WO2020109927A1 - Elデバイス用組成物 - Google Patents
Elデバイス用組成物 Download PDFInfo
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- WO2020109927A1 WO2020109927A1 PCT/IB2019/059953 IB2019059953W WO2020109927A1 WO 2020109927 A1 WO2020109927 A1 WO 2020109927A1 IB 2019059953 W IB2019059953 W IB 2019059953W WO 2020109927 A1 WO2020109927 A1 WO 2020109927A1
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- C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
- C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
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- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
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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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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
Definitions
- One aspect of the present invention relates to a composition for an EL device.
- the technical field of one embodiment of the invention disclosed in this specification and the like relates to an object, a method, or a manufacturing method.
- one embodiment of the present invention relates to a process, a machine, a manufacture, or a composition (composition of matter). Therefore, more specifically, as technical fields of one embodiment of the present invention disclosed in this specification, a semiconductor device, a display device, a liquid crystal display device, a light-emitting device, a lighting device, a power storage device, a memory device, an imaging device, and the like.
- a driving method or a manufacturing method thereof can be given as an example.
- An EL device (organic EL device) utilizing electroluminescence (EL) using an organic compound has been put into practical use.
- the basic configuration of these EL devices is one in which an organic compound layer (EL layer) containing a light emitting material is sandwiched between a pair of electrodes. Light is emitted from the light-emitting material by applying a voltage to this device, injecting carriers, and utilizing recombination energy of the carriers.
- Such an EL device is a self-luminous type, when it is used as a pixel of a display, it has advantages such as higher visibility than a liquid crystal and no need for a backlight, and is suitable as a flat panel display element.
- a display using such an EL device has a great advantage that it can be manufactured to be thin and lightweight. Another feature is that the response speed is very fast.
- these EL devices can continuously form a light emitting layer in a two-dimensional manner, it is possible to obtain planar light emission. This is a feature that is difficult to obtain with a point light source typified by an incandescent lamp or an LED, or a line light source typified by a fluorescent lamp, and is therefore highly useful as a surface light source applicable to lighting or the like.
- Such an EL device is manufactured by a wet method typified by an inkjet method, a dry method typified by a vapor deposition method, or the like, but it is easy to realize high definition and easily prolong the life. For these reasons, the production method by the vapor deposition method is currently the mainstream.
- a light emitting layer is formed by co-evaporating at least two kinds of substances, an emission center substance and a host material.
- Co-evaporation is an evaporation method in which different substances are simultaneously evaporated from different evaporation sources.
- three or more kinds of substances are co-evaporated. ..
- An aspect of the present invention is to provide a composition for a novel EL device. Alternatively, it is an object of one embodiment of the present invention to provide an EL device composition capable of easily manufacturing an EL device having stable characteristics. Alternatively, it is an object of one embodiment of the present invention to provide a composition for an EL device capable of manufacturing an EL device having stable characteristics at low cost.
- the present invention should solve any one of the above problems.
- One aspect of the present invention is a composition for an EL device containing at least two or more kinds of organic compounds, which is 5% measured by thermogravimetric measurement between the two or more kinds of organic compounds under a pressure of 0.1 Pa or less.
- the composition for an EL device has a difference in weight reduction temperature of 50 degrees or less.
- another embodiment of the present invention is a composition for an EL device, which comprises a first organic compound and a second organic compound, the first organic compound and the second organic compound.
- a composition for EL devices in which the difference in 5% weight loss temperature measured by thermogravimetry under a pressure of 0.1 Pa or less is 50 degrees or less.
- another embodiment of the present invention is the composition for an EL device having the above structure, in which the first organic compound has an electron-transporting property and the second organic compound has a hole-transporting property.
- another embodiment of the present invention is the composition for an EL device in the above structure, in which the first organic compound has a benzophlodiazine skeleton or a benzothiodiazine skeleton.
- the first organic compound is any one of a naphthoflopyrazine skeleton, a phenanthropyrazine skeleton, a naphthothiopyrazine skeleton, and a phenanthrothiopyrazine skeleton.
- composition for an EL device having the above structure in which the first organic compound is represented by the following general formula (G1).
- Q represents oxygen or sulfur.
- Ar 1 represents a substituted or unsubstituted fused aromatic ring.
- One of R 1 and R 2 represents hydrogen and the other represents a group having a total carbon number of 1 to 100 having a hole-transporting skeleton.
- composition for an EL device having the above structure in which the first organic compound is represented by the following structural formula (100).
- another embodiment of the present invention is the composition for an EL device in the above structure, wherein the first organic compound has a benzofuropyrimidine skeleton or a benzothiopyrimidine skeleton.
- composition for an EL device having the above structure in which the first organic compound is represented by the following general formula (G2).
- Q represents oxygen or sulfur.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon ring, and the substituent of the aromatic hydrocarbon ring is an alkyl group having 1 to 6 carbon atoms, Or an alkoxy group having 1 to 6 carbon atoms, a monocyclic saturated hydrocarbon group having 5 to 7 carbon atoms, a polycyclic saturated hydrocarbon group having 7 to 10 carbon atoms, or a cyano group, The number of carbon atoms forming the aromatic hydrocarbon ring is 6 or more and 25 or less. Further, m and n are 0 or 1, respectively.
- A is a group having 12 to 100 total carbon atoms, and is a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, a triphenylene ring, a heteroaromatic ring containing a dibenzothiophene ring, a heteroaromatic ring containing a dibenzofuran ring, or carbazole. It has one or more of a heteroaromatic ring containing a ring, a benzimidazole ring, and a triphenylamine structure.
- R 1 is hydrogen, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted monocyclic saturated hydrocarbon having 5 to 7 carbon atoms, a substituted or unsubstituted polycyclic saturated hydrocarbon having 7 to 10 carbon atoms It represents a hydrocarbon, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.
- another embodiment of the present invention is a composition for an EL device, in which the first organic compound is represented by the following structural formula (200) or the following structural formula (201).
- another embodiment of the present invention is the composition for an EL device having the above structure, in which the second organic compound has an aromatic amine skeleton.
- another embodiment of the present invention is the composition for an EL device having the above structure, in which the second organic compound has a carbazole skeleton.
- another embodiment of the present invention is the composition for an EL device having the above structure, in which the second organic compound has a triarylamine skeleton.
- another embodiment of the present invention is the composition for an EL device having the above structure, in which the second organic compound has a bicarbazole skeleton.
- another embodiment of the present invention is the composition for an EL device in which, in the above structure, the bicarbazole skeleton has two carbazolyl groups bonded to each other at any of the 2-position to the 4-position.
- another embodiment of the present invention is the composition for an EL device having the above structure, in which the second organic compound has a triarylamine skeleton and a carbazole skeleton.
- another embodiment of the present invention is the composition for an EL device in the above structure, wherein the nitrogen atom in the triarylamine and the carbazole skeleton are bonded via a phenylene group.
- another embodiment of the present invention is the composition for an EL device having the above structure, in which the carbazole skeleton is bonded at the 2nd to 4th or 9th position.
- another embodiment of the present invention is the composition for an EL device in the above structure, wherein the second organic compound has at least one fluorene skeleton.
- composition for an EL device which is a combination of the first organic compound and the second organic compound forming an exciplex in the above structure.
- another embodiment of the present invention is the composition for an EL device according to the above structure, wherein the difference between the 5% weight loss temperatures is 40 degrees or less.
- another embodiment of the present invention is the composition for an EL device, wherein the difference in the 5% weight loss temperature is 30 degrees or less in the above structure.
- the light emitting device in this specification includes an image display device using an EL device.
- a connector such as an anisotropic conductive film or TCP (Tape Carrier Package) is attached to the EL device, a module in which a printed wiring board is provided in front of the TCP, or a COG (Chip On Glass) method for the EL device.
- the light emitting device may include a module in which an IC (integrated circuit) is directly mounted. Further, the lighting equipment or the like may have a light emitting device.
- a novel EL device composition can be provided.
- an EL device composition which can easily manufacture an EL device having stable characteristics can be provided.
- an EL device composition capable of inexpensively producing an EL device having stable characteristics can be provided.
- FIGS. 1A to 1C are schematic diagrams of EL devices.
- 2A and 2B are conceptual diagrams of an active matrix light emitting device.
- 3A and 3B are conceptual diagrams of an active matrix light emitting device.
- FIG. 4 is a conceptual diagram of an active matrix light emitting device.
- 5A and 5B are conceptual diagrams of a passive matrix light emitting device.
- 6A and 6B are diagrams showing a lighting device.
- 7A, 7B1, 7B2, and 7C are diagrams showing electronic devices.
- 8A to 8C are diagrams showing electronic devices.
- FIG. 9 is a diagram illustrating a lighting device.
- FIG. 10 is a diagram showing a lighting device.
- FIG. 11 is a diagram showing an in-vehicle display device and a lighting device.
- FIG. 12A and 12B are diagrams illustrating electronic devices.
- 13A to 13C are diagrams showing electronic devices.
- 14A and 14B are schematic diagrams of a vapor deposition device.
- FIG. 15 is a diagram showing the luminance-current density characteristics of the EL device 1.
- FIG. 16 is a diagram showing the luminance-voltage characteristics of the EL device 1.
- FIG. 17 is a diagram showing current-voltage characteristics of the EL device 1.
- FIG. 18 is a diagram showing the external quantum efficiency-luminance characteristic of the EL device 1.
- FIG. 19 is a diagram showing an emission spectrum of the EL device 1.
- FIG. 20 is a diagram showing the luminance-current density characteristics of the EL device 2.
- FIG. 21 is a diagram showing the luminance-voltage characteristics of the EL device 2.
- FIG. 15 is a diagram showing the luminance-current density characteristics of the EL device 1.
- FIG. 16 is a diagram showing the luminance-voltage characteristics of the EL device 1.
- FIG. 22 is a diagram showing the current-voltage characteristics of the EL device 2.
- FIG. 23 is a diagram showing the external quantum efficiency-luminance characteristic of the EL device 2.
- FIG. 24 is a diagram showing an emission spectrum of the EL device 2.
- FIG. 25 is a diagram showing the luminance-current density characteristics of the EL device 3.
- FIG. 26 is a diagram showing the luminance-voltage characteristics of the EL device 3.
- FIG. 27 is a diagram showing current-voltage characteristics of the EL device 3.
- FIG. 28 is a diagram showing the external quantum efficiency-luminance characteristic of the EL device 3.
- FIG. 29 is a diagram showing an emission spectrum of the EL device 3.
- FIG. 30 is a diagram showing the luminance-time change characteristic of the EL device 1.
- FIG. 30 is a diagram showing the luminance-time change characteristic of the EL device 1.
- FIG. 31 is a diagram showing the luminance-time change characteristic of the EL device 2.
- FIG. 32 is a diagram showing the luminance-time change characteristic of the EL device 3.
- FIG. 33 is a diagram showing the luminance-current density characteristics of the EL device 4.
- FIG. 34 is a diagram showing the luminance-voltage characteristics of the EL device 4.
- FIG. 35 is a diagram showing current-voltage characteristics of the EL device 4.
- FIG. 36 is a diagram showing the external quantum efficiency-luminance characteristic of the EL device 4.
- FIG. 37 is a diagram showing an emission spectrum of the EL device 4.
- FIG. 38 is a diagram showing the luminance-time change characteristic of the EL device 4.
- FIG. 39 is a diagram showing the luminance-time change characteristic of the EL device 2 at high temperature.
- An organic EL device is usually formed by sandwiching an EL layer containing an organic compound between a pair of electrodes.
- the EL layer has a laminated structure in which the functions are separated.
- the laminated structure is, for example, a hole injection layer 111, a hole transport layer 112, a light emitting layer 113, an electron transport layer 114, an electron injection layer 115, a carrier block layer, like the EL layer 103 shown in FIG. 1A. It is composed of functional layers such as a charge generation layer.
- Each functional layer may be a layer made of a single substance or a layer in which a plurality of substances are mixed.
- the light emitting layer 113 often has a host-guest structure in order to suppress the quenching phenomenon due to the interference between excitons and to adjust the position of the light emitting region.
- the structure of the light emitting layer 113 is further developed from the above-described host-guest type, and is composed of three or more substances such as a host, an assist, and a guest, in response to a demand for an EL device that is more efficient and has a long life.
- the structure to be used is beginning to be put to practical use.
- the types of substances that can be mixed in one light emitting layer depend on the number of vapor deposition sources of the apparatus, and some investment is required to add vapor deposition sources.
- FIG. 14 is a schematic diagram when forming a layer in which three kinds of substances (compound 1, compound 2, and dopant) are mixed by vapor deposition. Since FIG. 14A shows a case where three kinds of substances are vapor-deposited from different vapor deposition sources, three vapor deposition sources are required. On the other hand, FIG. 14B shows a case where a composition in which two kinds of substances (compound 1 and compound 2) are mixed in advance is evaporated from one evaporation source. The evaporation source is enough. However, since the substance has its own vaporization temperature and sublimation temperature, it is difficult to form a layer with the target composition to the target film thickness, even if the film is formed using the materials that have been mixed in advance. Is.
- the method needs to be able to provide an EL device without characteristic fluctuation. is there.
- the evaporation temperature and sublimation temperature of a substance have unique values for each substance.
- a large amount of substances having lower temperatures may fly, and the composition of the substances inside the vapor deposition source may gradually change.
- the composition of the sample inside the vapor deposition source changes, the composition of the film changes with each repeated vapor deposition, resulting in a change in the characteristics of the EL device.
- the present inventors have investigated a composition for an EL device in which different substances are mixed in advance, and the composition of the EL device does not change even if repeated vapor deposition is performed using the composition. ..
- the composition for an EL device in which the difference in 5% weight loss temperature of the contained substances is 50° C. or less is unlikely to cause a composition change even during repeated vapor deposition, and the composition concerned. It was found that the characteristics of an EL device manufactured by using a material are unlikely to change significantly.
- one aspect of the present invention is a composition for an EL device containing at least two or more kinds of organic compounds, which is measured by thermogravimetric measurement between the two or more kinds of organic compounds under a pressure of 0.1 Pa or less.
- the composition for an EL device has a difference in 5% weight loss temperature of 50 degrees or less.
- the 5% weight loss temperature can be determined by performing a thermogravimetric measurement-differential thermal analysis (TG-DTA: Thermogravimetry-Differential Thermal Analysis) and determining the relationship between the weight and the temperature (thermogravimetric measurement).
- TG-DTA Thermogravimetry-Differential Thermal Analysis
- thermogravimetric measurement the measurement is preferably performed in an atmosphere of 0.1 Pa or less in consideration of the fact that the vapor deposition operation is performed in a pressure environment of 0.1 Pa or less.
- the pressure for vapor deposition is determined in advance, it is preferable to use the value measured under that pressure.
- the difference in 5% weight loss temperature is preferably 40°C or lower, more preferably 30°C or lower, and further preferably 20°C or lower.
- the composition for an EL device of one embodiment of the present invention is composed of two kinds of substances, a first organic compound and a second organic compound, the first organic compound has an electron transporting property, and It is preferable that the organic compound of 2 has a hole transporting property.
- the EL device composition is useful as a composition for forming the light emitting layer 113 in the EL device.
- a combination of the first organic compound and the second organic compound forming an exciplex is more useful as a composition for forming the light emitting layer 113.
- the mixing ratio is preferably 1:9 to 9:1 for the first organic compound:second organic compound, and more preferably 2:8 to 8:2 by weight.
- a composition for forming the hole-injection layer 111 by using the first organic compound as a material having a hole-transport property and the second organic compound as a substance having an electron-accepting property to the first organic compound It becomes useful as a thing.
- a composition for forming the electron-transporting layer 114 is obtained by using the first organic compound as a material having an electron-transporting property and the second organic compound as a substance having an electron-donating property to the first organic compound. It will be useful.
- the first organic compound when the first organic compound has an electron-transporting property and the second organic compound has a hole-transporting property, the first organic compound has a benzophrodiazine skeleton or a benzothiodiazine skeleton. It is effective to manufacture a more stable EL device.
- the first organic compound is more preferably any one of a naphthoflopyrazine skeleton, a phenanthropyrazine skeleton, a naphthothiopyrazine skeleton, or a phenanthrothiopyrazine skeleton. More preferably, it is an organic compound represented by G1).
- the EL device composition is useful as a composition for forming the light emitting layer 113 in the EL device.
- Q represents oxygen or sulfur.
- Ar 1 represents a substituted or unsubstituted fused aromatic ring.
- R 1 and R 2 represents hydrogen and the other represents a group having a total carbon number of 1 to 100 having a hole-transporting skeleton.
- the hole-transporting skeleton include a ⁇ -electron excess heteroaromatic ring skeleton such as a pyrrole skeleton, a furan skeleton, a thiophene skeleton, and a carbazole skeleton, a condensed aromatic hydrocarbon ring skeleton, and an aromatic amine skeleton.
- composition for an EL device having the above structure in which the first organic compound is represented by the following structural formula (100).
- the first organic compound has an electron transporting property and the second organic compound has a hole transporting property
- the first organic compound has a benzofuropyrimidine skeleton or a benzothiopyrimidine skeleton.
- Q represents oxygen or sulfur.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon ring, and the substituent of the aromatic hydrocarbon ring is an alkyl group having 1 to 6 carbon atoms, Or an alkoxy group having 1 to 6 carbon atoms, a monocyclic saturated hydrocarbon group having 5 to 7 carbon atoms, a polycyclic saturated hydrocarbon group having 7 to 10 carbon atoms, or a cyano group, The number of carbon atoms forming the aromatic hydrocarbon ring is 6 or more and 25 or less. Further, m and n are 0 or 1, respectively.
- A is a group having 12 to 100 total carbon atoms, and is a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, a triphenylene ring, a heteroaromatic ring containing a dibenzothiophene ring, a heteroaromatic ring containing a dibenzofuran ring, or carbazole. It has one or more of a heteroaromatic ring containing a ring, a benzimidazole ring, and a triphenylamine structure.
- R 1 is hydrogen, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted monocyclic saturated hydrocarbon having 5 to 7 carbon atoms, a substituted or unsubstituted polycyclic saturated hydrocarbon having 7 to 10 carbon atoms It represents a hydrocarbon, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms. Note that in the general formula (G2), m and n are preferably 0.
- another embodiment of the present invention is a composition for an EL device, in which the first organic compound is represented by the following structural formula (200) or the following structural formula (201).
- the second organic compound When the first organic compound has an electron transporting property and the second organic compound has a hole transporting property, the second organic compound has an aromatic amine skeleton, and thus the hole transporting property is It is preferable because it has high stability.
- the second organic compound preferably has a triarylamine skeleton, a carbazole skeleton, or both.
- the second organic compound is an organic compound having both the triarylamine skeleton and the carbazole skeleton
- the nitrogen atom in the triarylamine skeleton and the carbazole skeleton are bonded via a phenylene group. It is preferable that the organic compound is a stable and reliable compound.
- the second organic compound is an organic compound having both the triarylamine skeleton and the carbazole skeleton
- the carbazole skeleton is bonded to the amine at the 2-position to 4-position or 9-position. Is preferable from the viewpoint of reliability.
- the second organic compound is an organic compound having a carbazole skeleton
- the second organic compound is an organic compound having a bicarbazole skeleton because the hole transporting property is good and the stability is high.
- the bicarbazole skeleton preferably has a structure in which two carbazolyl groups are bonded to each other at any of the 2nd to 4th positions.
- the EL device manufactured using the EL device composition can be an EL device exhibiting good and stable characteristics.
- an EL device having good characteristics can be manufactured at low cost.
- FIG. 1 shows an EL device that can be manufactured using the composition for EL device shown in Embodiment Mode 1.
- the EL device shown in FIG. 1A has an anode 101, a cathode 102, and an EL layer 103.
- the EL layer 103 has various functional layers including a light emitting layer 113, and in addition to the above light emitting layer, a hole injection layer 111, a hole transport layer 112, an electron transport layer 114, and an electron injection layer.
- the layer 115 and the like may be included.
- the light-emitting layer 113 contains a light-emitting material, and the EL device described in this embodiment obtains light emission from the light-emitting material.
- the light emitting layer 113 may contain a host material or other materials.
- the anode 101 is preferably formed using a metal, an alloy, a conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more).
- a metal an alloy, a conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more).
- ITO indium oxide-tin oxide
- IWZO indium oxide-tin oxide
- these conductive metal oxide films are usually formed by a sputtering method, they may be formed by applying a sol-gel method or the like.
- indium oxide-zinc oxide As an example of a manufacturing method, there is a method of forming indium oxide-zinc oxide by a sputtering method using a target in which zinc oxide of 1 to 20 wt% is added to indium oxide.
- Indium oxide containing tungsten oxide and zinc oxide (IWZO) is formed by a sputtering method using a target containing 0.5 to 5 wt% of tungsten oxide and 0.1 to 1 wt% of zinc oxide with respect to indium oxide. You can also do it.
- Graphene can also be used. Note that by using a composite material described below for a layer of the EL layer 103 which is in contact with the anode 101, an electrode material can be selected regardless of a work function.
- the EL layer 103 preferably has a laminated structure, but the laminated structure is not particularly limited, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a carrier block layer.
- Various layer structures such as an exciton block layer and a charge generation layer can be applied.
- the electron transport layer 114 As described above, two types of configurations including the electron transport layer 114, the electron injection layer 115, and the charge generation layer 116 in addition to the hole injection layer 111, the hole transport layer 112, and the light emitting layer 113 will be described.
- the materials constituting each layer will be specifically shown below.
- the hole-injection layer 111 can be formed using a substance having an electron-accepting property.
- the substance having an electron accepting property include molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, and manganese oxide. Among them, molybdenum oxide is particularly preferable because it is stable in the air, has low hygroscopicity, and is easy to handle.
- organic compounds having an electron withdrawing group (a halogen group or a cyano group) can be given.
- the [3]radialene derivative having an electron-withdrawing group (in particular, a halogen group such as a fluoro group or a cyano group) is an organic compound which can be suitably used as a substance having an electron-accepting property because it has a very high electron-accepting property. ..
- Examples of such an organic compound include 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F4-TCNQ) and 3,6-difluoro-2,5.
- phthalocyanine-based complex compounds such as phthalocyanine (abbreviation: H 2 Pc) and copper phthalocyanine (CuPc), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation) : DPAB), N,N'-bis ⁇ 4-[bis(3-methylphenyl)amino]phenyl ⁇ -N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (abbreviation) : DNTPD) and other aromatic amine compounds can also be used.
- polymers such as poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS) can also be used.
- These substances having an electron-accepting property can extract an electron from an adjacent hole-transporting layer (or hole-transporting material) by applying an electric field, and by pulling out the electron, an adjacent hole-transporting layer (or positive hole-transporting layer) can be drawn. Holes can be injected (generated) into the hole transport material.
- a composite material in which a substance having a hole-transporting property contains a substance having an electron-accepting property can be used.
- a material for forming an electrode can be selected regardless of a work function. That is, not only a material having a high work function but also a material having a low work function can be used as the anode 101.
- the substance having an electron-accepting property the substance having an electron-accepting property described above can be used.
- the substance having a hole-transporting property used for the composite material various organic compounds such as an aromatic amine compound, a carbazole derivative, an aromatic hydrocarbon, and a high molecular compound (oligomer, dendrimer, polymer, or the like) can be used.
- the substance having a hole-transport property used for the composite material is preferably a substance having a hole mobility of 1 ⁇ 10 ⁇ 6 cm 2 /Vs or higher.
- organic compounds that can be used as the substance having a hole-transporting property in the composite material are specifically listed.
- N,N′-di(p-tolyl)-N,N′-diphenyl-p-phenylenediamine (abbreviation: DTDPPA), 4,4′-bis[ N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), N,N'-bis ⁇ 4-[bis(3-methylphenyl)amino]phenyl ⁇ -N,N'-diphenyl -(1,1'-biphenyl)-4,4'-diamine (abbreviation: DNTPD), 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B) ), 1,1-bis-(4-bis(4-methyl-phenyl)-amino-phenyl)-cyclohexane (abbreviation: DTDPPA), 4,4′-bis
- carbazole derivative examples include 3-[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1) and 3,6-bis[N-.
- PCzPCA2 (9-Phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), 3-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl) Amino]-9-phenylcarbazole (abbreviation: PCzPCN1), 4,4′-di(N-carbazolyl)biphenyl (abbreviation: CBP), 1,3,5-tris[4-(N-carbazolyl)phenyl]benzene( Abbreviation: TCPB), 9-[4-(10-phenyl-9-anthracenyl)phenyl]-9H-carbazole (abbreviation: CzPA), 1,4-bis[4-(N-carbazolyl)phenyl]-2,3.
- PCzPCN1 4,4′-di(N-carbazoly
- aromatic hydrocarbon examples include 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA), 2-tert-butyl-9,10-di(1-naphthyl).
- pentacene, coronene, etc. can also be used. It may have a vinyl skeleton.
- aromatic hydrocarbon having a vinyl group examples include 4,4′-bis(2,2-diphenylvinyl)biphenyl (abbreviation: DPVBi) and 9,10-bis[4-(2,2- And diphenylvinyl)phenyl]anthracene (abbreviation: DPVPA).
- poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), poly[N-(4- ⁇ N'-[4-(4-diphenylamino)) Phenyl]phenyl-N'-phenylamino ⁇ phenyl)methacrylamide] (abbreviation: PTPDMA), poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine] (abbreviation: Polymer compounds such as Poly-TPD) can also be used.
- PVK poly(N-vinylcarbazole)
- PVTPA poly(4-vinyltriphenylamine)
- PTPDMA poly[N-(4- ⁇ N'-[4-(4-diphenylamino)) Phenyl]phenyl-N'-phenylamino ⁇ phenyl)methacrylamide]
- the hole-transporting layer 112 is formed by including a material having a hole-transporting property.
- the material having a hole-transport property preferably has a hole mobility of 1 ⁇ 10 ⁇ 6 cm 2 /Vs or higher.
- Examples of the material having a hole-transporting property include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB) and N,N′-bis(3-methylphenyl).
- TPD 4,4'-bis[N-(spiro-9,9'-bifluorene-2- -N-phenylamino]biphenyl
- BSPB 4,4'-bis[N-(spiro-9,9'-bifluorene-2- -N-phenylamino]biphenyl
- BPAFLP 4-phenyl-4'-(9-phenylfluoren-9-yl)triphenylamine
- mBPAFLP 4-phenyl-3'-(9 -Phenylfluoren-9-yl)triphenylamine
- PCBA1BP 4,4' -Diphenyl-4"-(9-phenyl-9H-carbazol-3-yl)triphenylamine
- PCBBi1BP 4,4' -Diphenyl-4"-(9-phenyl-9H-carbazol-3-yl)triphenylamine
- mCP 4,4'-di(N-carbazolyl)biphenyl
- CBP 4,4'-di(N-carbazolyl)biphenyl
- CzTP 3,6-bis(3,5-diphenylphenyl)-9-phenylcarbazole
- PCCP 3,3′-bis(9-phenyl-9H-carbazole)
- PCCP 3,3′-bis(9-phenyl-9H-carbazole
- Tri(dibenzothiophene) (abbreviation: DBT3P-II), 2'8-diphenyl-4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]dibenzothiophene (abbreviation: DBTFLP-III), 4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-6-phenyldibenzothi
- a compound having a thiophene skeleton such as offene (abbreviation: DBTFLP-IV), 4,4′,4′′-(benzene-1,3,5-triyl)tri(dibenzofuran) (abbreviation: DBF3P-II), 4 Examples thereof include compounds having a furan skeleton such as - ⁇ 3-[3-(9-phenyl-9H-fluoren-9-yl)phenyl]phenyl ⁇ dibenzofuran (abbreviation: mmDBFF
- a compound having an aromatic amine skeleton and a compound having a carbazole skeleton are preferable because they have favorable reliability, high hole transporting properties, and contribute to reduction in driving voltage.
- the substances given as the material having a hole-transport property used for the composite material of the hole-injection layer 111 can also be preferably used as a material for forming the hole-transport layer 112.
- the light emitting layer 113 is a layer containing a host material and a light emitting material.
- the light emitting material may be a fluorescent light emitting material, a phosphorescent light emitting material, a material exhibiting thermally activated delayed fluorescence (TADF), or any other light emitting material.
- the light emitting layer 113 may be a single layer or a plurality of layers containing different light emitting materials.
- Examples of the fluorescent light-emitting substance that can be used as the light-emitting material in the light-emitting layer 113 include the following. Further, other fluorescent light emitting substances can be used.
- YGA2S 4-(9H-carbazol-9-yl)-4'-(10-phenyl-9-anthryl)triphenylamine
- YGAPA 4-(9H-carbazole-9- Yl)-4'-(9,10-diphenyl-2-anthryl)triphenylamine
- 2YGAPPA N,9-diphenyl-N-[4-(10-phenyl-9-anthryl)phenyl]-9H.
- PCAPA perylene, 2,5,8,11-tetra-tert-butylperylene
- TBP 2,5,8,11-tetra-tert-butylperylene
- PCBAPA 4-(10-phenyl-9-anthryl)-4'-( 9-phenyl-9H-carbazol-3-yl)triphenylamine
- PCBAPA N,N′′-(2-tert-butylanthracene-9,10-diyldi-4,1-phenylene)bis[N , N',N'-triphenyl-1,4-phenylenediamine]
- DPABPA N,9-diphenyl-N-[4-(9,10-diphenyl-2-anthryl)phenyl]-9H-.
- 1,6BnfAPrn-03 a condensed aromatic diamine compound represented by a pyrenediamine compound such as 1,6FLPAPrn, 1,6mMemFLPAPrn, and 1,6BnfAPrn-03 has a high hole trap property and is excellent in light emission efficiency and reliability.
- Examples of the phosphorescent substance that can be used as the light emitting material in the light emitting layer 113 include the following substances.
- Such an organometallic iridium complex having an imidazole skeleton and bis[2-(4',6'-difluorophenyl)pyridinato-N,C2 ' ]iridium(III) tetrakis(1-pyrazolyl)borate abbreviation: FIr6
- Bis[2-(4',6'-difluorophenyl)pyridinato-N,C2 ' ]iridium(III) picolinate abbreviation: FIrpic
- bis ⁇ 2-[3',5'-bis(trifluoromethyl) ) phenyl] pyridinato -N, C 2 ' ⁇ iridium (III) picolinate abbreviation: [Ir (CF 3 ppy) 2 (pic)]
- tris(4-methyl-6-phenylpyrimidinato)iridium(III) abbreviation: [Ir(mppm) 3 ]
- tris(4-t-butyl-6-phenylpyrimidinato)iridium(III) abbreviation: [Ir(tBuppm) 3 ]
- (acetylacetonato)bis(6-methyl-4-phenylpyrimidinato)iridium(III) abbreviation: [Ir(mppm) 2 (acac)]
- Acetylacetonato)bis(6-tert-butyl-4-phenylpyrimidinato)iridium(III) abbreviation: [Ir(tBuppm) 2 (acac)]
- Acetylacetonato)bis[6-(2- Norbornyl)-4-phenylpyrimidinato]iridium (III) abbreviation: [Ir(nbppm) 2
- organometallic iridium complex having a pyrimidine skeleton is particularly preferable because it is extremely excellent in reliability and light emission efficiency.
- known phosphorescent light emitting materials may be selected and used.
- Fullerene and its derivative, acridine and its derivative, eosin derivative, etc. can be used as the TADF material that can be used in the light emitting layer 113.
- a metal-containing porphyrin containing magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), palladium (Pd), or the like can be given.
- the metal-containing porphyrin include protoporphyrin-tin fluoride complex (SnF 2 (Proto IX)), mesoporphyrin-tin fluoride complex (SnF 2 (Meso IX)), hematoporphyrin represented by the following structural formulas.
- PCCzTzn 2- ⁇ 4-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl ⁇ -4,6-diphenyl-1,3,5 -Triazine
- PCCzPTzn 2-[4-(10H-phenoxazin-10-yl)phenyl]-4,6-diphenyl-1,3,5-triazine
- PXZ-TRZ 2-[4-(10H-phenoxazin-10-yl)phenyl]-4,6-diphenyl-1,3,5-triazine
- PXZ-TRZ 2-[4-(10H-phenoxazin-10-yl)phenyl]-4,6-diphenyl-1,3,5-triazine
- PXZ-TRZ 2-[4-(10H-phenoxazin-10-yl)phenyl]-4,6-diphenyl-1,3,5-triazine
- a pyridine skeleton, a diazine skeleton (pyrimidine skeleton, pyrazine skeleton, pyridazine skeleton) and a triazine skeleton are preferable because they are stable and have good reliability.
- a benzofuropyrimidine skeleton, a benzothienopyrimidine skeleton, a benzofuropyrazine skeleton, and a benzothienopyrazine skeleton have high acceptor properties and high reliability, which is preferable.
- an acridine skeleton, a phenoxazine skeleton, a phenothiazine skeleton, a furan skeleton, a thiophene skeleton, and a pyrrole skeleton are stable and have good reliability; It is preferable to have A dibenzofuran skeleton is preferable as the furan skeleton, and a dibenzothiophene skeleton is preferable as the thiophene skeleton.
- an indole skeleton, a carbazole skeleton, an indolocarbazole skeleton, a bicarbazole skeleton, and a 3-(9-phenyl-9H-carbazol-3-yl)-9H-carbazole skeleton are particularly preferable.
- a substance in which the ⁇ -electron excess type heteroaromatic ring and the ⁇ -electron deficient heteroaromatic ring are directly bound to each other has both the electron donating property of the ⁇ -electron excess heteroaromatic ring and the electron accepting property of the ⁇ -electron deficient heteroaromatic ring.
- an aromatic ring to which an electron-withdrawing group such as a cyano group is bonded may be used.
- an aromatic amine skeleton, a phenazine skeleton, or the like can be used as the ⁇ -electron excess skeleton.
- An aromatic ring or a heteroaromatic ring having a cyano group such as benzene, a carbonyl skeleton such as benzophenone, a phosphine oxide skeleton, a sulfone skeleton, or the like can be used.
- a ⁇ -electron-deficient skeleton and a ⁇ -electron-excess skeleton can be used in place of at least one of the ⁇ -electron-deficient heteroaromatic ring and the ⁇ -electron-excess heteroaromatic ring.
- the TADF material is a material having a small difference between the S1 level and the T1 level and having a function of converting energy from triplet excitation energy to singlet excitation energy by inverse intersystem crossing. Therefore, the triplet excitation energy can be up-converted (reverse intersystem crossing) to the singlet excitation energy with a small amount of thermal energy, and the singlet excited state can be efficiently generated. In addition, triplet excitation energy can be converted into light emission.
- an exciplex (also referred to as an exciplex, an exciplex, or an exciplex) that forms an excited state with two kinds of substances has an extremely small difference between the S1 level and the T1 level, and has triplet excitation energy as singlet excitation energy. It has a function as a TADF material that can be converted into.
- a phosphorescence spectrum observed at low temperature may be used as an index of the T1 level.
- a tangent line is drawn at the short wavelength side skirt of the fluorescence spectrum, the energy of the wavelength at the position where the extrapolation line intersects the X axis is set to the S1 level, and the tangent line is formed at the short wavelength side skirt of the phosphorescence spectrum.
- the difference between S1 and T1 is preferably 0.3 eV or less, and more preferably 0.2 eV or less.
- the S1 level of the host material is preferably higher than the S1 level of the TADF material.
- the T1 level of the host material is preferably higher than the T1 level of the TADF material.
- various carrier transporting materials such as a material having an electron transporting property, a material having a hole transporting property and the TADF material can be used.
- the substances mentioned as the material having a hole-transporting property contained in the hole-transporting layer 112 can be preferably used, and particularly, an organic compound having an aromatic amine skeleton is used. It is preferable to have a hole transporting property and a good stability. Further, among the organic compounds having an aromatic amine skeleton, those having a triarylamine skeleton, a carbazole skeleton, or both are preferable.
- the material having a hole-transporting property is an organic compound having both the triarylamine skeleton and the carbazole skeleton
- the nitrogen atom in the triarylamine skeleton and the carbazole skeleton are bonded to each other through a phenylene group. It is preferable that these organic compounds are stable and reliable.
- the material having a hole-transporting property is an organic compound having both the triarylamine skeleton and the carbazole skeleton
- the carbazole skeleton has the amine at the 2-position to 4-position or 9-position. It is preferable that they are bonded from the viewpoint of reliability.
- the material having a hole transporting property is an organic compound having a carbazole skeleton
- an organic compound having a bicarbazole skeleton is preferable because the hole transporting property is good and the stability is high.
- the bicarbazole skeleton preferably has a structure in which two carbazolyl groups are bonded to each other at any of the 2nd to 4th positions.
- Examples of the material having a hole transporting property having such a structure include the following.
- Examples of the material having an electron-transporting property include bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq 2 ), bis(2-methyl-8-quinolinolato)(4-phenylphenolato).
- a heterocyclic compound having a diazine skeleton and a heterocyclic compound having a pyridine skeleton have favorable reliability and are preferable.
- a heterocyclic compound having a diazine (pyrimidine or pyrazine) skeleton has a high electron-transporting property and contributes to a reduction in driving voltage.
- an organic compound having a benzofurodiazine skeleton or a benzothiodiazine skeleton is particularly preferable, and an organic compound represented by the following general formula (G1) is particularly preferable.
- Q represents oxygen or sulfur.
- Ar 1 represents a substituted or unsubstituted fused aromatic ring.
- R 1 and R 2 represents hydrogen and the other represents a group having a total carbon number of 1 to 100 having a hole-transporting skeleton.
- the hole-transporting skeleton include a ⁇ -electron excess heteroaromatic ring skeleton such as a pyrrole skeleton, a furan skeleton, a thiophene skeleton, and a carbazole skeleton, a condensed aromatic hydrocarbon ring skeleton, and an aromatic amine skeleton.
- an organic compound represented by the following structural formula (100) is particularly preferable.
- an organic compound having a benzofuropyrimidine skeleton or a benzothiopyrimidine skeleton is also preferable, and among them, an organic compound represented by the following general formula (G2) is preferable.
- Q represents oxygen or sulfur.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent a substituted or unsubstituted aromatic hydrocarbon ring, and the substituent of the aromatic hydrocarbon ring is an alkyl group having 1 to 6 carbon atoms, Or an alkoxy group having 1 to 6 carbon atoms, a monocyclic saturated hydrocarbon group having 5 to 7 carbon atoms, a polycyclic saturated hydrocarbon group having 7 to 10 carbon atoms, or a cyano group, The number of carbon atoms forming the aromatic hydrocarbon ring is 6 or more and 25 or less. Further, m and n are 0 or 1, respectively.
- A is a group having 12 to 100 total carbon atoms, and is a benzene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, a triphenylene ring, a heteroaromatic ring containing a dibenzothiophene ring, a heteroaromatic ring containing a dibenzofuran ring, or carbazole. It has one or more of a heteroaromatic ring containing a ring, a benzimidazole ring, and a triphenylamine structure.
- R 1 is hydrogen, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted monocyclic saturated hydrocarbon having 5 to 7 carbon atoms, a substituted or unsubstituted polycyclic saturated hydrocarbon having 7 to 10 carbon atoms It represents a hydrocarbon, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms. Note that in the general formula (G2), m and n are preferably 0.
- an organic compound having a benzoflodiazine skeleton or a benzothiodiazine skeleton or an organic compound having a benzofuropyrimidine skeleton or a benzothiopyrimidine skeleton which can be preferably used as a material having an electron transporting property,
- the following can be mentioned.
- the organic compound represented by the following structural formula (200) or (201) is particularly preferable.
- a material having an anthracene skeleton is suitable as the host material.
- a substance having an anthracene skeleton is used as a host material for a fluorescent substance, it is possible to realize a light emitting layer having good emission efficiency and durability. Since many materials having an anthracene skeleton have deep HOMO levels, one embodiment of the present invention can be preferably applied.
- a substance having a diphenylanthracene skeleton, particularly a substance having a 9,10-diphenylanthracene skeleton is preferable because it is chemically stable.
- the host material has a carbazole skeleton
- the hole injection/transport property is improved.
- the carbazole contains a benzocarbazole skeleton in which a benzene ring is further condensed
- the HOMO becomes shallower by about 0.1 eV than carbazole. It is more preferable because holes easily enter.
- the host material contains a dibenzocarbazole skeleton
- HOMO is shallower than that of carbazole by about 0.1 eV, holes are easily introduced, and hole transportability is excellent and heat resistance is also high, which is preferable. ..
- a material having a 9,10-diphenylanthracene skeleton and a carbazole skeleton (or a benzocarbazole skeleton or a dibenzocarbazole skeleton) at the same time is more preferable as the host material.
- a benzofluorene skeleton or a dibenzofluorene skeleton may be used instead of the carbazole skeleton.
- Examples of such a substance include 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: PCzPA), 3-[4-(1-naphthyl)- Phenyl]-9-phenyl-9H-carbazole (abbreviation: PCPN), 9-[4-(10-phenyl-9-anthracenyl)phenyl]-9H-carbazole (abbreviation: CzPA), 7-[4-(10- Phenyl-9-anthryl)phenyl]-7H-dibenzo[c,g]carbazole (abbreviation: cgDBCzPA), 6-[3-(9,10-diphenyl-2-anthryl)phenyl]-benzo[b]naphtho[1.
- PCzPA 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9
- 2-d]furan abbreviation: 2mBnfPPA
- 9-phenyl-10- ⁇ 4-(9-phenyl-9H-fluoren-9-yl)biphenyl-4′-yl ⁇ anthracene abbreviation: FLPPA
- CzPA, cgDBCzPA, 2mBnfPPA, and PCzPA are preferable choices because they show very good characteristics.
- the host material may be a material in which plural kinds of substances are mixed, and when the mixed host material is used, it is preferable to mix a material having an electron-transporting property and a material having a hole-transporting property. ..
- a material having an electron transporting property and a material having a hole transporting property By mixing a material having an electron transporting property and a material having a hole transporting property, the transportability of the light emitting layer 113 can be easily adjusted and the recombination region can be easily controlled.
- the composition for an EL device of one embodiment of the present invention can be favorably used in the production thereof.
- the EL device composition of one embodiment of the present invention is obtained by thermogravimetric measurement of two or more of the above-mentioned materials under a pressure of 0.1 Pa or less between the two or more organic compounds. The difference between the measured 5% weight loss temperatures is selected to be 50 degrees or less, and the mixture is obtained by mixing at an arbitrary ratio.
- the EL device composition is unlikely to undergo a large change in the composition itself or in the composition of a film formed by continuous vapor deposition. Therefore, the EL device manufactured using the EL device composition can be an EL device exhibiting good and stable characteristics.
- an EL device having good characteristics can be manufactured at low cost.
- the electron-transport layer 114 is a layer containing a substance having an electron-transport property.
- the substance having an electron-transporting property the substances listed as the substance having an electron-transporting property which can be used for the host material can be used.
- an alkali metal or an alkaline earth metal such as lithium fluoride (LiF), cesium fluoride (CsF), or calcium fluoride (CaF 2 ).
- a layer containing these compounds may be provided.
- the electron injection layer 115 a layer formed of a substance having an electron transporting property containing an alkali metal, an alkaline earth metal or a compound thereof, or an electride may be used. Examples of the electride include a substance obtained by adding a high concentration of electrons to a mixed oxide of calcium and aluminum.
- a substance having an electron-transport property (preferably an organic compound having a bipyridine skeleton) contains a fluoride of the above alkali metal or an alkaline earth metal at a concentration higher than or equal to a microcrystalline state (50 wt% or higher). It is also possible to use different layers. Since the layer is a layer having a low refractive index, it becomes possible to provide an EL device having better external quantum efficiency.
- a charge generation layer 116 may be provided instead of the electron injection layer 115 (FIG. 1B).
- the charge generation layer 116 is a layer that can inject holes into a cathode and electrons into a layer in contact with an anode by applying a potential.
- the charge generation layer 116 includes at least the P-type layer 117.
- the P-type layer 117 is preferably formed using the composite material mentioned as the material that can form the hole injection layer 111 described above. Further, the P-type layer 117 may be formed by stacking a film containing the above-described acceptor material as a material forming the composite material and a film containing a hole transport material. By applying a potential to the P-type layer 117, electrons are injected into the electron transport layer 114 and holes are injected into the cathode 102, and the EL device operates.
- the charge generation layer 116 preferably includes one or both of the electron relay layer 118 and the electron injection buffer layer 119.
- the electron relay layer 118 includes at least a substance having an electron transporting property, and has a function of preventing interaction between the electron injection buffer layer 119 and the P-type layer 117 and smoothly transferring electrons.
- the LUMO level of the substance having an electron transporting property included in the electron relay layer 118 is included in the LUMO level of the substance having an electron accepting property in the P-type layer 117 and the layer in contact with the charge generation layer 116 in the electron transporting layer 114. It is preferably between the LUMO level of the substance to be treated.
- the specific LUMO level of the substance having an electron-transporting property used for the electron relay layer 118 is ⁇ 5.0 eV or higher, preferably ⁇ 5.0 eV or higher and ⁇ 3.0 eV or lower.
- a phthalocyanine-based material or a metal complex having a metal-oxygen bond and an aromatic ligand is preferably used.
- the electron injection buffer layer 119 includes alkali metals, alkaline earth metals, rare earth metals, and compounds thereof (including alkali metal compounds (oxides such as lithium oxide, halides, carbonates such as lithium carbonate and cesium carbonate)). , Alkaline earth metal compounds (including oxides, halides, carbonates), or rare earth metal compounds (including oxides, halides, carbonates), etc. can be used. Is.
- the electron-injection buffer layer 119 is formed containing a substance having an electron-transporting property and a donor substance, an alkali metal, an alkaline earth metal, a rare earth metal, or a compound thereof
- Alkali metal compounds including oxides such as lithium oxide, halides, carbonates such as lithium carbonate and cesium carbonate
- alkaline earth metal compounds including oxides, halides and carbonates
- organic compounds such as tetrathianaphthacene (abbreviation: TTN), nickelocene, and decamethylnickelocene can also be used.
- TTN tetrathianaphthacene
- nickelocene nickelocene
- decamethylnickelocene can also be used.
- the substance having an electron-transporting property can be formed using a material similar to the material forming the electron-transporting layer 114 described above.
- a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a low work function (specifically, 3.8 eV or less) can be used as a material forming the cathode 102.
- a cathode material include alkali metals such as lithium (Li) and cesium (Cs), and Group 1 of the periodic table of elements such as magnesium (Mg), calcium (Ca), and strontium (Sr), or Examples thereof include elements belonging to Group 2, alloys containing these (MgAg, AlLi), rare earth metals such as europium (Eu), and ytterbium (Yb), and alloys containing these.
- any conductive material can be used as the cathode 102.
- These conductive materials can be formed by a dry method such as a vacuum evaporation method or a sputtering method, an inkjet method, a spin coating method, or the like. Further, it may be formed by a wet method using a sol-gel method, or may be formed by a wet method using a paste of a metal material.
- a method for forming the EL layer 103 various methods can be used regardless of a dry method or a wet method.
- a vacuum vapor deposition method, a gravure printing method, an offset printing method, a screen printing method, an inkjet method or a spin coating method may be used.
- an EL device having favorable and stable characteristics can be manufactured by using the composition for EL device of one embodiment of the present invention. .. Further, it is advantageous in terms of cost by suppressing an increase in equipment investment and maintenance work.
- each electrode or each layer described above may be formed by using different film forming methods.
- the structure of the layer provided between the anode 101 and the cathode 102 is not limited to the above. However, in order to suppress quenching caused by the proximity of the light emitting region and the metal used for the electrode or the carrier injection layer, the light emitting region in which holes and electrons are recombined at a site apart from the anode 101 and the cathode 102.
- the configuration provided with is preferable.
- the hole transport layer and the electron transport layer which are in contact with the light-emitting layer 113 in particular, the carrier transport layer near the recombination region in the light-emitting layer 113 suppresses energy transfer from excitons generated in the light-emitting layer, and thus the light-emitting layer is formed. It is preferable to use a light emitting material or a substance having a band gap larger than that of the light emitting material contained in the light emitting layer.
- FIG. 1C a mode of an EL device (also referred to as a stacked device or a tandem device) having a structure in which a plurality of light emitting units is stacked is described with reference to FIG. 1C.
- This EL device is an EL device having a plurality of light emitting units between an anode and a cathode.
- One light emitting unit has substantially the same structure as the EL layer 103 shown in FIG. 1A. That is, it can be said that the EL device shown in FIG. 1C is an EL device having a plurality of light emitting units, and the EL device shown in FIG. 1A or 1B is an EL device having one light emitting unit.
- a first light emitting unit 511 and a second light emitting unit 512 are stacked between an anode 501 and a cathode 502, and between the first light emitting unit 511 and the second light emitting unit 512. Is provided with a charge generation layer 513.
- the anode 501 and the cathode 502 correspond to the anode 101 and the cathode 102 in FIG. 1A, respectively, and the same ones described in the description of FIG. 1A can be applied.
- the first light emitting unit 511 and the second light emitting unit 512 may have the same configuration or different configurations.
- the charge generation layer 513 has a function of injecting electrons into one light emitting unit and injecting holes into the other light emitting unit when voltage is applied to the anode 501 and the cathode 502. That is, in FIG. 1C, when a voltage is applied so that the potential of the anode is higher than the potential of the cathode, the charge generation layer 513 injects electrons into the first light emitting unit 511 and the second light emitting unit 511. Any material that injects holes into 512 may be used.
- the charge generation layer 513 is preferably formed with the same structure as the charge generation layer 116 described in FIG. 1B. Since the composite material of an organic compound and a metal oxide is excellent in carrier injecting property and carrier transporting property, low voltage driving and low current driving can be realized. Note that when the surface of the light emitting unit on the anode side is in contact with the charge generation layer 513, the charge generation layer 513 can also serve as a hole injection layer of the light emission unit. It does not have to be provided.
- the electron injection buffer layer 119 plays a role of an electron injection layer in the light emitting unit on the anode side, and therefore the electron injection layer is not necessarily provided on the light emitting unit on the anode side. It need not be formed.
- FIG. 1C an EL device having two light emitting units has been described, but the above configuration can be similarly applied to an EL device having three or more light emitting units stacked.
- the EL device according to this embodiment by disposing a plurality of light emitting units between the pair of electrodes by the charge generation layer 513, high-luminance light emission is possible while keeping the current density low, and further, It is possible to realize a long-life EL device. Further, a light emitting device which can be driven at low voltage and consumes low power can be realized.
- the light emitting colors of the respective light emitting units different, it is possible to obtain light emission of a desired color in the EL device as a whole. For example, in an EL device having two light emitting units, by obtaining red and green light emitting colors in the first light emitting unit and blue light emitting color in the second light emitting unit, an EL device that emits white light as a whole of the EL device is obtained. It is also possible to obtain.
- FIG. 2A is a top view showing the light emitting device
- FIG. 2B is a cross-sectional view taken along line AB and CD in FIG. 2A.
- This light emitting device includes a drive circuit portion (source line drive circuit) 601, a pixel portion 602, and a drive circuit portion (gate line drive circuit) 603, which are shown by dotted lines, for controlling the light emission of the EL device.
- 604 is a sealing substrate
- 605 is a sealing material
- the inside surrounded by the sealing material 605 is a space 607.
- the lead wiring 608 is a wiring for transmitting a signal input to the source line driver circuit 601 and the gate line driver circuit 603, and a video signal, a clock signal, and Receives start signal, reset signal, etc.
- a printed wiring board PWB
- the light-emitting device in this specification includes not only the light-emitting device main body but also a state in which the FPC or PWB is attached thereto.
- a driver circuit portion and a pixel portion are formed over the element substrate 610, here, a source line driver circuit 601 which is a driver circuit portion and one pixel in the pixel portion 602 are shown.
- the element substrate 610 is made of a substrate made of glass, quartz, organic resin, metal, alloy, semiconductor, etc., or a plastic substrate made of FRP (Fiber Reinforced Plastics), PVF (polyvinyl fluoride), polyester or acrylic resin. do it.
- FRP Fiber Reinforced Plastics
- PVF polyvinyl fluoride
- the structure of a transistor used in a pixel or a driver circuit is not particularly limited.
- an inverted staggered transistor or a staggered transistor may be used.
- a top gate type transistor or a bottom gate type transistor may be used.
- the semiconductor material used for the transistor is not particularly limited, and for example, silicon, germanium, silicon carbide, gallium nitride, or the like can be used.
- an oxide semiconductor containing at least one of indium, gallium, and zinc such as an In—Ga—Zn-based metal oxide may be used.
- crystallinity of a semiconductor material used for a transistor either an amorphous semiconductor or a crystalline semiconductor (a microcrystalline semiconductor, a polycrystalline semiconductor, a single crystal semiconductor, or a semiconductor partially having a crystalline region). May be used. It is preferable to use a semiconductor having crystallinity because deterioration of transistor characteristics can be suppressed.
- an oxide semiconductor to a semiconductor device such as a transistor used for a touch sensor described later or the like in addition to the transistor provided in the pixel or the driver circuit.
- a semiconductor device such as a transistor used for a touch sensor described later or the like
- the oxide semiconductor preferably contains at least indium (In) or zinc (Zn). Further, the oxide semiconductor includes an oxide represented by an In-M-Zn-based oxide (M is a metal such as Al, Ti, Ga, Ge, Y, Zr, Sn, La, Ce, or Hf). Is more preferable.
- M is a metal such as Al, Ti, Ga, Ge, Y, Zr, Sn, La, Ce, or Hf. Is more preferable.
- oxide semiconductor which can be used in one embodiment of the present invention is described below.
- Oxide semiconductors are classified into single crystal oxide semiconductors and other non-single crystal oxide semiconductors.
- non-single-crystal oxide semiconductors include CAAC-OS (c-axis aligned crystal line oxide semiconductor), polycrystalline oxide semiconductor, nc-OS (nano crystalline oxide semiconductor), and pseudo-amorphous oxide semiconductor (a-).
- CAAC-OS c-axis aligned crystal line oxide semiconductor
- polycrystalline oxide semiconductor nc-OS (nano crystalline oxide semiconductor)
- nc-OS nano crystalline oxide semiconductor
- pseudo-amorphous oxide semiconductor a-like oxide semiconductor
- amorphous oxide semiconductor amorphous oxide semiconductor.
- the CAAC-OS has a crystal structure having c-axis orientation and a strain in which a plurality of nanocrystals are connected in the ab plane direction.
- the strain refers to a portion in which the orientation of the lattice arrangement is changed between a region where the lattice arrangement is uniform and another region where the lattice arrangement is uniform in the region where a plurality of nanocrystals are connected.
- the nanocrystal is basically a hexagon, but is not limited to a regular hexagon, and may be a non-regular hexagon.
- the strain may have a lattice arrangement such as a pentagon and a heptagon.
- a lattice arrangement such as a pentagon and a heptagon.
- the CAAC-OS is a layered crystal in which a layer containing indium and oxygen (hereinafter, an In layer) and a layer containing elements M, zinc, and oxygen (hereinafter, a (M,Zn) layer) are stacked. It tends to have a structure (also called a layered structure).
- indium and the element M can be replaced with each other, and when the element M of the (M,Zn) layer is replaced with indium, it can be expressed as an (In,M,Zn) layer.
- the indium of the In layer is replaced with the element M, it can be expressed as an (In,M) layer.
- CAAC-OS is an oxide semiconductor with high crystallinity.
- the CAAC-OS since it is difficult to confirm a clear crystal grain boundary, it can be said that the decrease in electron mobility due to the crystal grain boundary is unlikely to occur.
- the crystallinity of the oxide semiconductor may be degraded, such as by generation of contamination and defects impurities, CAAC-OS impurities and defects (oxygen deficiency (V O: oxygen vacancy also called), etc.) with little oxide It can be said to be a semiconductor. Therefore, the oxide semiconductor including the CAAC-OS has stable physical properties. Therefore, the oxide semiconductor including the CAAC-OS is highly heat resistant and highly reliable.
- the nc-OS has a periodic atomic arrangement in a minute region (for example, a region of 1 nm or more and 10 nm or less, particularly a region of 1 nm or more and 3 nm or less). Moreover, in the nc-OS, no regularity is found in the crystal orientation between different nanocrystals. Therefore, no orientation is seen in the entire film. Therefore, the nc-OS may be indistinguishable from the a-like OS or the amorphous oxide semiconductor depending on the analysis method.
- IGZO indium-gallium-zinc oxide
- IGZO which is a kind of oxide semiconductor containing indium, gallium, and zinc
- IGZO may have a stable structure by using the above-described nanocrystal.
- IGZO tends to have difficulty in crystal growth in the atmosphere, and thus a smaller crystal (for example, the above-mentioned nanocrystal) is used than a large crystal (here, a crystal of several mm or a crystal of several cm).
- a large crystal here, a crystal of several mm or a crystal of several cm.
- it may be structurally stable.
- the a-like OS is an oxide semiconductor having a structure between the nc-OS and the amorphous oxide semiconductor.
- the a-like OS has a void or a low density region. That is, the crystallinity of the a-like OS is lower than that of the nc-OS and the CAAC-OS.
- Oxide semiconductors have various structures and have different characteristics.
- the oxide semiconductor described here may include two or more of an amorphous oxide semiconductor, a polycrystalline oxide semiconductor, an a-like OS, an nc-OS, and a CAAC-OS.
- CAC Cloud-Aligned Composite
- the CAC-OS has a conductive function in a part of the material, an insulating function in a part of the material, and a function as a semiconductor in the whole material.
- a conductive function is a function of allowing electrons (or holes) serving as carriers to flow
- an insulating function is a function of not allowing electrons serving as carriers to flow. is there.
- the CAC-OS has a conductive region and an insulating region.
- the conductive region has the above-mentioned conductive function
- the insulating region has the above-mentioned insulating function.
- the conductive region and the insulating region may be separated at the nanoparticle level.
- the conductive region and the insulating region may be unevenly distributed in the material.
- the conductive region may be observed as a cloudy connection at the periphery and connected in a cloud shape.
- the conductive region and the insulating region may each be dispersed in the material in a size of 0.5 nm to 10 nm, preferably 0.5 nm to 3 nm.
- the CAC-OS is composed of components having different band gaps.
- the CAC-OS includes a component having a wide gap due to the insulating region and a component having a narrow gap due to the conductive region.
- a carrier when flowing a carrier, a carrier mainly flows in the component which has a narrow gap.
- the component having the narrow gap acts complementarily to the component having the wide gap, and the carrier also flows to the component having the wide gap in conjunction with the component having the narrow gap. Therefore, when the above CAC-OS is used for a channel formation region of a transistor, a high current driving force, that is, a large on-current and a high field-effect mobility can be obtained when the transistor is on.
- the CAC-OS can be referred to as a matrix composite material or a metal matrix composite material.
- the transistor including the above-described semiconductor layer can retain the charge accumulated in the capacitor through the transistor for a long period of time due to the low off-state current.
- the transistor including the above-described semiconductor layer can retain the charge accumulated in the capacitor through the transistor for a long period of time due to the low off-state current.
- a base film for stabilizing the characteristics of the transistor.
- an inorganic insulating film such as a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a silicon nitride oxide film can be used and can be formed in a single layer or stacked layers.
- the underlying film is formed by using a sputtering method, a CVD (Chemical Vapor Deposition) method (a plasma CVD method, a thermal CVD method, a MOCVD (Metal Organic CVD) method, etc.), an ALD (Atomic Layer Deposition) method, a coating method, a printing method, etc. it can.
- the base film may be omitted if it is not necessary.
- the FET 623 represents one of the transistors formed in the driver circuit portion 601.
- the driver circuit may be formed using various CMOS circuits, PMOS circuits, or NMOS circuits.
- CMOS circuits complementary metal-oxide-semiconductor circuits
- PMOS circuits PMOS circuits
- NMOS circuits CMOS circuits
- the driver circuit is not necessarily required and the driver circuit can be formed outside the substrate.
- the pixel portion 602 is formed by a plurality of pixels including the switching FET 611, the current control FET 612, and the anode 613 electrically connected to the drain thereof, but the pixel portion 602 is not limited to this and has three or more pixels. A pixel portion in which an FET and a capacitor are combined may be used.
- An insulator 614 is formed so as to cover the end portion of the anode 613.
- it can be formed by using a positive photosensitive acrylic resin film.
- a curved surface having a curvature is formed at an upper end portion or a lower end portion of the insulator 614 in order to improve coverage with an EL layer or the like which is formed later.
- a positive photosensitive acrylic resin is used as the material of the insulator 614
- a negative photosensitive resin or a positive photosensitive resin can be used as the insulator 614.
- An EL layer 616 and a cathode 617 are formed over the anode 613.
- a material used for the anode 613 which functions as an anode it is desirable to use a material having a high work function.
- a single layer film such as an ITO film or an indium tin oxide film containing silicon, an indium oxide film containing 2 to 20 wt% of zinc oxide, a titanium nitride film, a chromium film, a tungsten film, a Zn film, a Pt film, etc.
- a stacked layer of a titanium nitride film and a film containing aluminum as its main component a three-layer structure of a titanium nitride film, a film containing aluminum as its main component, and a titanium nitride film can be used. Note that when a stacked structure is used, resistance as a wiring is low, favorable ohmic contact can be obtained, and further, it can function as an anode.
- the EL layer 616 is formed by various methods such as an evaporation method using an evaporation mask, an inkjet method, and a spin coating method.
- the EL layer 616 includes the structure described in Embodiment Mode 2. Further, as the other material forming the EL layer 616, a low molecular compound or a high molecular compound (including an oligomer and a dendrimer) may be used.
- a material used for the cathode 617 which is formed over the EL layer 616 and functions as a cathode a material having a low work function (Al, Mg, Li, Ca, or an alloy or compound thereof (MgAg, MgIn, AlLi, or the like)) is used. Etc.) is preferably used. Note that when light generated in the EL layer 616 is transmitted through the cathode 617, the cathode 617 has a thin metal film and a transparent conductive film (ITO, indium oxide containing 2 to 20 wt% zinc oxide, A stack with indium tin oxide containing silicon, zinc oxide (ZnO), or the like is preferably used.
- ITO transparent conductive film
- An EL device 618 is formed by the anode 613, the EL layer 616, and the cathode 617.
- the EL device 618 is the EL device described in Embodiment 2. Note that although a plurality of EL devices is formed in the pixel portion, in the light-emitting device of this embodiment, both the EL device described in Embodiment 2 and an EL device having any other structure are mixed. You can do it.
- the sealing substrate 604 is attached to the element substrate 610 with the sealing material 605, whereby a structure where the EL device 618 is provided in the space 607 surrounded by the element substrate 610, the sealing substrate 604, and the sealing material 605 is obtained.
- the space 607 is filled with a filler, and may be filled with an inert gas (nitrogen, argon, etc.) or a sealant.
- epoxy resin or glass frit for the sealing material 605. Further, it is desirable that these materials are materials that are as impermeable to moisture and oxygen as possible. Further, as the material used for the sealing substrate 604, in addition to a glass substrate or a quartz substrate, a plastic substrate made of FRP (Fiber Reinforced Plastics), PVF (polyvinyl fluoride), polyester, acrylic resin, or the like can be used.
- FRP Fiber Reinforced Plastics
- PVF polyvinyl fluoride
- polyester acrylic resin, or the like
- a protective film may be provided on the cathode.
- the protective film may be formed of an organic resin film or an inorganic insulating film. Further, a protective film may be formed so as to cover the exposed portion of the sealing material 605. Further, the protective film can be provided so as to cover the surfaces and side surfaces of the pair of substrates, the exposed side surfaces of the sealing layer, the insulating layer, and the like.
- a material that does not easily pass impurities such as water can be used. Therefore, diffusion of impurities such as water from the outside to the inside can be effectively suppressed.
- oxides, nitrides, fluorides, sulfides, ternary compounds, metals or polymers, etc. can be used, and examples thereof include aluminum oxide, hafnium oxide, hafnium silicate, lanthanum oxide, and oxide.
- Materials such as oxides, sulfides containing manganese and zinc, sulfides containing cerium and strontium, oxides containing erbium and aluminum, oxides containing yttrium and zirconium, and the like can be used.
- the protective film is preferably formed by using a film forming method having good step coverage.
- a film forming method having good step coverage One of such methods is an atomic layer deposition (ALD) method.
- a material that can be formed by an ALD method is preferably used for the protective film.
- ALD method it is possible to form a dense protective film in which defects such as cracks and pinholes are reduced or which has a uniform thickness.
- the protective film by using the ALD method, it is possible to form a protective film that is uniform and has few defects even on the surface having a complicated uneven shape and the upper surface, the side surface, and the back surface of the touch panel.
- the light-emitting device manufactured using the EL device described in Embodiment 2 can be obtained.
- the light-emitting device in this embodiment uses the EL device described in Embodiment 2, a light-emitting device having favorable characteristics can be obtained. Specifically, the EL device described in Embodiment 2 has favorable emission efficiency and thus can be a light-emitting device with low power consumption.
- FIG. 3 shows an example of a light emitting device in which an EL device which emits white light is formed and a full color is formed by providing a coloring layer (color filter) or the like.
- the colored layers (red colored layer 1034R, green colored layer 1034G, and blue colored layer 1034B) are provided on the transparent base material 1033. Further, a black matrix 1035 may be further provided. The transparent base material 1033 provided with the coloring layer and the black matrix is aligned and fixed to the substrate 1001. Note that the coloring layer and the black matrix 1035 are covered with the overcoat layer 1036. Further, in FIG. 3A, there are a light-emitting layer that emits light to the outside without passing through the colored layer and a light-emitting layer that transmits light to the outside through the colored layers of each color. Since the light that passes through the white and colored layers becomes red, green, and blue, an image can be represented by pixels of four colors.
- FIG. 3B shows an example in which a coloring layer (a red coloring layer 1034R, a green coloring layer 1034G, and a blue coloring layer 1034B) is formed between the gate insulating film 1003 and the first interlayer insulating film 1020.
- the coloring layer may be provided between the substrate 1001 and the sealing substrate 1031.
- the light emitting device has a structure (bottom emission type) for extracting light to the side of the substrate 1001 on which the FET is formed, but a structure for extracting light to the sealing substrate 1031 side (top emission type). ) May be used as the light emitting device.
- a cross-sectional view of the top emission type light emitting device is shown in FIG.
- the substrate 1001 can be a substrate that does not transmit light.
- the connection electrode for connecting the FET and the anode of the EL device is manufactured, it is formed similarly to the bottom emission type light emitting device.
- a third interlayer insulating film 1037 is formed so as to cover the electrode 1022. This insulating film may play a role of flattening.
- the third interlayer insulating film 1037 can be formed using a material similar to that of the second interlayer insulating film or another known material.
- anodes 1024W, 1024R, 1024G, and 1024B of the EL device are anodes here, they may be cathodes. Further, in the case of a top emission type light emitting device as shown in FIG. 4, it is preferable that the anode be a reflective electrode.
- the EL layer 1028 has a structure described as the EL layer 103 in Embodiment 2 and has a device structure in which white light emission is obtained.
- the sealing substrate 1031 provided with colored layers can perform sealing.
- a black matrix 1035 may be provided on the sealing substrate 1031 so as to be located between pixels.
- the coloring layers (red coloring layer 1034R, green coloring layer 1034G, blue coloring layer 1034B) and the black matrix may be covered with the overcoat layer 1036. Note that a light-transmitting substrate is used as the sealing substrate 1031.
- full-color display is performed with four colors of red, green, blue, and white is shown, but there is no particular limitation, and four colors of red, yellow, green, and blue, and three colors of red, green, and blue are full-color. You may display.
- the microcavity structure can be preferably applied.
- An EL device having a microcavity structure can be obtained by using an anode as a reflective electrode and a cathode as a semi-transmissive/semi-reflective electrode. At least an EL layer is provided between the reflective electrode and the semi-transmissive/semi-reflective electrode, and at least a light emitting layer serving as a light emitting region is provided.
- the reflective electrode has a reflectance of visible light of 40% to 100%, preferably 70% to 100%, and a resistivity of 1 ⁇ 10 ⁇ 2 ⁇ cm or less.
- the semi-transmissive/semi-reflective electrode is a film having a visible light reflectance of 20% to 80%, preferably 40% to 70%, and a resistivity of 1 ⁇ 10 ⁇ 2 ⁇ cm or less. ..
- Light emitted from the light emitting layer included in the EL layer is reflected by the reflective electrode and the semi-transmissive/semi-reflective electrode and resonates.
- the optical distance between the reflective electrode and the semi-transmissive/semi-reflective electrode can be changed by changing the thickness of the transparent conductive film, the above-mentioned composite material, the carrier transport material, or the like.
- the light having the resonating wavelength can be strengthened and the light having the non-resonant wavelength can be attenuated.
- the light (first reflected light) reflected and returned by the reflective electrode causes a large interference with the light (first incident light) directly incident on the semi-transmissive/semi-reflective electrode from the light emitting layer, and thus is reflected. It is preferable to adjust the optical distance between the electrode and the light emitting layer to (2n-1) ⁇ /4 (where n is a natural number of 1 or more and ⁇ is the wavelength of the light emission to be amplified). By adjusting the optical distance, the phases of the first reflected light and the first incident light can be matched and the light emitted from the light emitting layer can be further amplified.
- the EL layer may have a structure having a plurality of light emitting layers or a structure having a single light emitting layer.
- the EL layer may have a structure having a plurality of light emitting layers or a structure having a single light emitting layer.
- a plurality of EL layers are provided in one EL device with a charge generation layer sandwiched therebetween, and a single or a plurality of light emitting layers are formed in each EL layer.
- microcavity structure By having a microcavity structure, it is possible to increase the emission intensity of the specific wavelength in the front direction, and thus it is possible to achieve low power consumption. Note that in the case of a light-emitting device which displays an image with sub-pixels of four colors of red, yellow, green, and blue, a micro-cavity structure adapted to the wavelength of each color can be applied to all sub-pixels in addition to the effect of improving the luminance by yellow emission. A light emitting device having favorable characteristics can be obtained.
- the light-emitting device in this embodiment uses the EL device described in Embodiment 2, a light-emitting device having favorable characteristics can be obtained. Specifically, the EL device described in Embodiment 2 has favorable emission efficiency and thus can be a light-emitting device with low power consumption.
- FIG. 5 shows a passive matrix light emitting device manufactured by applying the present invention.
- 5A is a perspective view showing the light emitting device
- FIG. 5B is a cross-sectional view taken along line XY of FIG. 5A.
- an EL layer 955 is provided over a substrate 951 between an electrode 952 and an electrode 956.
- the end portion of the electrode 952 is covered with an insulating layer 953.
- a partition layer 954 is provided over the insulating layer 953.
- the side wall of the partition layer 954 has an inclination such that the distance between one side wall and the other side wall becomes narrower as the side wall approaches the substrate surface.
- the cross section of the partition layer 954 in the short side direction has a trapezoidal shape, and the bottom side (the side facing the same direction as the surface direction of the insulating layer 953 and in contact with the insulating layer 953) is the upper side (the surface of the insulating layer 953).
- the direction is the same as the direction and is shorter than the side (not in contact with the insulating layer 953).
- the light emitting device described above is a light emitting device that can be suitably used as a display device that expresses an image because it can control a large number of minute EL devices arranged in a matrix.
- FIGS. 6B is a top view of the lighting device
- FIG. 6A is a cross-sectional view taken along the line ef in FIG. 6B.
- the anode 401 is formed over the light-transmitting substrate 400 which is a support.
- Anode 401 corresponds to anode 101 in the second embodiment.
- the anode 401 is formed using a light-transmitting material.
- a pad 412 for supplying a voltage to the cathode 404 is formed on the substrate 400.
- An EL layer 403 is formed on the anode 401.
- the EL layer 403 corresponds to the structure of the EL layer 103 in Embodiment 2 or the structure in which the light emitting units 511 and 512 and the charge generation layer 513 are combined. In addition, please refer to the said description about these structures.
- a cathode 404 is formed so as to cover the EL layer 403.
- Cathode 404 corresponds to cathode 102 in the second embodiment.
- the cathode 404 is formed of a material having high reflectance.
- the cathode 404 is supplied with a voltage by connecting to the pad 412.
- the lighting device described in this embodiment includes an EL device including the anode 401, the EL layer 403, and the cathode 404. Since the EL device has high emission efficiency, the lighting device in this embodiment can be a lighting device with low power consumption.
- the substrate 400 on which the EL device having the above structure is formed and the sealing substrate 407 are fixed to each other with sealing materials 405 and 406 and sealed, whereby the lighting device is completed.
- Either of the sealing materials 405 and 406 may be used.
- a desiccant can be mixed in the inner sealing material 406 (not shown in FIG. 6B), whereby moisture can be adsorbed and reliability is improved.
- the pad 412 and a part of the anode 401 can be used as an external input terminal by extending and providing the pad 412 and the anode 401 outside the sealing materials 405 and 406. Further, an IC chip 420 having a converter or the like may be provided thereon.
- the lighting device described in this embodiment uses the EL device described in Embodiment 2 as an EL device and can be a light-emitting device with low power consumption.
- Embodiment 5 examples of electronic devices each including the EL device described in Embodiment 2 are described.
- the EL device described in Embodiment 2 has high emission efficiency and low power consumption.
- the electronic device described in this embodiment can be an electronic device including a light-emitting portion with low power consumption.
- Examples of electronic equipment to which the EL device is applied include a television device (also referred to as a television or a television receiver), a monitor for a computer, a digital camera, a digital video camera, a digital photo frame, a mobile phone (a mobile phone, Large-sized game machines such as a portable game machine, a portable information terminal, a portable information terminal, a sound reproducing device, and a pachinko machine. Specific examples of these electronic devices are shown below.
- FIG. 7A shows an example of a television device.
- a display device 7103 is incorporated in a housing 7101 of the television device. Further, here, a structure is shown in which the housing 7101 is supported by a stand 7105. Images can be displayed on the display portion 7103, and the display portion 7103 is formed by arranging the EL devices described in Embodiment 2 in a matrix.
- the television device can be operated with an operation switch of the housing 7101 or a separate remote controller 7110.
- the operation key 7109 included in the remote controller 7110 can be used to operate a channel and volume, and an image displayed on the display portion 7103 can be operated.
- the remote controller 7110 may be provided with a display portion 7107 for displaying information output from the remote controller 7110.
- the television device is provided with a receiver, a modem, and the like.
- the receiver can receive general TV broadcasts, and by connecting to a wired or wireless communication network via a modem, it can be unidirectional (sender to receiver) or bidirectional (sender and receiver). It is also possible to perform information communication between the recipients, or between recipients).
- FIG. 7B1 is a computer, which includes a main body 7201, a housing 7202, a display portion 7203, a keyboard 7204, an external connection port 7205, a pointing device 7206, and the like. Note that this computer is manufactured by arranging the EL devices described in Embodiment 2 in a matrix and using them for the display portion 7203.
- the computer of FIG. 7B1 may have a configuration as shown in FIG. 7B2.
- the computer in FIG. 7B2 is provided with a second display portion 7210 instead of the keyboard 7204 and the pointing device 7206.
- the second display portion 7210 is a touch panel type, and input can be performed by operating the input display displayed on the second display portion 7210 with a finger or a dedicated pen. Further, the second display portion 7210 can display not only the input display but also other images.
- the display portion 7203 may also be a touch panel. Since the two screens are connected by the hinge, it is possible to prevent troubles such as damage or damage to the screens during storage or transportation.
- FIG. 7C shows an example of a mobile terminal.
- the mobile phone includes a display portion 7402 incorporated in a housing 7401, operation buttons 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like.
- the mobile phone includes a display portion 7402 which is manufactured by arranging the EL devices described in Embodiment 2 in a matrix.
- the mobile terminal illustrated in FIG. 7C can have a structure in which data can be input by touching the display portion 7402 with a finger or the like. In this case, operations such as making a call and composing a mail can be performed by touching the display portion 7402 with a finger or the like.
- the screen of the display portion 7402 mainly has three modes.
- the first is a display mode mainly for displaying images, and the second is an input mode mainly for inputting information such as characters.
- the third is a display+input mode in which the two modes of display mode and input mode are mixed.
- the display portion 7402 may be set to a character input mode mainly for inputting characters and input operation of characters displayed on the screen may be performed. In this case, it is preferable to display a keyboard or number buttons on most of the screen of the display portion 7402.
- the orientation (vertical or horizontal) of the mobile terminal is determined and the screen display of the display portion 7402 is automatically performed. It is possible to switch to each other.
- switching of the screen modes is performed by touching the display portion 7402 or operating the operation button 7403 of the housing 7401.
- the switching can be performed depending on the type of image displayed on the display portion 7402. For example, if the image signal displayed on the display unit is moving image data, the display mode is selected, and if it is text data, the input mode is selected.
- the screen mode is switched from the input mode to the display mode. You may control.
- the display portion 7402 can also function as an image sensor.
- personal identification can be performed by touching the display portion 7402 with a palm or a finger and capturing an image of a palm print, a fingerprint, or the like.
- a backlight that emits near-infrared light or a sensing light source that emits near-infrared light in the display portion an image of a finger vein, a palm vein, or the like can be taken.
- the applicable range of the light-emitting device including the EL device described in Embodiment 2 is extremely wide, and the light-emitting device can be applied to electronic devices in all fields.
- the EL device described in Embodiment 2 electronic devices with low power consumption can be obtained.
- FIG. 8A is a schematic diagram showing an example of a cleaning robot.
- the cleaning robot 5100 has a display 5101 arranged on the top surface, a plurality of cameras 5102 arranged on the side surface, a brush 5103, and operation buttons 5104. Although not shown, the cleaning robot 5100 has tires, a suction port, and the like on the lower surface.
- the cleaning robot 5100 additionally includes various sensors such as an infrared sensor, an ultrasonic sensor, an acceleration sensor, a piezo sensor, an optical sensor, and a gyro sensor.
- the cleaning robot 5100 also includes wireless communication means.
- the cleaning robot 5100 is self-propelled, detects dust 5120, and can suck dust from the suction port provided on the lower surface.
- the cleaning robot 5100 can analyze an image captured by the camera 5102 and determine the presence or absence of an obstacle such as a wall, furniture, or a step. In addition, when an object such as wiring that is likely to be entangled with the brush 5103 is detected by image analysis, the rotation of the brush 5103 can be stopped.
- the display 5101 can display the remaining amount of the battery, the amount of dust sucked, and the like.
- the display 5101 may display the route traveled by the cleaning robot 5100.
- the display 5101 may be a touch panel and the operation buttons 5104 may be provided on the display 5101.
- the cleaning robot 5100 can communicate with a mobile electronic device 5140 such as a smartphone.
- the image captured by the camera 5102 can be displayed on the mobile electronic device 5140. Therefore, the owner of the cleaning robot 5100 can know the state of the room even from the outside. Further, the display on the display 5101 can be confirmed with a mobile electronic device such as a smartphone.
- the light-emitting device described in Embodiment 3 can be used for the display 5101.
- the robot 2100 illustrated in FIG. 8B includes an arithmetic device 2110, an illuminance sensor 2101, a microphone 2102, an upper camera 2103, a speaker 2104, a display 2105, a lower camera 2106, an obstacle sensor 2107, and a moving mechanism 2108.
- the microphone 2102 has a function of detecting a user's voice and environmental sounds. Further, the speaker 2104 has a function of emitting sound. The robot 2100 can communicate with the user using the microphone 2102 and the speaker 2104.
- the display 2105 has a function of displaying various kinds of information.
- the robot 2100 can display the information desired by the user on the display 2105.
- the display 2105 may be equipped with a touch panel. Further, the display 2105 may be a removable information terminal, and by installing it at a fixed position of the robot 2100, charging and data transfer are possible.
- the upper camera 2103 and the lower camera 2106 have a function of capturing an image of the surroundings of the robot 2100. Further, the obstacle sensor 2107 can detect the presence or absence of an obstacle in the traveling direction when the robot 2100 moves forward by using the moving mechanism 2108. The robot 2100 can recognize the surrounding environment and safely move using the upper camera 2103, the lower camera 2106, and the obstacle sensor 2107.
- the light-emitting device described in Embodiment 3 can be used for the display 2105.
- FIG. 8C is a diagram showing an example of a goggle type display.
- the goggle type display includes, for example, a housing 5000, a display unit 5001, a speaker 5003, an LED lamp 5004, operation keys 5005 (including a power switch or an operation switch), a connection terminal 5006, a sensor 5007 (force, displacement, position, speed). , Acceleration, angular velocity, rotation speed, distance, light, liquid, magnetism, temperature, chemical substance, voice, time, hardness, electric field, current, voltage, power, radiation, flow rate, humidity, gradient, vibration, odor, or infrared (Including a function of measuring), a microphone 5008, a display portion 5002, a supporting portion 5012, an earphone 5013, and the like.
- the light-emitting device described in Embodiment 3 can be used for the display portion 5001 and the second display portion 5002.
- FIG. 9 illustrates an example in which the EL device described in Embodiment 2 is used for a table lamp which is a lighting device.
- the table lamp illustrated in FIG. 9 includes a housing 2001 and a light source 2002, and the lighting device described in Embodiment 3 may be used as the light source 2002.
- FIG. 10 shows an example in which the EL device described in Embodiment 2 is used as an indoor lighting device 3001.
- the EL device described in Embodiment 2 has high emission efficiency, and thus can be an illumination device with low power consumption. Since the EL device described in Embodiment 2 can have a large area, it can be used as a large-area lighting device. Further, since the EL device described in Embodiment 2 is thin, it can be used as a thin lighting device.
- the EL device described in Embodiment 2 can be mounted on a windshield or a dashboard of an automobile.
- FIG. 11 shows a mode in which the EL device described in Embodiment 2 is used for a windshield or a dashboard of an automobile.
- Display regions 5200 to 5203 are display regions provided using the EL device described in Embodiment 2.
- a display area 5200 and a display area 5201 are a display device provided with the EL device described in Embodiment 2 which is provided on a windshield of an automobile.
- the EL device described in Embodiment 2 can be a display device in a so-called see-through state in which the opposite side can be seen through by forming an anode and a cathode with a light-transmitting electrode. If the display is a see-through state, even if it is installed on the windshield of an automobile, it can be installed without obstructing the view.
- a light-transmitting transistor such as an organic transistor formed using an organic semiconductor material or a transistor formed using an oxide semiconductor is preferably used.
- a display region 5202 is a display device including the EL device described in Embodiment 2 which is provided in the pillar portion.
- the display area 5203 provided in the dashboard portion supplements the blind spot and enhances safety by displaying the image blocked by the vehicle body from the image pickup means provided outside the vehicle. You can By displaying the image so as to complement the invisible part, it is possible to confirm the safety more naturally and comfortably.
- the display area 5203 can also provide various information by displaying navigation information, a speedometer or a tachometer, a mileage, a fuel gauge, a gear state, an air conditioner setting, and the like. With respect to the display, its display items and layout can be changed appropriately according to the preference of the user. Note that these pieces of information can be displayed in the display areas 5200 to 5202.
- the display regions 5200 to 5203 can also be used as a lighting device.
- FIG. 12A and 12B show a portable information terminal 5150 that can be folded.
- the foldable portable information terminal 5150 includes a housing 5151, a display area 5152, and a bent portion 5153.
- FIG. 12A shows the mobile information terminal 5150 in an expanded state.
- FIG. 12B shows the portable information terminal 5150 in a folded state. Despite having a large display area 5152, the portable information terminal 5150 is compact and highly portable when folded.
- the display region 5152 can be folded in half by the bent portion 5153.
- the bent portion 5153 is composed of a stretchable member and a plurality of support members, and when it is folded, the stretchable member stretches.
- the bent portion 5153 is folded with a radius of curvature of 2 mm or more, preferably 3 mm or more.
- the display area 5152 may be a touch panel (input/output device) equipped with a touch sensor (input device).
- the light-emitting device described in Embodiment 3 can be used for the display region 5152.
- FIG. 13A to 13C show a foldable portable information terminal 9310.
- FIG. 13A shows the portable information terminal 9310 in the expanded state.
- FIG. 13B shows the portable information terminal 9310 in a state where it is being changed from one of the expanded state and the folded state to the other.
- FIG. 13C shows the portable information terminal 9310 in a folded state.
- the portable information terminal 9310 has excellent portability in a folded state and excellent displayability in a folded state due to a wide display area without a seam.
- the display panel 9311 is supported by three housings 9315 connected by a hinge 9313.
- the display panel 9311 may be a touch panel (input/output device) provided with a touch sensor (input device).
- the display panel 9311 can be reversibly deformed from the unfolded state to the folded state of the portable information terminal 9310 by bending between the two housings 9315 through the hinge 9313.
- the light-emitting device described in Embodiment 3 can be used for the display panel 9311.
- EL devices 1 and 2 manufactured using the EL device composition of one embodiment of the present invention described in the embodiment mode and EL devices manufactured using the comparative EL device composition were manufactured.
- the device 3 will be described.
- the structural formulas of the organic compounds used in this example are shown below.
- indium tin oxide containing silicon oxide (ITSO) was formed over a glass substrate by a sputtering method to form the anode 101.
- the film thickness was 70 nm and the electrode area was 2 mm ⁇ 2 mm.
- the substrate surface was washed with water, baked at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
- the substrate is introduced into a vacuum vapor deposition apparatus whose internal pressure is reduced to about 10 ⁇ 4 Pa, and vacuum baking is performed at 170° C. for 30 minutes in a heating chamber in the vacuum vapor deposition apparatus, and then the substrate is released for about 30 minutes.
- the substrate on which the anode 101 is formed is fixed to a substrate holder provided in a vacuum vapor deposition device so that the surface on which the anode 101 is formed faces downward, and vapor deposition using resistance heating is performed on the anode 101.
- DBT3P-II 4,4′,4′′-(benzene-1,3,5-triyl)tri(dibenzothiophene)
- VI molybdenum oxide
- N-(1,1′-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazole-represented by the above structural formula (ii) is formed on the hole injection layer 111.
- 3-yl)phenyl]-9,9-dimethyl-9H-fluoren-2-amine (abbreviation: PCBBiF) was evaporated to have a thickness of 20 nm, whereby the hole-transporting layer 112 was formed.
- a composition obtained by previously mixing fluoren-2-amine (abbreviation: PCBAF) in a weight ratio of 0.8:0.2 ( 9 mDBtBPNfpr:PCBAF) and the structural formula (v) above.
- PCBAF fluoren-2-amine
- lithium fluoride (LiF) is evaporated to a thickness of 1 nm to form an electron-injecting layer 115, and then aluminum is evaporated to a thickness of 200 nm, whereby the cathode 102 is formed.
- EL device 1 lithium fluoride (LiF) is evaporated to a thickness of 1 nm to form an electron-injecting layer 115, and then aluminum is evaporated to a thickness of 200 nm, whereby the cathode 102 is formed.
- PCBAF in the light emitting layer of the EL device 1 is represented by N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-bis(9,9-) represented by the structural formula (vii).
- Dimethyl-9H-fluoren-2-yl)amine abbreviation: PCBFF was used, and the same procedure as in EL device 1 was performed.
- -9H-carbazole (abbreviation: mPCCzPTzn-02) was used, and the same procedure as in EL device 1 was performed.
- 8((beta)N2)-4mDBtPBfpm and PCBNBF were vapor-deposited from the same vapor deposition source as a sample of the composition which was mixed beforehand.
- the device structures of the EL devices 1 to 3 are summarized in the table below.
- Table 2 shows the vacuum (1 ⁇ 10 ⁇ 2 Pa or so) of the organic compound of each of the two devices used as the composition mixed in advance when forming the light emitting layer 113 of the EL devices 1 to 3 by vapor deposition.
- the result of having measured the 5% weight loss temperature in () is shown.
- the 5% weight loss temperature was determined by thermogravimetry-differential thermal analysis (TG-DTA: Thermogravimetry-Differential Thermal Analysis), and from the relationship between weight and temperature (thermogravimetric measurement).
- TG-DTA2410SA manufactured by Bruker AXS KK
- the difference in the 5% weight loss temperature of the organic compound contained in the sample of the premixed composition was 43°C for EL device 1, 21°C for EL device 2 and 66°C for EL device 3. It was
- the luminance-current density characteristic of the EL device 1 is shown in FIG. 15, the luminance-voltage characteristic is shown in FIG. 16, the current-voltage characteristic is shown in FIG. 17, the external quantum efficiency-luminance characteristic is shown in FIG. 18, the emission spectrum is shown in FIG.
- the luminance-current density characteristic of the EL device 2 is shown in FIG. 20, the luminance-voltage characteristic is shown in FIG. 21, the current-voltage characteristic is shown in FIG. 22, the external quantum efficiency-luminance characteristic is shown in FIG. 23, the emission spectrum is shown in FIG.
- FIG. 25 shows the luminance-current density characteristic of the EL device 3
- FIG. 26 shows the luminance-voltage characteristic
- FIG. 27 shows the current-voltage characteristic
- FIG. 28 shows the external quantum efficiency-luminance characteristic
- FIG. 29 shows the emission spectrum. It was
- the following table shows the main characteristics of each EL device near a luminance of 1000 cd/cm 2 .
- the characteristics of the devices that are vapor-deposited by different vapor deposition sources are also shown as references.
- the EL device 1 and the EL device 2 all showed equally good initial characteristics.
- the EL device 3 is an EL device having a large variation in characteristics.
- FIGS. 30 to 32 and FIG. 39 show graphs showing changes in luminance with respect to driving time at a current density of 75 mA/cm 2
- FIG. 30 shows the results of the EL device 1
- FIGS. 31 and 39 show the results of the EL device 2
- FIG. 32 shows the results of the EL device 3.
- FIG. 39 is a graph showing changes in luminance with respect to driving time at a high temperature of 85° C. From these results, it was found that both the EL device 1 and the EL device 2 have similarly good life. On the other hand, the EL device 3 had a large variation in life, and the device characteristics were not stable.
- the composition of one embodiment of the present invention in which the difference in 5% weight loss temperature under high vacuum of the material forming the composition in which two kinds of materials which are evaporation samples are mixed is 50° C. or lower
- the EL device 1 and the EL device 2 which are manufactured by using the thing are the EL devices in which the characteristics are less deteriorated due to the continuous vapor deposition.
- the EL device 3 using a sample having a difference of 66° C. in the 5% weight loss temperature of the material constituting the composition which is the sample for vapor deposition under high vacuum is an EL device having a large deterioration or variation in characteristics. I understood it.
- the measurement was performed by Acquity UPLC (registered trademark) manufactured by Waters.
- the column used was Acquity UPLC BEH C8 (2.1 ⁇ 100 mm 1.7 ⁇ m), and the column temperature was 40° C.
- mobile phase A was acetonitrile and mobile phase B was a 0.1% formic acid aqueous solution.
- the injection amount of the sample was 5.0 ⁇ L. The results are shown in the table below.
- the proportion of 9mDBtBPNfpr and PCBFF in the EL device vapor-deposited using the EL device composition of one embodiment of the present invention is almost the same as the composition of the EL device composition premixed, and The composition of the sample remaining in the vapor deposition source had a similar composition. That is, it was found that the composition for an EL device of one embodiment of the present invention was a composition for an EL device in which a vapor-deposited film was unlikely to undergo a compositional change even if repeated vapor deposition was performed. Further, as a result, it was found that the characteristics of EL devices manufactured using the composition are less likely to vary greatly.
- an EL device 4 manufactured using the EL device composition of one embodiment of the present invention described in the embodiment mode will be described.
- the structural formulas of the organic compounds used in this example are shown below.
- indium tin oxide containing silicon oxide (ITSO) was formed over a glass substrate by a sputtering method to form the anode 101.
- the film thickness was 70 nm and the electrode area was 2 mm ⁇ 2 mm.
- the substrate surface was washed with water, baked at 200° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
- the substrate is introduced into a vacuum vapor deposition apparatus whose internal pressure is reduced to about 10 ⁇ 4 Pa, and vacuum baking is performed at 170° C. for 30 minutes in a heating chamber in the vacuum vapor deposition apparatus, and then the substrate is released for about 30 minutes.
- the substrate on which the anode 101 is formed is fixed to a substrate holder provided in a vacuum vapor deposition device so that the surface on which the anode 101 is formed faces downward, and vapor deposition using resistance heating is performed on the anode 101.
- DBT3P-II 4,4′,4′′-(benzene-1,3,5-triyl)tri(dibenzothiophene)
- VI molybdenum oxide
- mBPCCBP -4-yl-9H,9'H-3,3'-bicarbazole
- mBPCCBP -4-yl-9H,9'H-3,3'-bicarbazole
- 8BP-4mDBtPBfpm and mBPCCBP were vapor-deposited by the same vapor deposition source as a premixed sample.
- lithium fluoride (LiF) is evaporated to a thickness of 1 nm to form an electron-injecting layer 115, and then aluminum is evaporated to a thickness of 200 nm, whereby the cathode 102 is formed.
- EL device 4 lithium fluoride (LiF) is evaporated to a thickness of 1 nm to form an electron-injecting layer 115, and then aluminum is evaporated to a thickness of 200 nm, whereby the cathode 102 is formed.
- the device structure of the EL device 4 is summarized in the table below.
- 5% in vacuum (about 1 ⁇ 10 ⁇ 2 Pa) of two kinds of organic compounds of each device used as a composition premixed when the light emitting layer 113 of the EL device 4 was formed by vapor deposition The result of having measured the weight reduction temperature is shown.
- the 5% weight loss temperature was determined by thermogravimetry-differential thermal analysis (TG-DTA: Thermogravimetry-Differential Thermal Analysis), and from the relationship between weight and temperature (thermogravimetric measurement).
- TG-DTA2410SA Thermogravimetry-Differential Thermal Analysis
- the difference in 5% weight loss temperature of the organic compounds contained in the sample of the premixed composition used for manufacturing EL device 4 was 14°C.
- the operation of sealing the EL device 4 with a glass substrate in a glove box in a nitrogen atmosphere so that the EL device is not exposed to the atmosphere applying a sealing material around the device and performing UV treatment at the time of sealing, at 80° C.) After heat treatment for 1 hour), the initial characteristics were measured.
- the measuring method is the same as in Example 1.
- FIG. 33 shows the luminance-current density characteristics
- FIG. 34 shows the luminance-voltage characteristics
- FIG. 35 shows the current-voltage characteristics
- FIG. 36 shows the external quantum efficiency-luminance characteristics
- FIG. 37 shows the emission spectrum.
- the following table shows the main characteristics of the EL device 4 near a luminance of 1000 cd/cm 2 .
- the characteristics of the device that is vapor-deposited by different vapor deposition sources are also shown as the reference.
- each EL device was a device having an equally good life.
- the composition of one embodiment of the present invention in which the difference in 5% weight loss temperature under high vacuum of the materials constituting the composition in which two kinds of materials which are evaporation samples are mixed is 50° C. or less is used. It was found that the EL device 4 manufactured as described above is an EL device in which the characteristics and the lifetime are less deteriorated due to continuous vapor deposition.
- Step 1 Synthesis of 6-chloro-3-(2-methoxynaphthalen-1-yl)pyrazin-2-amine> First, 4.37 g of 3-bromo-6-chloropyrazin-2-amine, 4.23 g of 2-methoxynaphthalene-1-boronic acid, 4.14 g of potassium fluoride, and 75 mL of dehydrated tetrahydrofuran were placed in a three-necked flask equipped with a reflux tube. And the inside was replaced with nitrogen.
- Step 1 The synthetic scheme of Step 1 is shown below.
- Step 2 Synthesis of 9-chloronaphtho[1′,2′:4,5]furo[2,3-b]pyrazine>
- 2.18 g of 6-chloro-3-(2-methoxynaphthalen-1-yl)pyrazin-2-amine obtained in Step 1 above 63 mL of dehydrated tetrahydrofuran and 84 mL of glacial acetic acid were placed in a three-necked flask, and the inside was replaced with nitrogen. Replaced. After cooling the flask to ⁇ 10° C., 2.8 mL of tert-butyl nitrite was added dropwise, and the mixture was stirred at ⁇ 10° C.
- Step 2 The synthetic scheme of Step 2 is shown below.
- Step 3 9-[(3′-dibenzothiophen-4-yl)biphenyl-3-yl]naphtho[1′,2′:4,5]furo[2,3-b]pyrazine (abbreviation: 9mDBtBPNfpr) Synthesis> Furthermore, 1.48 g of 9-chloronaphtho[1',2':4,5]furo[2,3-b]pyrazine obtained in Step 2 above, 3'-(4-dibenzothiophene)-1,1'- Biphenyl-3-boronic acid (3.41 g), 2M aqueous potassium carbonate solution (8.8 mL), toluene (100 mL) and ethanol (10 mL) were placed in a three-necked flask, and the inside of the flask was replaced with nitrogen.
- 9mDBtBPNfpr 9mDBtBPNfpr
- the obtained suspension was suction filtered and washed with water and ethanol.
- the obtained solid was dissolved in toluene, filtered through a filter aid in which Celite, alumina, and Celite were laminated in this order, and then recrystallized with a mixed solvent of toluene and hexane to obtain the target product (pale yellow solid, Yield 2.66 g, yield 82%).
- This filter cake was dissolved with hot toluene and passed through a filter aid filled with Celite, alumina, and Celite in this order.
- the obtained solution was concentrated, dried, and recrystallized from toluene to obtain 1.16 g of a target white solid in a yield of 65%.
- 1.15 g of the obtained white solid was purified by sublimation by the train sublimation method.
- the sublimation purification conditions were such that the pressure was 2.64 Pa and the solid was heated at 365° C. while flowing an argon gas at a flow rate of 10 mL/min. After sublimation purification, 0.958 g (recovery rate 83%, white solid) of 8( ⁇ N2)-4mDBtPBfpm of the present invention was obtained.
- the synthetic scheme is shown below.
- This mixture was heated to 60° C., 23.3 mg of palladium(II) acetate and 66.4 mg of di(1-adamantyl)-n-butylphosphine were added, and the mixture was stirred at 120° C. for 27 hours.
- Water was added to this reaction solution and suction filtration was performed, and the obtained filter cake was washed with water, ethanol and toluene.
- This filter cake was dissolved with hot toluene and passed through a filter aid filled with Celite, alumina, and Celite in this order.
- the obtained solution was concentrated, dried, and recrystallized with toluene to obtain 1.28 g of a target white solid in a yield of 74%.
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Abstract
Description
図2Aおよび図2Bは、アクティブマトリクス型発光装置の概念図である。
図3Aおよび図3Bは、アクティブマトリクス型発光装置の概念図である。
図4は、アクティブマトリクス型発光装置の概念図である。
図5Aおよび図5Bは、パッシブマトリクス型発光装置の概念図である。
図6Aおよび図6Bは、照明装置を表す図である。
図7A、図7B1、図7B2および図7Cは、電子機器を表す図である。
図8A乃至図8Cは、電子機器を表す図である。
図9は、照明装置を表す図である。
図10は、照明装置を表す図である。
図11は、車載表示装置及び照明装置を表す図である。
図12Aおよび図12Bは、電子機器を表す図である。
図13A乃至図13Cは、電子機器を表す図である。
図14Aおよび図14Bは、蒸着装置の模式図である。
図15は、ELデバイス1の輝度−電流密度特性を表す図である。
図16は、ELデバイス1の輝度−電圧特性を表す図である。
図17は、ELデバイス1の電流−電圧特性を表す図である。
図18は、ELデバイス1の外部量子効率−輝度特性を表す図である。
図19は、ELデバイス1の発光スペクトルを表す図である。
図20は、ELデバイス2の輝度−電流密度特性を表す図である。
図21は、ELデバイス2の輝度−電圧特性を表す図である。
図22は、ELデバイス2の電流−電圧特性を表す図である。
図23は、ELデバイス2の外部量子効率−輝度特性を表す図である。
図24は、ELデバイス2の発光スペクトルを表す図である。
図25は、ELデバイス3の輝度−電流密度特性を表す図である。
図26は、ELデバイス3の輝度−電圧特性を表す図である。
図27は、ELデバイス3の電流−電圧特性を表す図である。
図28は、ELデバイス3の外部量子効率−輝度特性を表す図である。
図29は、ELデバイス3の発光スペクトルを表す図である。
図30は、ELデバイス1の輝度−時間変化特性を表す図である。
図31は、ELデバイス2の輝度−時間変化特性を表す図である。
図32は、ELデバイス3の輝度−時間変化特性を表す図である。
図33は、ELデバイス4の輝度−電流密度特性を表す図である。
図34は、ELデバイス4の輝度−電圧特性を表す図である。
図35は、ELデバイス4の電流−電圧特性を表す図である。
図36は、ELデバイス4の外部量子効率−輝度特性を表す図である。
図37は、ELデバイス4の発光スペクトルを表す図である。
図38は、ELデバイス4の輝度−時間変化特性を表す図である。
図39は、ELデバイス2の高温における輝度−時間変化特性を表す図である。
有機ELデバイスは通常一対の電極間に有機化合物を含むEL層を挟んで形成されている。EL層は、機能分離された積層構造を有する。その積層構造は例えば図1Aに示したEL層103のように、正孔注入層111、正孔輸送層112、発光層113、電子輸送層114、電子注入層115などの他、キャリアブロック層、電荷発生層などの各機能層から構成される。
本実施の形態では、実施の形態1で示したELデバイス用組成物を用いて作製することが可能なELデバイスの詳しい態様について説明する。図1に、実施の形態1で示したELデバイス用組成物を用いて作製することが可能なELデバイスを示す。図1Aに示したELデバイスは、陽極101と、陰極102、EL層103を有する。
本実施の形態では、実施の形態2に記載のELデバイスを用いた発光装置について説明する。
本実施の形態では、実施の形態2に記載のELデバイスを照明装置として用いる例を図6を参照しながら説明する。図6Bは照明装置の上面図、図6Aは図6Bにおけるe−f断面図である。
本実施の形態では、実施の形態2に記載のELデバイスをその一部に含む電子機器の例について説明する。実施の形態2に記載のELデバイスは発光効率が良好であり、消費電力が小さいELデバイスである。その結果、本実施の形態に記載の電子機器は、消費電力が小さい発光部を有する電子機器とすることが可能である。
まず、ガラス基板上に、酸化珪素を含むインジウム錫酸化物(ITSO)をスパッタリング法にて成膜し、陽極101を形成した。なお、その膜厚は70nmとし、電極面積は2mm×2mmとした。
ELデバイス2はELデバイス1の発光層におけるPCBAFを上記構造式(vii)で表されるN−[4−(9−フェニル−9H−カルバゾール−3−イル)フェニル]−ビス(9,9−ジメチル−9H−フルオレン−2−イル)アミン(略称:PCBFF)に変えた他は、ELデバイス1と同様に作製した。なお、発光層113を形成する際、9mDBtBPNfprとPCBFFはあらかじめ重量比が0.8:0.2(=9mDBtBPNfpr:PCBFF)となるように混合した組成物の試料として、同一の蒸着源により蒸着した。
ELデバイス3は、ELデバイス1の正孔輸送層112におけるPCBBiFを上記構造式(viii)で表される4,4’−ジフェニル−4’’−(9−フェニル−9H−カルバゾール−3−イル)トリフェニルアミン(略称:PCBBi1BP)に変え、発光層113を上記構造式(ix)で表される8−(2,2’−ビナフチル−6−イル)−4−[3−(ジベンゾチオフェン−4−イル)フェニル−[1]ベンゾフロ[3,2−d]ピリミジン(略称:8(βN2)−4mDBtPBfpm)と、上記構造式(x)で表される9,9−ジメチル−N−[4−(1−ナフチル)フェニル]−N−[4−(9−フェニル−9H−カルバゾール−3−イル)フェニル]−9H−フルオレン−2−アミン(略称:PCBNBF)とをあらかじめ重量比が0.7:0.3(=8(βN2)−4mDBtPBfpm):PCBNBF)となるように混合した組成物と、[Ir(dmdppr−m5CP)2(dpm)])とを、重量比で1:0.1(=[8(βN2)−4mDBtPBfpmとPCBNBFを混合した組成物]:[Ir(dmdppr−m5CP)2(dpm)])となるように40nm共蒸着して形成し、電子輸送層114における9mDBtBPNfprを、上記構造式(xi)で表される9−[3−(4,6−ジフェニル−1,3,5−トリアジン−2−イル)フェニル]−9’−フェニル−2,3’−ビ−9H−カルバゾール(略称:mPCCzPTzn−02)に変えた他はELデバイス1と同様に作製した。なお、発光層113を形成する際、8(βN2)−4mDBtPBfpmとPCBNBFはあらかじめ混合した組成物の試料として、同一の蒸着源により蒸着した。
まず、ガラス基板上に、酸化珪素を含むインジウム錫酸化物(ITSO)をスパッタリング法にて成膜し、陽極101を形成した。なお、その膜厚は70nmとし、電極面積は2mm×2mmとした。
実施例で使用した9mDBtBPNfpr、8(βN2)−4mDBtPBfpmおよび8BP−4mDBtPBfpmは未公開の物質であるため、各々の合成方法について説明する。
実施例1において、構造式(iii)として示した9−[(3’−ジベンゾチオフェン−4−イル)ビフェニル−3−イル]ナフト[1’,2’:4,5]フロ[2,3−b]ピラジン(略称:9mDBtBPNfpr)の合成方法について説明する。なお、9mDBtBPNfprの構造を以下に示す。
まず、3−ブロモ−6−クロロピラジン−2−アミン4.37gと2−メトキシナフタレン−1−ボロン酸4.23g、フッ化カリウム4.14g、脱水テトラヒドロフラン75mLを、還流管を付けた三口フラスコに入れ、内部を窒素置換した。フラスコ内を減圧下で撹拌することで脱気した後、トリス(ジベンジリデンアセトン)ジパラジウム(0)(略称:Pd2(dba)3)0.57g、トリ−tert−ブチルホスフィン(略称:t−Bu3P)4.5mLを加え、80℃で54時間撹拌し、反応させた。
次に、上記ステップ1で得た6−クロロ−3−(2−メトキシナフタレン−1−イル)ピラジン−2−アミン2.18gと脱水テトラヒドロフラン63mL、氷酢酸84mLを三口フラスコに入れ、内部を窒素置換した。フラスコを−10℃に冷却した後、亜硝酸tert−ブチル2.8mLを滴下し、−10℃で30分、0℃で3時間攪拌した。所定時間経過後、得られた懸濁液に水250mLを加え、吸引ろ過することにより、目的のピラジン誘導体を得た(黄白色粉末、収量1.48g、収率77%)。ステップ2の合成スキームを下に示す。
さらに、上記ステップ2で得た9−クロロナフト[1’,2’:4,5]フロ[2,3−b]ピラジン1.48g、3’−(4−ジベンゾチオフェン)−1,1’−ビフェニル−3−ボロン酸3.41g、2M炭酸カリウム水溶液8.8mL、トルエン100mL、エタノール10mLを三口フラスコに入れ、内部を窒素置換した。フラスコ内を減圧下で撹拌することで脱気した後、ビス(トリフェニルホスフィン)パラジウム(II)ジクロリド(略称:PdCl2(PPh3)2)0.84gを加え、80℃で18時間撹拌し、反応させた。
実施例1において、構造式(ix)として示した8−[(2,2’−ビナフタレン)−6−イル]−4−[3−(ジベンゾチオフェン−4−イル)フェニル−[1]ベンゾフロ[3,2−d]ピリミジン(略称:8(βN2)−4mDBtPBfpm)の合成方法について説明する。8(βN2)−4mDBtPBfpmの構造を以下に示す。
8−クロロ−4−[3−(ジベンゾチオフェン−4−イル)フェニル]−[1]ベンゾフロ[3,2−d]ピリミジン1.21g、[2,2’−ビナフタレン]−6−イルボロン酸0.857g、リン酸三カリウム1.67g、ジグリム26mL、t−ブタノール0.583gを三口フラスコに入れ、フラスコ内を減圧下攪拌することで脱気し、窒素置換した。
実施例2において、構造式(xii)として示した8−(1,1’−ビフェニル−4−イル)−4−[3−(ジベンゾチオフェン−4−イル)フェニル]−[1]ベンゾフロ[3,2−d]ピリミジン(略称:8BP−4mDBtPBfpm)の合成方法について説明する。8BP−4mDBtPBfpmの構造を以下に示す。
8−クロロ−4−[3−(ジベンゾチオフェン−4−イル)フェニル]−[1]ベンゾフロ[3,2−d]ピリミジン1.37g、4−ビフェニルボロン酸0.657g、リン酸三カリウム1.91g、ジグリム30mL、t−ブタノール0.662gを三口フラスコに入れ、フラスコ内を減圧下攪拌することで脱気し、窒素置換した。
Claims (22)
- 少なくとも2種以上の有機化合物を含むELデバイス用組成物であって、
前記2種以上の有機化合物間の0.1Pa以下の圧力下における熱重量測定で測定した5%重量減少温度の差が、50度以下であるELデバイス用組成物。 - 第1の有機化合物と、
第2の有機化合物とを含むELデバイス用組成物であって、
前記第1の有機化合物と、前記第2の有機化合物との間の0.1Pa以下の圧力下における熱重量測定で測定した5%重量減少温度の差が、50度以下であるELデバイス用組成物。 - 請求項2において、
前記第1の有機化合物が電子輸送性を有し、
前記第2の有機化合物が正孔輸送性を有するELデバイス用組成物。 - 請求項2または請求項3において、
前記第1の有機化合物が、ベンゾフロジアジン骨格またはベンゾチオジアジン骨格を有するELデバイス用組成物。 - 請求項2または請求項3において、
前記第1の有機化合物がナフトフロピラジン骨格、フェナントロフロピラジン骨格、ナフトチオピラジン骨格、またはフェナントロチオピラジン骨格のいずれか一を有するELデバイス用組成物。 - 請求項2または請求項3において、
前記第1の有機化合物がベンゾフロピリミジン骨格またはベンゾチオピリミジン骨格を有するELデバイス用組成物。 - 請求項2または請求項3において、
前記第1の有機化合物が下記一般式(G2)で表されるELデバイス用組成物。
(式中、Qは酸素または硫黄を表す。Ar1、Ar2、Ar3、およびAr4はそれぞれ独立に、置換もしくは無置換の芳香族炭化水素環を表し、前記芳香族炭化水素環の置換基は、炭素数1乃至6のアルキル基、または炭素数1乃至6のアルコキシ基、または炭素数5乃至7の単環式飽和炭化水素基、または炭素数7乃至10の多環式飽和炭化水素基、またはシアノ基のいずれか一であり、前記芳香族炭化水素環を形成する炭素数は6以上25以下である。また、mおよびnはそれぞれ0または1である。また、Aは総炭素数12乃至100の基であり、かつ、ベンゼン環、ナフタレン環、フルオレン環、フェナントレン環、トリフェニレン環、ジベンゾチオフェン環を含む複素芳香環、ジベンゾフラン環を含む複素芳香環、カルバゾール環を含む複素芳香環、ベンゾイミダゾール環、トリフェニルアミン構造のいずれか一または複数を有する。また、R1は、水素、炭素数1乃至6のアルキル基、置換もしくは無置換の炭素数5乃至7の単環式飽和炭化水素、置換もしくは無置換の炭素数7乃至10の多環式飽和炭化水素、置換もしくは無置換の炭素数6乃至13のアリール基、または置換もしくは無置換の炭素数3乃至12のヘテロアリール基を表す。) - 請求項2乃至請求項10のいずれか一項において、
前記第2の有機化合物が芳香族アミン骨格を有するELデバイス用組成物。 - 請求項2乃至請求項10のいずれか一項において、
前記第2の有機化合物がカルバゾール骨格を有するELデバイス用組成物。 - 請求項2乃至請求項10のいずれか一項において、
前記第2の有機化合物がトリアリールアミン骨格を有するELデバイス用組成物。 - 請求項2乃至請求項10のいずれか一項において、
前記第2の有機化合物がビカルバゾール骨格を有するELデバイス用組成物。 - 前記請求項14において、
前記ビカルバゾール骨格は、2位乃至4位のいずれかにおいて2つのカルバゾリル基が互いに結合するELデバイス用組成物。 - 請求項2乃至請求項10のいずれか一項において、
前記第2の有機化合物がトリアリールアミン骨格とカルバゾール骨格とを有するELデバイス用組成物。 - 請求項16において、
前記トリアリールアミンにおける窒素原子と前記カルバゾール骨格とが、フェニレン基を介して結合するELデバイス用組成物。 - 請求項16または請求項17において、
前記カルバゾール骨格が2位乃至4位または9位で結合するELデバイス用組成物。 - 請求項2乃至請求項18のいずれか一項において、
前記第2の有機化合物が少なくとも一つのフルオレン骨格を有するELデバイス用組成物。 - 請求項2乃至請求項19のいずれか一項において、
前記第1の有機化合物と前記第2の有機化合物とが励起錯体を形成する組み合わせであるELデバイス用組成物。 - 請求項1乃至請求項20のいずれか一項において、
前記5%重量減少温度の差が、40度以下であるELデバイス用組成物。 - 請求項1乃至請求項20のいずれか一項において、
前記5%重量減少温度の差が、30度以下であるELデバイス用組成物。
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| CN201980069664.4A CN112912461A (zh) | 2018-11-30 | 2019-11-20 | El器件用组成物 |
| KR1020217019521A KR20210096169A (ko) | 2018-11-30 | 2019-11-20 | El 디바이스용 조성물 |
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| WO2022229780A1 (ja) * | 2021-04-30 | 2022-11-03 | 株式会社半導体エネルギー研究所 | 発光装置および電子機器 |
Also Published As
| Publication number | Publication date |
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| JP2025113293A (ja) | 2025-08-01 |
| US20210395271A1 (en) | 2021-12-23 |
| KR20210096169A (ko) | 2021-08-04 |
| JP2023174743A (ja) | 2023-12-08 |
| US12145946B2 (en) | 2024-11-19 |
| CN112912461A (zh) | 2021-06-04 |
| JPWO2020109927A1 (ja) | 2021-12-16 |
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