has (1) high excited triplet level, (2) bipolar transportability, and (3) stable thin film state. And can be used as a constituent material of an electron transport layer, a hole blocking layer, or a light emitting layer.
- an organic EL element using the compound, the luminance and light emission efficiency of the conventional organic EL element can be remarkably improved, and thus the performance of the mobile electronic product can be improved.
Abstract
Description
1993年にプリンストン大学のM.A.Baldoらは、イリジウム錯体を用いた燐光発光素子によって8%の外部量子効率を実現させた。
窒素置換した反応容器に、アニリン14.6mlと予め脱水した1,2-ジクロロベンゼン180mlを加え、室温にて、三塩化リン2.87mlを滴下した後、100℃まで加熱して2時間撹拌した。50℃以下まで冷却した後、6-ブロモピリジン-2-カルボン酸-N’-(6-ブロモピリジン-2-カルボニル)ヒドラジド11.0gを加え、165℃まで加熱して7時間攪拌した。反応溶液を50℃まで冷却した後、水を加え、さらに1時間撹拌した。反応溶液をクロロホルムで抽出し、有機層を炭酸カリウム水溶液で洗浄した後、硫酸マグネシウムで乾燥し、減圧下濃縮した。得られた固形物をカラムクロマトグラフ(担体:シリカゲル、溶離液:クロロホルム/ヘキサン=3/7、v/v)で精製することによって、3,5-ビス(6-ブロモピリジン-2-イル)-4-フェニル-[1,2,4]トリアゾール2.9g(収率23%)の白色粉体を得た。
融点 ガラス転移点
本発明実施例1の化合物 313℃ 117℃
仕事関数
本発明実施例1の化合物 5.75eV
CBP 6.00eV
励起三重項レベル
本発明実施例1の化合物 3.02eV
CBP 2.56eV
FIrpic 2.62eV
比較のために、実施例5における発光層5として前記TPBIと青色燐光発光体FIrpicを、蒸着速度比がTPBI:FIrpic=91:9となる蒸着速度で二元蒸着を行い、膜厚20nmとなるように形成した以外は実施例5と同様の条件で有機EL素子を作製した。作製した有機EL素子について、大気中、常温で特性測定を行なった。
作製した有機EL素子に直流電圧を印加したときの発光特性の測定結果を表1にまとめて示した。
2 透明電極
3 正孔輸送層
4 電子阻止層
5 発光層
6 電子輸送層
7 電子注入層
8 陰極
Claims (9)
- 下記一般式(1)で表される置換されたピリジル基が連結したトリアゾール環構造を有する化合物。
(式中、Arは置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基または置換もしくは無置換の縮合多環芳香族基を表し、R1は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基または置換もしくは無置換の縮合多環芳香族基を表し、R2、R3、R4、R5およびR6は、それらのうちの2つがトリアゾール環またはカルバゾリル基との連結基であり、他は同一でも異なってもよく水素原子、重水素原子、フッ素原子、シアノ基、炭素原子数1ないし6の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基または置換もしくは無置換の縮合多環芳香族基を表し、R7、R8、R9、R10、R11、R12、R13およびR14は、同一でも異なってもよく水素原子、重水素原子、フッ素原子、シアノ基、炭素原子数1ないし6の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基または置換もしくは無置換の縮合多環芳香族基を表し、mは0または1を表し、nは1または2の整数を表す。ただし、mとnの和は2であるものとする。) - 前記一般式(1)においてm=1、n=1である、請求項1記載のトリアゾール環構造を有する化合物。
- 前記一般式(1)においてm=0、n=2である、請求項1記載のトリアゾール環構造を有する化合物。
- 一対の電極とその間に挟まれた少なくとも一層の有機層を有する有機エレクトロルミネッセンス素子において、下記一般式(1)で表される置換されたピリジル基が連結したトリアゾール環構造を有する化合物が、少なくとも1つの有機層の構成材料として用いられていることを特徴とする有機エレクトロルミネッセンス素子。
(式中、Arは置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基または置換もしくは無置換の縮合多環芳香族基を表し、R1は置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基または置換もしくは無置換の縮合多環芳香族基を表し、R2、R3、R4、R5およびR6は、それらのうちの2つがトリアゾール環またはカルバゾリル基との連結基であり、他は同一でも異なってもよく水素原子、重水素原子、フッ素原子、シアノ基、炭素原子数1ないし6の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基または置換もしくは無置換の縮合多環芳香族基を表し、R7、R8、R9、R10、R11、R12、R13およびR14は、同一でも異なってもよく水素原子、重水素原子、フッ素原子、シアノ基、炭素原子数1ないし6の直鎖状もしくは分岐状のアルキル基、置換もしくは無置換の芳香族炭化水素基、置換もしくは無置換の芳香族複素環基または置換もしくは無置換の縮合多環芳香族基を表し、mは0または1を表し、nは1または2の整数を表す。ただし、mとnの和は2であるものとする。) - 前記一般式(1)においてm=1、n=1である、請求項4記載の有機エレクトロルミネッセンス素子。
- 前記一般式(1)においてm=0、n=2である、請求項4記載の有機エレクトロルミネッセンス素子。
- 前記有機層が電子輸送層であって、該電子輸送中に、前記一般式(1)で表される化合物が、少なくとも一つの構成材料として用いられていることを特徴とする請求項4記載の有機エレクトロルミネッセンス素子。
- 前記有機層が正孔阻止層であって、該正孔阻止層中に、前記一般式(1)で表される化合物が、少なくとも一つの構成材料として用いられていることを特徴とする請求項4記載の有機エレクトロルミネッセンス素子。
- 前記有機層が発光層であって、該発光層中に、前記一般式(1)で表される化合物が、少なくとも一つの構成材料として用いられていることを特徴とする請求項4記載の有機エレクトロルミネッセンス素子。
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US13/138,184 US20110272679A1 (en) | 2009-01-22 | 2010-01-19 | Compound having triazole ring structure to which pyridyl group is bonded, and organic electroluminescent device |
EP10733337A EP2380888A4 (en) | 2009-01-22 | 2010-01-19 | COMPOUND HAVING A TRIAZOLE CORE STRUCTURE WITH A PYRIDYL GROUP ATTACHED THERETO, AND ORGANIC ELECTROLUMINESCENT ELEMENT |
CN201080005323XA CN102292327A (zh) | 2009-01-22 | 2010-01-19 | 具有连接有吡啶基的三唑环结构的化合物以及有机电致发光器件 |
JP2010547431A JPWO2010084729A1 (ja) | 2009-01-22 | 2010-01-19 | ピリジル基が連結したトリアゾール環構造を有する化合物および有機エレクトロルミネッセンス素子 |
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EP (1) | EP2380888A4 (ja) |
JP (1) | JPWO2010084729A1 (ja) |
KR (1) | KR20110116184A (ja) |
CN (1) | CN102292327A (ja) |
TW (1) | TW201035075A (ja) |
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Cited By (7)
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WO2004092442A1 (de) | 2003-04-15 | 2004-10-28 | Hahn-Meitner-Institut Berlin Gmbh | Elektrochemisches verfahren zur direkten nanostrukturierbaren materialabscheidung auf einem substrat und mit dem verfahren hergestelltes halbleiterbauelement |
CN102911162A (zh) * | 2011-08-05 | 2013-02-06 | 财团法人工业技术研究院 | 有机化合物及包含其的有机电激发光装置 |
JP2013033958A (ja) * | 2011-07-06 | 2013-02-14 | Semiconductor Energy Lab Co Ltd | 発光素子、発光装置、表示装置、照明装置及び電子機器 |
EP2489664A4 (en) * | 2009-10-16 | 2013-04-03 | Idemitsu Kosan Co | AROMATIC COMPOUND CONTAINING FLUORENE, MATERIAL FOR ORGANIC ELECTROLUMINESCENCE ELEMENT, AND ORGANIC ELECTROLUMINESCENT ELEMENT USING SUCH MATERIAL |
US9178164B2 (en) | 2011-08-05 | 2015-11-03 | Industrial Technology Research Institute | Organic compound and organic electroluminescent device employing the same |
JP2017503347A (ja) * | 2013-12-27 | 2017-01-26 | ドゥーサン コーポレイション | 有機電界発光素子 |
KR20180121852A (ko) * | 2012-08-03 | 2018-11-09 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 발광 소자 |
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CN101506207B (zh) * | 2006-08-18 | 2013-11-13 | 保土谷化学工业株式会社 | 具有其上连结有取代的吡啶基的吡啶并吲哚环结构的化合物和有机电致发光器件 |
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- 2010-01-19 KR KR1020117019339A patent/KR20110116184A/ko not_active Application Discontinuation
- 2010-01-19 US US13/138,184 patent/US20110272679A1/en not_active Abandoned
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- 2010-01-19 CN CN201080005323XA patent/CN102292327A/zh active Pending
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WO2004092442A1 (de) | 2003-04-15 | 2004-10-28 | Hahn-Meitner-Institut Berlin Gmbh | Elektrochemisches verfahren zur direkten nanostrukturierbaren materialabscheidung auf einem substrat und mit dem verfahren hergestelltes halbleiterbauelement |
EP2489664A4 (en) * | 2009-10-16 | 2013-04-03 | Idemitsu Kosan Co | AROMATIC COMPOUND CONTAINING FLUORENE, MATERIAL FOR ORGANIC ELECTROLUMINESCENCE ELEMENT, AND ORGANIC ELECTROLUMINESCENT ELEMENT USING SUCH MATERIAL |
US9266851B2 (en) | 2009-10-16 | 2016-02-23 | Idemitsu Kosan Co., Ltd. | Fluorene-containing aromatic compound, material for organic electroluminescent element, and organic electroluminescent element using same |
JP2013033958A (ja) * | 2011-07-06 | 2013-02-14 | Semiconductor Energy Lab Co Ltd | 発光素子、発光装置、表示装置、照明装置及び電子機器 |
CN102911162A (zh) * | 2011-08-05 | 2013-02-06 | 财团法人工业技术研究院 | 有机化合物及包含其的有机电激发光装置 |
US9178164B2 (en) | 2011-08-05 | 2015-11-03 | Industrial Technology Research Institute | Organic compound and organic electroluminescent device employing the same |
US10644254B2 (en) | 2012-08-03 | 2020-05-05 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element |
KR20180121852A (ko) * | 2012-08-03 | 2018-11-09 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 발광 소자 |
US10505132B2 (en) | 2012-08-03 | 2019-12-10 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element |
US10734594B2 (en) | 2012-08-03 | 2020-08-04 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element |
KR102207668B1 (ko) * | 2012-08-03 | 2021-01-25 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 발광 소자 |
US11355722B2 (en) | 2012-08-03 | 2022-06-07 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element |
US11730007B2 (en) | 2012-08-03 | 2023-08-15 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element |
JP2017503347A (ja) * | 2013-12-27 | 2017-01-26 | ドゥーサン コーポレイション | 有機電界発光素子 |
Also Published As
Publication number | Publication date |
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EP2380888A1 (en) | 2011-10-26 |
EP2380888A4 (en) | 2012-09-19 |
KR20110116184A (ko) | 2011-10-25 |
JPWO2010084729A1 (ja) | 2012-07-12 |
TW201035075A (en) | 2010-10-01 |
US20110272679A1 (en) | 2011-11-10 |
CN102292327A (zh) | 2011-12-21 |
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