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WO2019043501A1 - Dispositif électronique, élément électroluminescent, batterie solaire, dispositif électroluminescent, appareil électronique et dispositif d'éclairage - Google Patents

Dispositif électronique, élément électroluminescent, batterie solaire, dispositif électroluminescent, appareil électronique et dispositif d'éclairage Download PDF

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Publication number
WO2019043501A1
WO2019043501A1 PCT/IB2018/056298 IB2018056298W WO2019043501A1 WO 2019043501 A1 WO2019043501 A1 WO 2019043501A1 IB 2018056298 W IB2018056298 W IB 2018056298W WO 2019043501 A1 WO2019043501 A1 WO 2019043501A1
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layer
substance
light
electronic device
emitting element
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PCT/IB2018/056298
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English (en)
Japanese (ja)
Inventor
渡部剛吉
大澤信晴
瀬尾哲史
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株式会社半導体エネルギー研究所
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Publication of WO2019043501A1 publication Critical patent/WO2019043501A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/875—Arrangements for extracting light from the devices
    • H10K59/879—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses

Definitions

  • One embodiment of the present invention relates to a light-emitting element, a display module, a lighting module, a display device, a light-emitting device, an electronic device, and a lighting device.
  • a light-emitting element a display module, a lighting module, a display device, a light-emitting device, an electronic device, and a lighting device.
  • the technical field of one embodiment of the invention disclosed in the present specification and the like relates to an object, a method, or a method of manufacturing.
  • one aspect of the present invention relates to a process, a machine, a manufacture, or a composition (composition of matter).
  • the technical field of one embodiment of the present invention disclosed in the present specification more specifically includes a semiconductor device, a display device, a liquid crystal display device, a light emitting device, a lighting device, a power storage device, a storage device, an imaging device, and the like.
  • a driving method or a manufacturing method thereof can be mentioned as an example.
  • organic EL element utilizing electroluminescence (EL) using an organic compound
  • the basic configuration of these light emitting elements is one in which an organic compound layer (EL layer) containing a light emitting material is sandwiched between a pair of electrodes. A voltage is applied to this element to inject carriers, and by using the recombination energy of the carriers, light emission from the light-emitting material can be obtained.
  • EL layer organic compound layer
  • Such a light emitting element is self-luminous, when it is used as a pixel of a display, it has advantages such as high visibility and no need for a backlight as compared to liquid crystal, and is suitable as a flat panel display element.
  • a display using such a light emitting element can be manufactured to be thin and light, which is also a great advantage. Furthermore, it is one of the features that the response speed is very fast.
  • these light emitting elements can form light emitting layers continuously in two dimensions, light emission can be obtained in a planar manner. This is a feature that is difficult to obtain with point light sources represented by incandescent bulbs and LEDs, or linear light sources represented by fluorescent lamps, and therefore has high utility value as a surface light source applicable to illumination and the like.
  • Non-Patent Document 1 One of the problems often encountered when talking about organic EL elements is low light extraction efficiency.
  • the attenuation of light emission due to reflection caused by the difference in refractive index is a major factor to lower the efficiency of the device, and in order to reduce this influence, a layer of low refractive index material is formed inside the EL layer.
  • a layer of low refractive index material is formed inside the EL layer.
  • a light emitting element having this configuration can be a light emitting element having higher light emission efficiency than a light emitting element having a conventional configuration, but such a layer adversely affects other important characteristics of the light emitting element. It is not easy to form it inside the EL layer without giving it.
  • an object of one embodiment of the present invention is to provide a novel light emitting element.
  • Another object is to provide a light-emitting element with high luminous efficiency.
  • another object of the present invention is to provide a highly reliable light-emitting device, an electronic device, and a display device.
  • another object of the present invention is to provide a light-emitting device with low power consumption, an electronic device, and a display device.
  • the present invention should solve any one of the above-mentioned problems.
  • One embodiment of the present invention comprises a first electrode, a second electrode, and a first layer sandwiched between the first electrode and the second electrode, the first layer being And at least a second layer and a third layer, wherein the second layer is located between the third layer and the first electrode, and the second layer is formed of a first substance and a second substance.
  • the second substance includes a second substance and a third substance, the first substance is a compound containing fluorine, the second substance is an organic compound having a hole transporting property, and the third substance is the third substance. It is an electronic device which is a substance showing an electron accepting property to the substance of 2.
  • another embodiment of the present invention is an electronic device having the above-described structure, in which the refractive index of the second layer is lower than the refractive index of the third layer.
  • another configuration of the present invention is the electronic device having the above configuration, wherein the refractive index of the second layer is lower than that of the third layer by 0.1 or more.
  • another embodiment of the present invention is the electronic device having the above-described structure, in which the refractive index of the second layer is 1.70 or less.
  • another embodiment of the present invention is the electronic device as described above, wherein the first substance is any of an alkali metal fluoride, an alkaline earth metal fluoride and an alkyl fluoride.
  • another embodiment of the present invention is the electronic device as described above, wherein the first substance is a fluoride of an alkaline earth metal.
  • another embodiment of the present invention is the electronic device as described above, in which the first substance is any of lithium fluoride, calcium fluoride and magnesium fluoride.
  • another embodiment of the present invention is the electronic device as described above, in which the first substance is fluorinated alkyl.
  • the third substance includes a transition metal oxide, an oxide of a metal belonging to Groups 4 to 8 in the periodic table of the elements, and an electron-withdrawing group. It is an electronic device which is any one or more of organic compounds.
  • another embodiment of the present invention is the electronic device having the above structure, wherein the third substance is an organic compound having an electron withdrawing group.
  • another embodiment of the present invention is the electronic device as described above, in which the electron withdrawing group is a fluoro group or a cyano group.
  • another aspect of the present invention is the above structure, wherein the third substance is titanium oxide, vanadium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, rhenium oxide, ruthenium oxide, chromium Oxide, zirconium oxide, hafnium oxide, silver oxide, 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane, chloranil, 2,3,6,7,10 , 11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane, ⁇ , ⁇ ', ⁇ ' Electronic device which is one or more selected from '-1,2,3-cyclopropanetriylidenetris [4-cyano-2,3,5,6-tetrafluorobenzeneacetonitrile] The scan is.
  • another embodiment of the present invention is the electronic device having the above-described structure, in which the third substance is molybdenum oxide.
  • another embodiment of the present invention is the electronic device as described above, wherein the second substance is a ⁇ electron excess heteroaromatic compound or an aromatic amine compound.
  • another embodiment of the present invention is the electronic device having the above structure in which the HOMO level of the second substance is -5.7 eV or more.
  • another embodiment of the present invention is the electronic device having the above structure, in which the HOMO level of the second substance is ⁇ 5.5 eV or more.
  • another embodiment of the present invention is the electronic device according to the above configuration, in which the first electrode transmits visible light.
  • another embodiment of the present invention is the electronic device having the above structure, in which the atomic ratio of fluorine atoms in the second layer is 20% or more.
  • another aspect of the present invention is the electronic device having a spin density of 1.0 ⁇ 10 18 spins / cm 3 or more when ESR measurement is performed on the material forming the second layer in the above configuration. .
  • the first layer further includes a fourth layer, and the fourth layer is between the second layer and the third layer. And disposed in contact with the second layer, the fourth layer includes a fourth substance and a fifth substance, and the fourth substance is an organic material having a hole transportability.
  • the electronic device is a compound, and the fifth substance is a substance that exhibits an electron accepting property to the fourth substance.
  • another embodiment of the present invention is the electronic device as described above, in which the fourth substance is a ⁇ electron excess heteroaromatic compound or an aromatic amine compound.
  • the fifth substance includes a transition metal oxide, an oxide of a metal belonging to Groups 4 to 8 of the periodic table of the elements, and an electron-withdrawing group. It is an electronic device which is any one or more of organic compounds.
  • another embodiment of the present invention is the electronic device having the above structure, wherein the fifth substance is an organic compound having an electron withdrawing group.
  • another embodiment of the present invention is the electronic device as described above, in which the electron withdrawing group is a fluoro group or a cyano group.
  • the fifth substance according to the present invention is titanium oxide, vanadium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, rhenium oxide, ruthenium oxide, Chromium oxide, zirconium oxide, hafnium oxide, silver oxide, 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane, chloranil, 2,3,6,7, 10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane, ⁇ , ⁇ ′, ⁇ '' 1,2,3-cyclopropanetriylidenetris tris [4-cyano-2,3,5,6-tetrafluorobenzeneacetonitrile] selected from one or more electron A chair.
  • another embodiment of the present invention is the electronic device having the above structure, wherein the fifth substance is molybdenum oxide.
  • the first layer further includes a fifth layer, and the fifth layer is between the second layer and the third layer.
  • the electronic device is positioned and provided in contact with the third layer, and the fifth layer is a substance having a hole transporting property.
  • the first layer further includes a sixth layer, and the sixth layer is between the third layer and the second electrode.
  • the sixth layer is an electronic device having the same configuration as the second layer.
  • another embodiment of the present invention is the electronic device as described above, in which the first substance is a fluoride of an alkali metal or an alkaline earth metal.
  • an optical distance from a light emitting region in the third layer to an interface on the first electrode side of the second layer is from the light emitting element It is an electronic device that is an odd multiple of a quarter of the wavelength of emitted light, or a value close thereto.
  • the molar ratio of the first substance to the third substance contained in the second layer is higher in the first substance than in the first substance. It is.
  • the ratio of the first substance to the third substance contained in the second layer is such that the first substance is the third substance. It is an electronic device that is twice or more.
  • another embodiment of the present invention is the light emitting element having the above structure, wherein the third layer includes a light emitting material.
  • another embodiment of the present invention is a solar cell in the above-described configuration, wherein the third layer includes a material that absorbs light.
  • another embodiment of the present invention is an electronic device including the sensor, the operation button, the speaker, or the microphone in the above configuration.
  • another embodiment of the present invention is a light-emitting device including the above light-emitting element, a transistor, or a substrate.
  • another embodiment of the present invention is a lighting device including the light emitting device and a housing.
  • another embodiment of the present invention is an alkali metal atom or an alkaline earth metal atom, a fluorine atom, a transition metal atom or a metal atom belonging to Groups 4 to 8 of the periodic table, a carbon atom, and oxygen It is an electronic device which has a layer containing and.
  • another aspect of the present invention is a fluoride of an alkali metal or a fluoride of an alkaline earth metal, an oxide of a transition metal or an oxide of a metal belonging to periodic table groups 4 to 8, carbon It is an electronic device which has a layer containing and.
  • another embodiment of the present invention is the electronic device having the above structure, in which the atomic ratio of the fluorine atom in the layer is 20% or more.
  • another embodiment of the present invention is the electronic device having the above-described structure, in which the refractive index of the layer is 1.7 or less.
  • the light emitting device in the present specification includes an image display device using a light emitting element.
  • a module in which a connector such as an anisotropic conductive film or TCP (Tape Carrier Package) is attached to a light emitting element a module in which a printed wiring board is provided ahead of TCP, or a COG (Chip On Glass) method for a light emitting element
  • the light emitting device may also include a module in which an IC (integrated circuit) is directly mounted.
  • lighting devices and the like may have a light emitting device.
  • a novel light emitting element can be provided.
  • a light-emitting element with a long lifetime can be provided.
  • a light-emitting element with high luminous efficiency can be provided.
  • a highly reliable light-emitting device, an electronic device, and a display device can each be provided.
  • a light-emitting device, an electronic device, and a display device with low power consumption can be provided.
  • FIG. 2 is a schematic view of a light emitting element.
  • FIG. 2 is a conceptual diagram of an active matrix light-emitting device.
  • FIG. 2 is a conceptual diagram of an active matrix light-emitting device.
  • FIG. 2 is a conceptual diagram of an active matrix light-emitting device.
  • FIG. 1 is a conceptual diagram of a passive matrix light-emitting device.
  • FIG. FIG. FIG. FIG. FIG. FIG. FIG. FIG. 6 is a diagram illustrating an in-vehicle display device and a lighting device.
  • FIG. FIG. The luminance-current density characteristics of the light-emitting element 1 to the light-emitting element 3, the comparative light-emitting element 1, and the comparative light-emitting element 2.
  • the luminance-current density characteristics of the light-emitting element 6 and the comparative light-emitting element 6 The luminance-current density characteristics of the light-emitting element 6 and the comparative light-emitting element 5.
  • Current efficiency-luminance characteristics of the light-emitting element 6 and the comparative light-emitting element 5 Brightness-voltage characteristics of the light-emitting element 6 and the comparative light-emitting element 5
  • Current-voltage characteristics of the light-emitting element 6 and the comparative light-emitting element 5 External quantum efficiency-luminance characteristics of the light emitting element 6 and the comparative light emitting element 5
  • Emission spectra of the light-emitting element 6 and the comparative light-emitting element 5 Brightness-current density characteristics of the light-emitting element 7 and the comparative light-emitting element 6
  • Current efficiency-luminance characteristics of the light-emitting element 7 and the comparative light-emitting element 6 Brightness-voltage characteristics of the light-emitting element 7
  • the refractive index n includes n Ordinary which is a refractive index of an ordinary ray, n Extra-ordinary which is a refractive index of an extraordinary ray, and n average which is an average value of the both.
  • n average may be read as “no ordinary” when anisotropic analysis is performed, and “n Ordinary” when anisotropic analysis is performed. Note that the value obtained by dividing the sum of the value of n Ordinary and the value of n Extra-ordinary by 3 is n average.
  • FIG. 1A illustrates an electronic device of one embodiment of the present invention.
  • An electronic device according to one embodiment of the present invention includes a first electrode 10, a second electrode 11, and a first layer 12 including an organic compound sandwiched therebetween.
  • the first layer 12 has a second layer 13 and a third layer 14.
  • the second layer 13 is located between the first electrode 10 and the third layer 14.
  • the second layer 13 contains a first substance, a second substance, and a third substance, the first substance is a compound containing fluorine, and the second substance is an organic material having a hole transportability. It is a compound, and the third substance is a substance that exhibits electron acceptability to the second substance.
  • the second layer 13 has the above-described configuration, and thus has a feature that the refractive index is lower than that of the layers adjacent to and in contact with each other.
  • a material including the first substance, the second substance and the third substance may be referred to as a novel composite material.
  • the refractive index of the conventional composite material composed of only two types of the second substance and the third substance is greater than 1.7, but the first substance, the second substance and the third
  • the refractive index of the second layer 13 made of a substance can be 1.7 or less. It is effective that the second layer 13 has a refractive index lower than that of the third layer 14 by 0.1 or more, which is preferable.
  • the third layer 14 is a layer having a light-related function such as emitting or absorbing light, such as a light emitting layer or a photoelectric conversion layer.
  • the light emitting layer emits light when current flows, and the photoelectric conversion layer absorbs light to generate voltage or current.
  • the second layer 13 having a low refractive index due to the presence of the second layer 13 having a low refractive index, it is possible to cause the reflection of the light in the light emitting element, to intensify the light to be taken out, or to reabsorb the light which could not be absorbed. It is possible to cause the reflection of the light in the light emitting element, to intensify the light to be taken out, or to reabsorb the light which could not be absorbed. It is possible to cause the reflection of the light in the light emitting element, to intensify the light to be taken out, or to reabsorb the light which could not be absorbed. It is possible to cause the reflection of the light in the light emitting element, to intensify the light to be taken out, or to reabsorb the light which could not be absorbed. It is possible to cause the reflection of the light in the light emitting element, to intensify the light to be taken out, or to reabsorb the light which could not be absorbed. It is possible to cause the reflection of the light in the light emit
  • the second layer 13 and the third layer 14 when the second layer 13 and the third layer 14 are closer than the wavelength of the light, the second layer 13 having a low refractive index affects the refractive index of the third layer 14. In some cases, light confinement such as substrate mode and thin film mode may be alleviated.
  • the most important point of the present invention is that such a low refractive index layer can be formed in the device without adversely affecting the characteristics of the electronic device.
  • the low refractive index and the high carrier transportability or the reliability when used in a light emitting device are in a trade-off relationship.
  • the reason is that the carrier transportability and reliability in organic compounds are largely derived from the presence of unsaturated bonds, and organic compounds having many unsaturated bonds tend to have high refractive index.
  • the refractive index of a material is ⁇ where ⁇ is the permeability of the material, ⁇ is the permittivity of the material, ⁇ 0 is the permeability of vacuum, and ⁇ 0 is the permittivity of vacuum, and the square root of ( ⁇ / ⁇ o ⁇ o ) As the non-dielectric constant is larger, the refractive index tends to be larger. In organic compounds, a substance with more unsaturated bonds tends to have a larger dielectric constant because charge transfer in the molecule is easier, and as a result, the presence of unsaturated bonds is a factor that increases the refractive index. Become.
  • the organic compound exhibiting high carrier transportability is an unsaturated hydrocarbon having a wide ⁇ conjugated system, and the organic compound which can give high reliability when used as a material for a light emitting device is rigid due to the unsaturated bond. It is known that the unsaturated hydrocarbon has a high structure and a high Tg. Therefore, if an organic compound with fewer unsaturated bonds is selected to form a layer having a small refractive index, the drive voltage does not increase due to the poor carrier transportability of the organic compound, and the organic compound does not have a rigid structure. It is easy to cause the decrease of reliability due to
  • the layer containing the first substance, the second substance and the third substance (the second layer 13) is used as the layer having a small refractive index, without sacrificing other characteristics.
  • the light emission efficiency can be improved. Details will be described below.
  • the second layer 13 which is a low refractive index layer is composed of a novel composite material containing a first substance, a second substance and a third substance.
  • the first substance is a compound containing fluorine
  • the second substance is an organic compound having a hole transporting property
  • the third substance is an organic compound having an electron accepting property to the second substance.
  • alkali metal fluorides alkaline earth metal fluorides and alkyl fluorides can be mentioned.
  • Lithium fluoride is preferred as the alkali metal fluoride.
  • the alkaline earth metal fluoride calcium fluoride or magnesium fluoride is preferred.
  • the fluorinated alkyl perfluorotetracosane, polytetrafluoroethylene and the like are preferable.
  • the first substance is preferably a fluoride of an alkaline earth metal because the lifetime of the light-emitting element is improved, and alkyl fluoride is preferable in view of productivity and a low sublimation temperature.
  • the second substance preferably has a hole mobility of 10 ⁇ 6 cm 2 / Vs or more.
  • the second substance is preferably a ⁇ electron excess heteroaromatic compound or an aromatic amine compound because of its high electron donating property.
  • the material that can be used as the second substance include 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: aromatic amine such as DPA3B), 3- [N- (9-phenylcarbazol-3-yl) -N-phenylamino] -9-phen
  • the aromatic hydrocarbon may have a vinyl skeleton.
  • Examples of the aromatic hydrocarbon having a vinyl group include 4,4′-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi), 9,10-bis [4- (2,2- And diphenylvinyl) phenyl] anthracene (abbreviation: DPVPA) and the like.
  • NPB N, N′-bis (3-methylphenyl) -N, N′-diphenyl- [4] 1,1'-biphenyl] -4,4'-diamine
  • TPD 1,1'-biphenyl] -4,4'-diamine
  • BSPB 4,4'-bis [N- (spiro-9,9'-bifluoren-2-yl) -N-phenylamino] biphenyl
  • BPAFLP 4-phenyl-4 ′-(9-phenylfluoren-9-yl) triphenylamine
  • mBPAFLP 4-phenyl-3 ′-(9-phenylfluoren-9-yl) tril Phenylamine
  • mBPAFLP 4-phenyl-4 ′-(9-phenyl-9H-carbazol-3-yl)
  • the second substance has a HOMO level of -5.7 eV or more, preferably -5.5 eV or more, so that holes can be injected smoothly and the characteristics are better. This is a preferable configuration because
  • the third substance is a transition metal oxide, an oxide of a metal belonging to Groups 4 to 8 of the periodic table, an organic compound having an electron-withdrawing group (in particular, a halogen group such as a fluoro group or a cyano group) From the above, a substance which exhibits electron acceptability may be selected as the second substance.
  • transition metal oxides and oxides of metals belonging to Groups 4 to 8 in the periodic table of elements include vanadium oxides, niobium oxides, tantalum oxides, chromium oxides, molybdenum oxides, tungsten oxides
  • Manganese oxide, rhenium oxide, titanium oxide, ruthenium oxide, zirconium oxide, hafnium oxide and silver oxide are preferable because they exhibit high acceptor properties.
  • molybdenum oxide is particularly preferable because it is stable in the air, has low hygroscopicity, and is easy to handle.
  • organic compounds having the above-mentioned electron withdrawing group include 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F 4 -TCNQ), chloranil 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (substantially: HAT-CN), 1,3,4,5,7,8 -Hexafluorotetracyano-naphthoquinodimethane (abbreviation: F6-TCNNQ) etc. can be mentioned.
  • F 4 -TCNQ 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane
  • chloranil 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene substantially: HAT-CN
  • a compound in which an electron withdrawing group is bonded to a condensed aromatic ring having a plurality of hetero atoms such as HAT-CN, is thermally stable and preferable.
  • [3] radialene derivatives having an electron withdrawing group are preferable because they have very high electron accepting properties, and specifically, ⁇ , ⁇ ′, ⁇ ′ ′- 1,2,3-cyclopropanetriylidenetris [4-cyano-2,3,5,6-tetrafluorobenzeneacetonitrile], ⁇ , ⁇ ′, ⁇ ′ ′-1,2,3-cyclopropanetriylidenetris [2,6-Dichloro-3,5-difluoro-4- (trifluoromethyl) benzeneacetonitrile], ⁇ , ⁇ ′, ⁇ ′ ′-1,2,3-cycloprop
  • a composite material obtained by co-evaporation of two types of materials, a second substance and a third substance, has been used as a material for forming a hole injection layer of a light emitting element from before. It is used suitably.
  • this composite material uses an organic compound having high carrier (hole) transportability (that is, many unsaturated bonds and relatively high refractive index) and an oxide of a metal having a refractive index higher than the organic compound. Therefore, its refractive index is often greater than 17.
  • a layer made of a composite material which is conventionally formed by co-evaporation of two kinds of materials of a second substance and a third substance (mainly used as a hole injection layer) Is formed by co-evaporation of the three materials of the first substance, the second substance and the third substance.
  • the first substance, alkali metal or alkaline earth metal fluoride, and alkyl fluoride co-evaporate with the second substance and the third substance because their refractive index is as low as 1.2 to 1.4.
  • the refractive index of the second layer 13 can be reduced.
  • these first substances are substances having an electron donating property as understood from the fact that they may be used at the interface between the cathode and the organic layer in order to improve the electron injecting property in the organic EL element. That is, the second layer 13 in one embodiment of the present invention can also be referred to as a layer simultaneously including the first substance that is electron donating and the third substance that is electron accepting. It is common to think that if the electron accepting substance and the electron donating substance are used in the same layer, the effect may be offset and the characteristics of the device may be deteriorated.
  • the first substance, fluoride of alkali metal or alkaline earth metal is basically an insulator.
  • the first substance when used as the electron injection layer of the organic EL element, it is used as an extremely thin film of about 0.1 nm to 1 nm in order to prevent an increase in drive voltage. Therefore, using the first substance for the second layer 13 has a concern such as an increase in driving voltage.
  • the layer containing the first substance which is a fluoride of an alkali metal or alkaline earth metal or an alkyl fluoride is an electronic device as described above, in particular, an organic compound having a hole transportability.
  • an organic compound having a hole transportability is usually not considered.
  • the present inventors have found that the second layer 13 containing the novel composite material consisting of the first substance, the second substance and the third substance is the second substance and the second substance when used in an electronic device. It has been found to exhibit the same electrical properties as the layers of the previous composite material consisting of only three materials.
  • a second layer 13 which is a layer of a novel composite material consisting of a first substance, a second substance and a third substance is the same as a layer of a conventional composite material consisting of a second substance and a third substance
  • the layer having a low refractive index can be obtained by including the first substance having a low refractive index while having the following characteristics. That is, it has been found that a layer having the same characteristics as the hole injection layer used conventionally and having a low refractive index can be realized.
  • the present inventors also similarly apply to the case where the molar ratio of the first substance to the third substance and the molar ratio of the first substance to the second substance are larger in the first substance. It has been found to exhibit good properties. Therefore, in one embodiment of the present invention, a large amount of the first substance having a low refractive index can be contained in the second layer 13, and the refractive index of the second layer 13 can be significantly reduced.
  • the present invention has characteristics equivalent to those of a conventional composite material composed of a second substance and a third substance, hardly being adversely affected by the electrical characteristics of the first substance, And a layer with a low refractive index can be provided. Also, it does not change even if the first substance is the largest component of the second layer 13.
  • the spin density of various materials was measured using the ESR method. It is known that the composite material composed of the second substance and the third substance shows an increase in spin density by being a composite material as compared to the case where each material alone is used. In the new composite material using the same substance as the second substance and the third substance constituting the composite material as the second substance and the third substance, the spin density is measured by changing the first substance. It was found that the spin density value was different depending on the type of the first substance.
  • Lithium fluoride, sodium fluoride, potassium fluoride, calcium fluoride and magnesium fluoride were used as the first substance, but fluoride was added to any of the novel composite materials using fluoride. The decrease in spin density was observed compared to the composites that did not
  • a novel composite material having a spin density of 1.0 ⁇ 10 18 spins / cm 3 or more can be formed in the device without adversely affecting other characteristics of the electronic device.
  • the absorption spectrum of the material was also measured. It has been found that, in the composite material forming the charge transfer complex, absorption based on the absorption of the charge transfer complex which is not observed in the case of the material alone appears.
  • the conventional composite material the co-deposited film of the second material and the third material
  • the new composite material the first material, the second material
  • the intensity of the absorption was different depending on the presence or absence of the first substance and the type thereof, as in the above-mentioned spin density.
  • lithium fluoride, sodium fluoride, potassium fluoride, calcium fluoride and magnesium fluoride are used as in the above-mentioned ESR measurement. It was found that in any of the novel composite materials using fluoride, the absorption due to the charge transfer complex is smaller than in the composite material without the addition of fluoride.
  • the distance between the second layer 13 and the third layer 14 is four minutes of the wavelength of the light emitted by the light emitting layer, in the case where the third layer 14 emits light, that is, the light emitting layer.
  • An odd multiple of 1 is a preferable configuration because it increases the light that can be extracted by the amplification effect due to interference.
  • the third layer 14 is a photoelectric conversion layer, for example, light having a small absorption can be obtained by setting the third layer 14 to an integral multiple of one quarter of the wavelength at which the absorbance is small. It becomes easy to reflect and the efficiency improvement can be expected by increasing the chance of absorption in the third layer 14.
  • the refractive index of the second layer can be lowered more than the refractive index of the peripheral material, and the performance of the electronic device is improved. Is possible.
  • FIG. 1B illustrates a light-emitting element which is one embodiment of the present invention.
  • the light-emitting element of one embodiment of the present invention includes the first electrode 101, the second electrode 102, and the EL layer 103, and the EL layer 103 has a low refractive index which is part or all of the hole injection layer 111.
  • a layer 111-L and a light emitting layer 113 are provided.
  • the EL layer 103 may further include a hole transport layer 112, an electron transport layer 114, an electron injection layer 115, and the like.
  • the structure of the light-emitting element including the electron-transporting layer 114 and the electron injection layer 115 is illustrated, the light-emitting element of one embodiment of the present invention has the low refractive index layer 111 even if it has a structure having other functional layers. A structure without any or plural layers other than L and the light emitting layer 113 may be employed.
  • the first electrode 101 is preferably formed using a metal, an alloy, a conductive compound, a mixture thereof, or the like with a high work function (specifically, 4.0 eV or more).
  • a metal an alloy, a conductive compound, a mixture thereof, or the like with a high work function (specifically, 4.0 eV or more).
  • ITO Indium Tin Oxide
  • silicon or indium oxide-tin oxide containing silicon oxide silicon oxide
  • indium oxide-zinc oxide tungsten oxide and indium oxide containing zinc oxide
  • IWZO indium oxide containing zinc oxide
  • These conductive metal oxide films are generally formed by sputtering, but may be formed by applying sol-gel method or the like.
  • indium oxide containing tungsten oxide and zinc oxide is formed by sputtering 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.
  • gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium Pd) or nitrides of metal materials (eg, titanium nitride) and the like can be mentioned.
  • Graphene can also be used. Note that by using a composite material described later for the layer in contact with the first electrode 101 in the EL layer 103, an electrode material can be selected
  • the low refractive index layer 111 -L has the same structure as the second layer 13 described above with reference to FIG.
  • the first hole injection layer 111-1 is a layer made of a composite material including the second substance and the third substance described as the substance constituting the second layer 13.
  • the hole injection layer 111 is formed of the low refractive index layer 111-L formed on the first electrode side and the first hole injection layer 111 formed on the hole transport layer 112 side.
  • the configuration of the hole injection layer 111 is not limited to this, and at least the low refractive index layer 111 -L may be provided.
  • the hole injection layer 111 may be composed of only the low refractive index layer 111 -L, and further, a second hole injection layer between the low refractive index layer 111 -L and the first electrode 101.
  • the second low refractive index layer may be formed between the first hole injection layer 111-1 and the hole transport layer 112.
  • the hole transport layer 112 is formed to include a material having a hole transportability, and as the material, the same material as the second substance used for the second layer 13 described above can be used.
  • the hole injection layer 111 contains a metal oxide (third substance), there is a possibility that the hole injection layer 111 and the light emitting layer 113 may be quenched when they are in contact with each other. 112 is preferably formed.
  • the light emitting layer 113 contains a light emitting material and may contain a host material.
  • the light emitting material may be a fluorescent light emitting material, a phosphorescent light emitting material, or a material exhibiting thermally activated delayed fluorescence (TADF).
  • TADF thermally activated delayed fluorescence
  • it may be a single layer or may be composed of a plurality of layers containing different light emitting materials.
  • Examples of the material that can be used as a fluorescent substance in the light emitting layer 113 include the following. In addition, other fluorescent substances can also be used.
  • Examples of the material that can be used as the phosphorescent material in the light emitting layer 113 include the following.
  • organometallic iridium complex having a pyrimidine skeleton is particularly preferable because it is remarkably excellent in reliability and light emission efficiency.
  • known phosphorescent light emitting materials may be selected and used.
  • TADF materials fullerenes and their derivatives, acridine derivatives such as proflavin, eosin and the like can be used.
  • metal-containing porphyrins including magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), palladium (Pd), and the like can be used.
  • metal-containing porphyrin examples include protoporphyrin-tin fluoride complex (SnF 2 (Proto IX)), mesoporphyrin-tin fluoride complex (SnF 2 (Meso IX)), and hematoporphyrin represented by the following structural formula -Tin fluoride complex (SnF 2 (Hemato IX)), coproporphyrin tetramethyl ester-tin fluoride complex (SnF 2 (Copro III-4Me)), octaethyl porphyrin-tin fluoride complex (SnF 2 (OEP)) And ethioporphyrin-tin fluoride complex (SnF 2 (Etio I)), octaethyl porphyrin-platinum chloride complex (PtCl 2 OEP), and the like.
  • SnF 2 Proto IX
  • SnF 2 (Meso IX) mesop
  • the heterocyclic compound has a ⁇ electron excess heteroaromatic ring and a ⁇ electron deficient heteroaromatic ring, and thus is high in electron transportability and hole transportability, which is preferable.
  • the substance in which the ⁇ electron excess heteroaromatic ring and the ⁇ electron deficiency heteroaromatic ring are directly bonded has both the donor property of the ⁇ electron excess heteroaromatic ring and the acceptor activity of the ⁇ electron deficiency heteroaromatic ring. Since the energy difference between the S 1 level and the T 1 level is reduced, it is particularly preferable because thermally activated delayed fluorescence can be efficiently obtained.
  • an aromatic ring to which an electron withdrawing group such as a cyano group is bonded may be used instead of the ⁇ electron deficient heteroaromatic ring.
  • various carrier transporting materials such as a material having an electron transporting property and a material having a hole transporting property can be used.
  • NPB 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • TPD 4,4′-bis [N- (spiro-9,9'-bifluoren-2-yl] ) -N-phenylamino] biphenyl
  • BSPB 4,4'-bis [N- (spiro-9,9'-bifluoren-2-yl] ) -N-phenylamino] biphenyl
  • BPAFLP 4-phenyl-4 ′-(9-phenylfluoren-9-yl) triphenylamine
  • mBPAFLP 4-phenyl-3 ′-(9-) Phenylfluoren-9-yl) triphenylamine
  • mBPAFLP 4-phenyl-4 ′-(9-phenyl-9H-
  • bis (10-hydroxybenzo [h] quinolinato) beryllium (II) (abbreviation: BeBq 2 ), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) Aluminum (III) (abbreviation: BAlq), bis (8-quinolinolato) zinc (II) (abbreviation: Znq), bis [2- (2-benzoxazolyl) phenolato] zinc (II) (abbreviation: ZnPBO), Metal complexes such as bis [2- (2-benzothiazolyl) phenolato] zinc (II) (abbreviation: ZnBTZ) or 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4 -Oxadiazole (abbreviation: PBD), 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphen
  • a heterocyclic compound having a diazine skeleton and a heterocyclic compound having a pyridine skeleton are preferable because they have excellent reliability.
  • a heterocyclic compound having a diazine (pyrimidine or pyrazine) skeleton has high electron transportability and also contributes to reduction in driving voltage.
  • a material having an anthracene skeleton is suitable as a host material.
  • a substance having an anthracene skeleton is used as a host material of a fluorescent substance, it is possible to realize a light emitting layer having good luminous efficiency and durability.
  • a substance having an anthracene skeleton to be used as a host material a substance having a diphenylanthracene skeleton, particularly a 9,10-diphenylanthracene skeleton is preferable because it is chemically stable.
  • the host material having a carbazole skeleton is preferable because the injection and transport properties of holes are enhanced.
  • the HOMO level is about 0.1 eV compared to carbazole. It is more preferable because it becomes high and holes can easily enter.
  • the host material contains a dibenzocarbazole skeleton, the HOMO level is higher than that of carbazole by about 0.1 eV, holes are easily contained, the hole transportability is also excellent, and the heat resistance is also high. It is.
  • the host material is a substance simultaneously having a 9,10-diphenylanthracene skeleton and a carbazole skeleton (or a benzocarbazole skeleton or a dibenzocarbazole skeleton).
  • a benzofluorene skeleton or a dibenzofluorene skeleton may be used instead of the carbazole skeleton.
  • Such substances 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 , 2-d] furan (abbreviation: 2mBnfPPA), 9-phenyl-10- ⁇ 4-
  • the host material may be a material in which a plurality of substances are mixed, and in the case of using a mixed host material, it is preferable to mix a material having an electron transporting property and a material having a hole transporting property .
  • an exciplex may be formed by these mixed materials.
  • energy transfer becomes smooth and light emission can be efficiently obtained.
  • the driving voltage is also reduced, which is preferable.
  • the electron transporting layer 114 is a layer containing a substance having an electron transporting property.
  • the substance having an electron transporting property those mentioned as the substance having an electron transporting property which can be used for the host material can be used.
  • An alkali metal such as lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF 2 ) or the like is used as the electron injection layer 115 between the electron transport layer 114 and the second electrode 102.
  • Earth metals or compounds thereof may be provided.
  • electride which contains an alkali metal or an alkaline earth metal or a compound thereof in a layer formed of a substance having an electron transporting property. Examples of electride include a substance in which electrons are added to a mixed oxide of calcium and aluminum at a high concentration, and the like.
  • a charge generation layer 116 may be provided (FIG. 1C).
  • the charge generation layer 116 is a layer capable of injecting holes into a layer in contact with the cathode side of the layer and applying electrons into a layer in contact with the anode side by applying a potential.
  • Charge generation layer 116 includes at least P-type layer 117.
  • the P-type layer 117 is preferably formed using the composite material mentioned as the material which can constitute the above-mentioned hole injection layer 111. Further, the P-type layer 117 may be formed by laminating a film containing the above-described acceptor material as a material constituting the composite material and a film containing the 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 second electrode 102 which is a cathode, whereby the light emitting element operates.
  • the charge generation layer 116 be provided with any one or both of the electron relay layer 118 and the electron injection buffer layer 119.
  • the electron relay layer 118 contains at least a substance having an electron transporting property, and has a function of preventing the interaction between the electron injection buffer layer 119 and the P-type layer 117 and smoothly passing electrons.
  • the LUMO level of the substance having electron transportability contained in the electron relay layer 118 is the same as the LUMO level of the acceptor substance in the P-type layer 117 and the substance contained in the layer in contact with the charge generation layer 116 in the electron transport layer 114. It is preferable that it is between LUMO levels.
  • a specific energy level of the LUMO level of the substance having an electron transporting property used for the electron relay layer 118 is preferably ⁇ 5.0 eV or more, preferably ⁇ 5.0 eV or more and ⁇ 3.0 eV or less. It is preferable to use a phthalocyanine material or a metal complex having a metal-oxygen bond and an aromatic ligand as the substance having an electron transporting property used for the electron relay layer 118.
  • the electron injection buffer layer 119 includes alkali metals, alkaline earth metals, rare earth metals, and compounds thereof (alkali metal compounds (including oxides such as lithium oxide, halides, and carbonates such as lithium carbonate and cesium carbonate).
  • alkali metal compounds including oxides such as lithium oxide, halides, and carbonates such as lithium carbonate and cesium carbonate.
  • alkaline earth metal compounds including oxides, halides and carbonates
  • rare earth metals including oxides, halides and carbonates
  • the electron injecting buffer layer 119 includes an electron transporting substance and a donor substance
  • an alkali metal, an alkaline earth metal, a rare earth metal, and a compound thereof may be used as the donor substance.
  • 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, decamethyl nickelocene, and the like can also be used.
  • TTN tetrathianaphthacene
  • nickelocene decamethyl nickelocene, and the like
  • a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like with a low work function can be used.
  • cathode materials 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). Elements belonging to Group 2, alloys containing these (MgAg, AlLi), rare earth metals such as europium (Eu), ytterbium (Yb) and alloys containing these are listed.
  • indium oxide-tin oxide containing Al, Ag, ITO, silicon or silicon oxide regardless of the magnitude of work function
  • Various conductive materials can be used as the second electrode 102. These conductive materials can be deposited by a dry method such as vacuum evaporation or sputtering, an inkjet method, a spin coating method, or the like. Alternatively, 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 of forming the EL layer 103 various methods can be used regardless of a dry method or a wet method.
  • a vacuum evaporation method, a gravure printing method, an offset printing method, a screen printing method, an inkjet method, a spin coating method, or the like may be used.
  • each electrode or each layer described above may be formed using different film formation methods.
  • the structure of a layer provided between the first electrode 101 and the second electrode 102 is not limited to the above. However, holes and electrons are separated from the first electrode 101 and the second electrode 102 so as to suppress quenching caused by the proximity of the light emitting region and the metal used for the electrode and the carrier injection layer. It is preferable to provide a light emitting region in which the light emitting molecules recombine.
  • a hole transporting layer or an electron transporting layer in contact with the light emitting layer 113, in particular, a carrier transporting layer close to a recombination region in the light emitting layer 113 has a band gap for suppressing energy transfer from excitons generated in the light emitting layer. It is preferable to use a light emitting material that constitutes the light emitting layer or a material having a band gap larger than the band gap of the light emitting material contained in the light emitting layer.
  • a light emitting element also referred to as a stacked element or a tandem element in which a plurality of light emitting units are stacked
  • This light emitting element is a light emitting element having a plurality of light emitting units between the anode and the cathode.
  • One light emitting unit has almost the same structure as the EL layer 103 shown in FIG. That is, the light emitting element shown in FIG. 1D is a light emitting element having a plurality of light emitting units, and the light emitting element shown in FIG. 1B or 1C is a light emitting element having one light emitting unit. It can be said that there is.
  • a first light emitting unit 511 and a second light emitting unit 512 are stacked between the first electrode 501 and the second electrode 502, and the first light emitting unit 511 and the second light emitting unit 512 are stacked.
  • a charge generation layer 513 is provided between the second light emitting unit 512 and the second light emitting unit 512.
  • the first electrode 501 and the second electrode 502 correspond to the first electrode 101 and the second electrode 102 in FIG. 1B, respectively, and the same ones described in the description of FIG. 1B are applied. can do.
  • 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 first electrode 501 and the second electrode 502. That is, in FIG. 1D, in the case where a voltage is applied such that the potential of the first electrode is higher than the potential of the second electrode, the charge generation layer 513 generates electrons in the first light emitting unit 511. And the holes may be injected into the second light emitting unit 512.
  • the charge generation layer 513 is preferably formed to have the same structure as the charge generation layer 116 described with reference to FIG.
  • the composite material of the organic compound and the metal oxide is excellent in the carrier injection property and the carrier transport property, so that low voltage drive and low current drive can be realized. Note that when the anode side surface of the light emitting unit is in contact with the charge generation layer 513, the charge generation layer 513 can also play a role of a hole injection layer of the light emission unit. It is not necessary to provide it.
  • the electron injection buffer layer 119 plays a role of the electron injection layer in the light emitting unit on the anode side, and therefore the electron light emitting unit on the anode side does not necessarily have to be formed. .
  • FIG. 1D illustrates a light emitting element having two light emitting units
  • the present invention can be similarly applied to a light emitting element in which three or more light emitting units are stacked.
  • the light-emitting element according to this embodiment by arranging a plurality of light-emitting units between a pair of electrodes by the charge generation layer 513, high-intensity light emission is possible while maintaining a low current density, and further A long life element can be realized.
  • a light-emitting device which can be driven at low voltage and consumes low power can be realized.
  • light emission of a desired color can be obtained as the whole light emitting element.
  • a light emitting element having two light emitting units a light emitting element emitting white light as a whole light emitting element 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 It is also possible to get.
  • FIG. 2A is a top view of the light emitting device
  • FIG. 2B is a cross-sectional view of FIG. 2A taken along the lines A-B and C-D.
  • the 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 light emission of the light emitting element.
  • reference numeral 604 denotes a sealing substrate
  • reference numeral 605 denotes 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 and a clock signal from an FPC (flexible printed circuit) 609 serving as an external input terminal. Receive start signal, reset signal, etc. Although only the FPC is illustrated here, a printed wiring board (PWB) may be attached to the FPC.
  • the light emitting device in the present specification includes not only the light emitting device main body but also a state in which an FPC or a 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 can be manufactured using a substrate made of glass, quartz, an organic resin, metal, an alloy, a semiconductor, or the like, as well as a plastic substrate made of FRP (Fiber Reinforced Plastics), PVF (polyvinyl fluoride), polyester, acrylic or the like. Just do it.
  • FRP Fiber Reinforced Plastics
  • PVF polyvinyl fluoride
  • the structure of the transistor used for the pixel and the driver circuit is not particularly limited.
  • a reverse staggered transistor or a staggered transistor may be used.
  • a top gate transistor or a bottom gate 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.
  • the crystallinity of the semiconductor material used for the transistor is not particularly limited either, and any of an amorphous semiconductor and a semiconductor having crystallinity (a microcrystalline semiconductor, a polycrystalline semiconductor, a single crystal semiconductor, or a semiconductor having a crystalline region in part) May be used.
  • a semiconductor having crystallinity is preferable because deterioration of transistor characteristics can be suppressed.
  • an oxide semiconductor is preferably applied to a semiconductor device such as a transistor used for a touch sensor or the like described later, in addition to a transistor provided in the pixel or the driver circuit.
  • a semiconductor device such as a transistor used for a touch sensor or the like described later
  • an oxide semiconductor having a wider band gap than silicon is preferably used. With the use of an oxide semiconductor with a wider band gap than silicon, current in the off state of the transistor can be reduced.
  • the oxide semiconductor preferably contains at least indium (In) or zinc (Zn). And an oxide semiconductor containing 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 preferred.
  • M is a metal such as Al, Ti, Ga, Ge, Y, Zr, Sn, La, Ce, or Hf.
  • the semiconductor layer has a plurality of crystal parts, and in the crystal parts, the c-axis is oriented perpendicularly to the formation surface of the semiconductor layer or the top surface of the semiconductor layer, and grain boundaries between adjacent crystal parts It is preferable to use an oxide semiconductor film which does not have
  • the low off-state current of the transistor including the above semiconductor layer can hold charge stored in the capacitor through the transistor for a long time.
  • a base film is preferably provided.
  • 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 manufactured in a single layer or stacked layers.
  • the base film is formed by sputtering, CVD (Chemical Vapor Deposition) (plasma CVD, thermal CVD, MOCVD (Metal Organic CVD), etc.), atomic layer deposition (ALD), coating, printing, etc. it can.
  • CVD Chemical Vapor Deposition
  • MOCVD Metal Organic CVD
  • ALD atomic layer deposition
  • the undercoating film may not be provided 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 of various CMOS circuits, PMOS circuits, or NMOS circuits. Further, although the driver integrated type in which the drive circuit is formed on the substrate is shown in this embodiment mode, the driver circuit is not necessarily required, and the drive circuit can be formed not on the substrate but on the outside.
  • the pixel portion 602 is formed of a plurality of pixels including the switching FET 611, the current control FET 612, and the first electrode 613 electrically connected to the drain thereof, the present invention is not limited to this.
  • the pixel portion may be a combination of three or more FETs and a capacitor.
  • an insulator 614 is formed to cover an end portion of the first electrode 613.
  • it can be formed by using a positive photosensitive acrylic film.
  • a curved surface having a curvature is formed at the upper end portion or the lower end portion of the insulator 614.
  • positive photosensitive acrylic is used as the material of the insulator 614
  • any of negative photosensitive resin and positive photosensitive resin can be used as the insulator 614.
  • an EL layer 616 and a second electrode 617 are formed over the first electrode 613.
  • a material used for the first electrode 613 which functions as an anode a material having a high work function is preferably used.
  • a stacked layer of a titanium nitride film and a film containing aluminum as a main component a three-layer structure of a titanium nitride film, a film containing aluminum as a main component, and a titanium nitride film can be used. Note that when a stacked structure is employed, the resistance as a wiring is low, a favorable ohmic contact can be obtained, and the electrode can further 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, a spin coating method, or the like.
  • the EL layer 616 includes the structure as described in Embodiment 1.
  • a low molecular weight compound or a high molecular weight compound may be used as another material forming the EL layer 616.
  • a material formed on the EL layer 616 and used for the second electrode 617 functioning as a cathode a material having a low work function (Al, Mg, Li, Ca, or an alloy or compound thereof (MgAg, MgIn, It is preferable to use AlLi etc.).
  • a metal thin film with a thin film thickness and a transparent conductive film ITO, oxidation of 2 to 20 wt%) are used as the second electrode 617. It is preferable to use a stack of indium oxide containing zinc, indium tin oxide containing silicon, zinc oxide (ZnO), and the like.
  • a light emitting element is formed by the first electrode 613, the EL layer 616, and the second electrode 617.
  • the light-emitting element is the light-emitting element described in Embodiment 1. Note that although a plurality of light emitting elements are formed in the pixel portion, the light emitting device in this embodiment includes both the light emitting element described in Embodiment 1 and a light emitting element having other configuration. It may be done.
  • the sealing substrate 604 by bonding the sealing substrate 604 to the element substrate 610 with the sealant 605, the light emitting element 618 is provided in the space 607 surrounded by the element substrate 610, the sealing substrate 604, and the sealant 605.
  • the space 607 may be filled with a sealing material.
  • an epoxy resin or glass frit is preferably used for the sealant 605.
  • these materials do not transmit moisture and oxygen as much as possible.
  • a plastic substrate made of FRP (Fiber Reinforced Plastics), PVF (polyvinyl fluoride), polyester, acrylic, or the like can be used as a material used for the sealing substrate 604.
  • a protective film may be provided on the second electrode 617.
  • the protective film may be formed of an organic resin film or an inorganic insulating film.
  • 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 exposed side surfaces of the surfaces and side surfaces of the pair of substrates, the sealing layer, the insulating layer, and the like.
  • the protective film a material that does not easily transmit impurities such as water can be used. Therefore, the diffusion of impurities such as water from the outside into the inside can be effectively suppressed.
  • oxides, nitrides, fluorides, sulfides, ternary compounds, metals or polymers can be used.
  • the protective film is preferably formed by using a film forming method with good step coverage (step coverage).
  • a film forming method with good step coverage (step coverage).
  • One such method is atomic layer deposition (ALD).
  • ALD atomic layer deposition
  • ALD method it is possible to form a dense protective film with reduced defects such as cracks and pinholes or with a uniform thickness. Moreover, the damage given to a process member at the time of forming a protective film can be reduced.
  • the protective film by forming the protective film using the ALD method, it is possible to form a protective film which is uniform and has few defects even on the surface having a complicated uneven shape, and on the upper surface, the side surface, and the back surface of the touch panel.
  • the light-emitting device in this embodiment uses the light-emitting element described in Embodiment 1; thus, a light-emitting device with favorable characteristics can be obtained. Specifically, since the light-emitting element described in Embodiment 1 is a light-emitting element with a long lifetime, the light-emitting device can have high reliability. In addition, since the light-emitting device using the light-emitting element described in Embodiment 1 has high light emission efficiency, the light-emitting device can consume less power.
  • FIG. 3 illustrates an example of a light-emitting device in which a light-emitting element exhibiting white light emission is formed and a full color is achieved by providing a coloring layer (color filter) or the like.
  • a driver circuit portion 1041 first electrodes 1024W, 1024R, 1024G and 1024B of light emitting elements, partition walls 1025, an EL layer 1028, second electrodes 1029 of light emitting elements, a sealing substrate 1031, a sealing material 1032, and the like are illustrated. ing.
  • the coloring layers (red coloring layer 1034R, green coloring layer 1034G, blue coloring layer 1034B) are provided over the transparent base 1033.
  • a black matrix 1035 may be further provided.
  • the transparent substrate 1033 provided with the colored layer and the black matrix is aligned and fixed to the substrate 1001.
  • the colored layer and the black matrix 1035 are covered with an overcoat layer 1036.
  • FIG. 3B shows an example of forming a coloring layer (red coloring layer 1034R, green coloring layer 1034G, blue coloring layer 1034B) 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 where the FET is formed, a structure for extracting light emission to the sealing substrate 1031 side (top emission type It is good also as a light-emitting device.
  • a cross-sectional view of the top emission type light emitting device is shown in FIG. In this case, a substrate which does not transmit light can be used as the substrate 1001. Until a connection electrode for connecting the FET and the anode of the light emitting element is manufactured, it is formed in the same manner as the bottom emission type light emitting device. Thereafter, a third interlayer insulating film 1037 is formed to cover the electrode 1022. This insulating film may play a role of planarization.
  • the third interlayer insulating film 1037 can be formed using other known materials in addition to the same material as the second interlayer insulating film.
  • the first electrodes 1024 W, 1024 R, 1024 G, and 1024 B of the light emitting element are here an anode, but may be a cathode. In the case of a top emission type light emitting device as shown in FIG. 4, it is preferable that the first electrode be a reflective electrode.
  • the structure of the EL layer 1028 is a structure as described for the EL layer 103 in Embodiment 1 and an element structure in which white light emission can be obtained.
  • sealing can be performed with a sealing substrate 1031 provided with colored layers (red colored layer 1034 R, green colored layer 1034 G, and blue colored layer 1034 B).
  • the sealing substrate 1031 may be provided with a black matrix 1035 so as to be located between pixels.
  • the colored layer (red colored layer 1034R, green colored layer 1034G, blue colored layer 1034B) or a black matrix may be covered with an overcoat layer 1036.
  • a light-transmitting substrate is used for the sealing substrate 1031.
  • full color display in four colors of red, green, blue and white is shown here, it is not particularly limited, and full color in four colors of red, yellow, green and blue and three colors of red, green and blue You may display it.
  • a light emitting element having a microcavity structure can be obtained by using the first electrode as a reflective electrode and the second electrode as a semi-transmissive and semi-reflective electrode. At least an EL layer is provided between the reflective electrode and the semi-transmissive and semi-reflective electrode, and a light-emitting layer which is at least a light emitting region is provided.
  • the reflective electrode is a film having a visible light reflectance of 40% to 100%, preferably 70% to 100%, and a resistivity of 1 ⁇ 10 ⁇ 2 ⁇ cm or less.
  • the transflective / semireflective 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.
  • the light emitted from the light emitting layer included in the EL layer is reflected by the reflective electrode and the semi-transmissive and semi-reflective electrode to resonate.
  • the light emitting element can change the optical distance between the reflective electrode and the semi-transmissive and semi-reflective electrode by changing the thickness of the transparent conductive film, the above-described composite material, carrier transport material, and the like.
  • light of a resonating wavelength can be intensified between the reflective electrode and the semi-transmissive / semi-reflective electrode, and light of a non-resonant wavelength can be attenuated.
  • the light reflected back by the reflective electrode causes a large interference with the light (first incident light) directly incident on the semi-transmissive and semi-reflective electrode from the light-emitting layer, and thus is reflected.
  • the EL layer may have a plurality of light emitting layers or may have a single light emitting layer.
  • the present invention may be applied to a configuration in which a plurality of EL layers are provided in one light emitting element with a charge generation layer interposed therebetween, and one or more light emitting layers are formed in each of the EL layers.
  • microcavity structure By having the microcavity structure, it is possible to intensify the light emission intensity in the front direction of the specific wavelength, so that power consumption can be reduced.
  • a microcavity structure adapted to the wavelength of each color can be applied to all sub-pixels, in addition to the luminance improvement effect by yellow light. A light emitting device with favorable characteristics can be obtained.
  • the light-emitting device in this embodiment uses the light-emitting element described in Embodiment 1; thus, a light-emitting device with favorable characteristics can be obtained. Specifically, since the light-emitting element described in Embodiment 1 is a light-emitting element with a long lifetime, the light-emitting device can have high reliability. In addition, since the light-emitting device using the light-emitting element described in Embodiment 1 has high light emission efficiency, the light-emitting device can consume less power.
  • FIG. 5 shows a passive matrix light emitting device manufactured by applying the present invention.
  • 5A is a perspective view of the light emitting device
  • FIG. 5B is a cross-sectional view of FIG. 5A taken along the line X-Y.
  • an EL layer 955 is provided between the electrode 952 and the electrode 956 over the substrate 951.
  • the end of the electrode 952 is covered with an insulating layer 953.
  • a partition layer 954 is provided over the insulating layer 953.
  • the side walls of the partition layer 954 have a slope such that the distance between one side wall and the other side wall becomes narrower as the wall surface becomes closer to the substrate surface.
  • the cross section in the short side direction of the partition layer 954 has a trapezoidal shape, and the base (the side similar to the surface direction of the insulating layer 953 and the side in contact with the insulating layer 953) is the upper side (the surface of the insulating layer 953). It is oriented in the same direction as the direction and shorter than the side not in contact with the insulating layer 953).
  • the partition layer 954 By providing the partition layer 954 in this manner, defects of the light-emitting element due to static electricity or the like can be prevented.
  • the light-emitting element described in Embodiment 1 is used also in a passive matrix light-emitting device, so that a highly reliable light-emitting device or a light-emitting device with low power consumption can be obtained.
  • the light emitting device described above can control a large number of minute light emitting elements arranged in a matrix, and thus can be suitably used as a display device for expressing an image.
  • FIG. 6 (B) is a top view of the lighting device
  • FIG. 6 (A) is a cross-sectional view taken along the line ef in FIG.
  • the first electrode 401 is formed over a light-transmitting substrate 400 which is a support.
  • the first electrode 401 corresponds to the first electrode 101 in Embodiment 1.
  • the first electrode 401 is formed of a light-transmitting material.
  • a pad 412 for applying a voltage to the second electrode 404 is formed on the substrate 400.
  • An EL layer 403 is formed over the first electrode 401.
  • the EL layer 403 corresponds to the structure of the EL layer 103 in Embodiment 1 or a 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.
  • the second electrode 404 is formed to cover the EL layer 403.
  • the second electrode 404 corresponds to the second electrode 102 in Embodiment 1.
  • the second electrode 404 is formed of a material with high reflectance.
  • the second electrode 404 is connected to the pad 412 to supply a voltage.
  • the lighting device described in this embodiment includes the light-emitting element including the first electrode 401, the EL layer 403, and the second electrode 404 as described above. Since the light-emitting element is a light-emitting element with high luminous efficiency, the lighting device in this embodiment can be a lighting device with low power consumption.
  • the substrate 400 on which the light-emitting element having the above structure is formed is fixed to the sealing substrate 407 with the sealants 405 and 406 and sealed, whereby a lighting device is completed.
  • Either of the sealing materials 405 and 406 may be used.
  • a desiccant can be mixed with the inner sealing material 406 (not shown in FIG. 6B), which can adsorb moisture, which leads to improvement in reliability.
  • the pad 412 and a part of the first electrode 401 can be extended outside the sealants 405 and 406 to be an external input terminal.
  • an IC chip 420 or the like mounted with a converter or the like may be provided thereon.
  • the lighting device described in this embodiment uses the light-emitting element described in Embodiment 1 as an EL element, and can be a highly reliable light-emitting device. In addition, a light-emitting device with low power consumption can be provided.
  • Embodiment 4 In this embodiment, an example of an electronic device in which the light-emitting element described in Embodiment 1 is included in part thereof will be described.
  • the light-emitting element described in Embodiment 1 has a good lifetime and is a light-emitting element with good reliability.
  • the electronic device described in this embodiment can be an electronic device having a light emitting portion with high reliability.
  • a television set also referred to as a television or a television receiver
  • a monitor for a computer for example, a digital camera, a digital video camera, a digital photo frame, a mobile phone (mobile phone, Examples include large-sized game machines such as portable game machines, portable information terminals, sound reproduction devices, and pachinko machines. Specific examples of these electronic devices are shown below.
  • FIG. 7A illustrates an example of a television set.
  • a display portion 7103 is incorporated in a housing 7101. Further, here, a structure in which the housing 7101 is supported by the stand 7105 is shown. A video can be displayed by the display portion 7103.
  • the display portion 7103 is formed by arranging the light-emitting elements described in Embodiment 1 in a matrix.
  • the television set can be operated by an operation switch of the housing 7101 or a separate remote controller 7110. Channels and volume can be controlled with an operation key 7109 of the remote controller 7110, and an image displayed on the display portion 7103 can be manipulated. Further, the remote control 7110 may be provided with a display portion 7107 for displaying information output from the remote control 7110.
  • the television set is provided with a receiver, a modem, and the like.
  • Receivers can receive general television broadcasts, and by connecting to a wired or wireless communication network via a modem, one-way (sender to receiver) or two-way (sender and receiver) It is also possible to perform information communication between receivers or between receivers.
  • FIG. 7B1 illustrates 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 light-emitting elements described in Embodiment 1 in a matrix and using them for the display portion 7203.
  • the computer shown in FIG. 7 (B1) may have a form as shown in FIG. 7 (B2).
  • the computer illustrated 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 an input can be performed by operating the display for input displayed on the second display portion 7210 with a finger or a dedicated pen. Further, the second display unit 7210 can display not only the input display but also other images.
  • the display portion 7203 may also be a touch panel.
  • FIG. 7C shows an example of a portable terminal.
  • the portable terminal includes an operation button 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like in addition to the display portion 7402 incorporated in the housing 7401.
  • the portable terminal includes the display portion 7402 which is manufactured by arranging the light-emitting elements described in Embodiment 1 in a matrix.
  • the portable terminal illustrated in FIG. 7C can have a structure in which information 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 creating an e-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 an image
  • the second is an input mode mainly for inputting information such as characters.
  • the third is a display + input mode in which two modes of the display mode and the input mode are mixed.
  • the display portion 7402 may be in a text input mode mainly for text input, and text input operation can be performed on the screen. In this case, it is preferable to display a keyboard or a number button on most of the screen of the display portion 7402.
  • the orientation (vertical or horizontal) of the portable terminal is determined, and the screen display of the display portion 7402 is automatically performed. Can be switched on and off.
  • the screen mode is switched by touching the display portion 7402 or operating the operation button 7403 of the housing 7401.
  • switching can be performed according to the type of image displayed on the display portion 7402.
  • the display mode is switched if the image signal displayed on the display unit is data of a moving image, and the input mode is switched if it is text data.
  • the input mode a signal detected by the light sensor of the display portion 7402 is detected, and when there is no input by a touch operation on the display portion 7402, 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. For example, personal identification can be performed by touching the display portion 7402 with a palm or a finger and capturing a palm print, a fingerprint, or the like.
  • personal identification can be performed by touching the display portion 7402 with a palm or a finger and capturing a palm print, a fingerprint, or the like.
  • a backlight which emits near-infrared light or a sensing light source which emits near-infrared light is used for the display portion, an image of a finger vein, a palm vein, or the like can be taken.
  • the application range of the light-emitting device including the light-emitting element described in Embodiment 1 is so wide that the light-emitting device can be applied to electronic devices in various fields.
  • a highly reliable electronic device can be obtained.
  • FIG. 8A is a schematic view showing an example of the cleaning robot.
  • the cleaning robot 5100 has a display 5101 disposed on the upper surface, a plurality of cameras 5102 disposed on the side, a brush 5103, and an operation button 5104.
  • the lower surface of the cleaning robot 5100 is provided with a tire, a suction port, and the like.
  • the cleaning robot 5100 further 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 is provided with a wireless communication means.
  • the cleaning robot 5100 can self-propelled, detect the dust 5120, and can suction the dust from the suction port provided on the lower surface.
  • the cleaning robot 5100 can analyze the image captured by the camera 5102 to determine the presence or absence of an obstacle such as a wall, furniture, or a step. In addition, when an object that is likely to be entangled in the brush 5103 such as wiring 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 suctioned dust, and the like.
  • the path traveled by the cleaning robot 5100 may be displayed on the display 5101.
  • the display 5101 may be a touch panel, and the operation button 5104 may be provided on the display 5101.
  • the cleaning robot 5100 can communicate with a portable electronic device 5140 such as a smartphone.
  • the image captured by the camera 5102 can be displayed on the portable electronic device 5140. Therefore, the owner of the cleaning robot 5100 can know the state of the room even from outside.
  • the display of the display 5101 can also be confirmed by a portable electronic device such as a smartphone.
  • the light-emitting device of one embodiment of the present invention 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 movement mechanism 2108.
  • the microphone 2102 has a function of detecting the user's speech and environmental sounds.
  • 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 information.
  • the robot 2100 can display information desired by the user on the display 2105.
  • the display 2105 may have a touch panel.
  • the display 2105 may be an information terminal that can be removed, and by installing the robot 2100 in a fixed position, charging and data transfer can be performed.
  • the upper camera 2103 and the lower camera 2106 have a function of imaging the periphery 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 advances using the movement mechanism 2108. The robot 2100 can recognize the surrounding environment and move safely by using the upper camera 2103, the lower camera 2106 and the obstacle sensor 2107.
  • FIG. 8C is a diagram showing an example of the goggle type display.
  • the goggle type display includes, for example, a housing 5000, a display portion 5001, a speaker 5003, an LED lamp 5004, an operation key (including a power switch or an operation switch), a connection terminal 5006, a sensor 5007 (force, displacement, position, speed, Measurement of acceleration, angular velocity, number of rotations, distance, light, liquid, magnetism, temperature, chemicals, voice, time, hardness, electric field, current, voltage, power, radiation, flow rate, humidity, inclination, vibration, odor or infrared light Function), a microphone 5008, a second display portion 5002, a support portion 5012, an earphone 5013, and the like.
  • the light-emitting device of one embodiment of the present invention can be used for the display portion 5001 and the second display portion 5002.
  • FIG. 9 illustrates an example in which the light-emitting element described in Embodiment 1 is used for a desk 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 illustrates an example in which the light-emitting element described in Embodiment 1 is used as a lighting device 3001 in a room. Since the light-emitting element described in Embodiment 1 is a highly reliable light-emitting element, the lighting device can have high reliability. In addition, since the light-emitting element described in Embodiment 1 can have a large area, it can be used as a large-area lighting device. In addition, since the light-emitting element described in Embodiment 1 is thin, it can be used as a thin lighting device.
  • the light emitting device described in Embodiment 1 can also be mounted on the windshield or dashboard of a car.
  • FIG. 11 shows an embodiment in which the light-emitting element described in Embodiment 1 is used for a windshield or a dashboard of a car.
  • the display regions 5200 to 5203 are displays provided using the light-emitting element described in Embodiment 1.
  • a display region 5200 and a display region 5201 are display devices provided with the light-emitting element described in Embodiment 1 provided on a windshield of a car.
  • the light-emitting element described in Embodiment 1 can be a display device in a so-called see-through state, in which the opposite side can be seen through, by manufacturing the first electrode and the second electrode with a light-transmitting electrode. . If it is a see-through display, even if it is installed on the windshield of a car, it can be installed without obstructing the view. Note that in the case where a transistor or the like for driving is provided, a light-transmitting transistor such as an organic transistor made of an organic semiconductor material or a transistor using an oxide semiconductor is preferably used.
  • the display region 5202 is a display device provided with the light-emitting element described in Embodiment 1 provided in a pillar portion.
  • the display area 5203 provided in the dashboard part compensates for the blind spot and enhances the safety by projecting the image from the imaging means provided outside the car, with the view blocked by the vehicle body. Can. By projecting the image so as to complement the invisible part, it is possible to check the safety more naturally and without discomfort.
  • the display area 5203 can also provide various other information such as navigation information, speedometers and tachometers, travel distance, fuel, gear status, settings of the air conditioner, and the like.
  • the display items can be changed as appropriate in accordance with the preference of the user. Note that these pieces of information can also be provided in the display area 5200 to the display area 5202.
  • the display regions 5200 to 5203 can also be used as lighting devices.
  • FIG. 12A and 12B illustrate a foldable portable information terminal 5150.
  • the foldable portable information terminal 5150 includes a housing 5151, a display area 5152, and a bending portion 5153.
  • FIG. 12A shows the portable information terminal 5150 in the expanded state.
  • FIG. 12B shows the portable information terminal in a folded state.
  • the portable information terminal 5150 has a large display area 5152, it is compact and portable when folded.
  • the display region 5152 can be folded in half by the bent portion 5153.
  • the bending portion 5153 is composed of an expandable member and a plurality of support members, and in the case of folding, the expandable member extends.
  • the bent portion 5153 is folded with a curvature radius of 2 mm or more, preferably 3 mm or more.
  • the display area 5152 may be a touch panel (input / output device) that controls a touch sensor (input device).
  • the light-emitting device of one embodiment of the present invention can be used for the display region 5152.
  • FIGS. 13 (A) to 13 (C) show a foldable portable information terminal 9310.
  • the portable information terminal 9310 in the expanded state is shown in FIG.
  • FIG. 13B shows the portable information terminal 9310 in the middle of changing from one of the expanded state or the folded state to the other.
  • FIG. 13C shows the portable information terminal 9310 in a folded state.
  • the portable information terminal 9310 is excellent in portability in the folded state, and in the expanded state, is excellent in viewability of display due to a wide seamless display area.
  • the display panel 9311 is supported by three housings 9315 connected by hinges 9313.
  • the display panel 9311 may be a touch panel (input / output device) on which a touch sensor (input device) is mounted.
  • the display panel 9311 can be reversibly deformed into a folded state from a state in which the portable information terminal 9310 is expanded by bending between the two housings 9315 via the hinges 9313.
  • the light-emitting device of one embodiment of the present invention can be used for the display panel 9311.
  • the light-emitting elements 1 to 3, the comparative light-emitting element 1, and the comparative light-emitting element 2 of one embodiment of the present invention described in Embodiment 1 will be described.
  • Structural formulas of organic compounds used in Light-emitting Elements 1 to 3, Comparative Light-emitting Element 1, and Comparative Light-emitting Element 2 are shown below.
  • indium tin oxide (ITSO) containing silicon oxide was deposited over a glass substrate by a sputtering method to form a first electrode 101.
  • the film thickness was 70 nm, and the electrode area was 2 mm ⁇ 2 mm.
  • the substrate surface was washed with water and baked at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
  • the substrate is introduced into a vacuum deposition apparatus whose inside is depressurized to about 10 -4 Pa, and vacuum baking is performed at 170 ° C. for 30 minutes in a heating chamber in the vacuum deposition apparatus, and then the substrate is released for about 30 minutes. It was cold.
  • PCCP 3,3′-bis (9-phenyl-9H-carbazole) represented by the above structural formula (iii) is vapor deposited on the hole injection layer 111 to a film thickness of 20 nm.
  • the hole transport layer 112 was formed.
  • 4,6-bis [3- (9H-carbazol-9-yl) phenyl] pyrimidine represented by the above structural formula (iv), PCCP, and the above structural formula (v) And tris (2-phenylpyridinato-N, C 2 ') iridium (III) (abbreviation: [Ir (ppy) 3 ]) in a weight ratio of 0.5: 0.5: 0.1
  • 4, 6mCzP2Pm: PCCP: [Ir ( 20 nm co-evaporation was carried out so that it might become ppy) 3 ])
  • the light emitting layer 113 was formed.
  • 4,6mCzP2Pm is deposited on the light emitting layer 113 to a film thickness of 20 nm, and then bathophenanthroline (abbreviation: BPhen) represented by the above structural formula (vi) is deposited to a film thickness of 10 nm. , And the electron transport layer 114 were formed.
  • BPhen bathophenanthroline
  • lithium fluoride (LiF) is evaporated to a film thickness of 1 nm to form an electron injection layer 115, and subsequently, aluminum is evaporated to a film thickness of 200 nm.
  • the second electrode 102 was formed to fabricate a light emitting element 1 of this example.
  • 30 nm co-evaporation of m-MTDATA and molybdenum (VI) oxide in a weight ratio of 2: 1 ( m-MTDATA: molybdenum oxide)
  • the element structures of the light emitting element 1 to the light emitting element 3, the comparative light emitting element 1, and the comparative light emitting element 2 are summarized in the following table.
  • the luminance-current density characteristics of Light-emitting elements 1 to 3, Comparative light-emitting element 1 and Comparative light-emitting element 2 are shown in FIG. 14, current efficiency-luminance characteristics are shown in FIG. 15, luminance-voltage characteristics are shown in FIG. The characteristics are shown in FIG. 17, the external quantum efficiency-luminance characteristics in FIG. 18, and the emission spectrum in FIG. Also, showing the main characteristics in the vicinity of 1000 cd / m 2 of the light-emitting elements shown in Table 2.
  • Light-emitting Elements 1 to 3 which are one embodiment of the present invention are elements which generally exhibit very good light-emitting efficiency with an external quantum efficiency of 27% or more.
  • the comparative light emitting element 1 and the comparative light emitting element 2 have lower external quantum efficiency of 24% to 25%, but the efficiency is lower than that of the light emitting elements 1 to 3.
  • the comparative light-emitting element 1 has a structure in which only the fluoride of an alkali metal or the fluoride of an alkaline earth metal is removed from the structures of the light-emitting elements 1 to 3.
  • the comparative light-emitting element 2 has a structure of the light-emitting elements 1 to
  • the element 3 has a conventional configuration in which a three-layer hole injection layer is formed of a composite material layer consisting of one type of hole transport material and an electron accepting material. From this, it includes an alkali metal fluoride or an alkaline earth metal fluoride (first substance), a hole transport material (second substance), and an electron accepting substance (third substance). It has been found that provision of a low refractive index layer formed of a composite material in the hole injection layer has an effect of largely increasing the light emission efficiency of the light emitting element.
  • the refractive index of a single film of each material that can be used as the first substance, the second substance, and the third substance is shown in Table 3, a composite material of the second substance and the third substance (the following , And OMOx), and the refractive index of a novel composite material (hereinafter also referred to as F-OMOx) composed of the first substance, the second substance and the third substance is shown in Table 4. Note that since the film formed of the second substance and the mixed film containing the second substance are anisotropic, the refractive index indicates nordary. The refractive index shows a value near 532 nm.
  • the composite material (OMO x) composed of the second substance having hole transportability and the third substance having a high refractive index is equal to or higher than the refractive index of the second substance It can be seen that the material has a refractive index of
  • the novel composite material which is a material further including an alkali metal fluoride in the composite material, significantly reduces its refractive index. From Table 3, it can be seen that the first substance, fluoride of alkali metal or alkaline earth metal, is a substance with a small refractive index, but the refraction of the new composite material by containing a large amount of such materials. The rate is considered to be decreasing.
  • the absorbance measurement and ESR measurement of a thin film of a composite material containing an alkali metal fluoride or an alkaline earth metal fluoride, a hole transport material, and an electron accepting material were measured.
  • the results are shown in FIG. 20 and Table 5.
  • a sample was produced by forming a co-deposited film of the above-mentioned material 50 nm on a quartz substrate.
  • Absorbance measurement was carried out at room temperature using a spectrophotometer U4100 manufactured by Hitachi High-Technologies Corporation.
  • the ESR measurement was performed at room temperature with a magnetic field modulation frequency of 100 kHz by an electron spin resonance apparatus E500 manufactured by Bruker.
  • Sample 1 is m-MTDATA single film
  • sample 2 is co-deposited film of m-MTDATA and molybdenum oxide (2: 1)
  • sample 3 is co-deposited film of sodium fluoride, m-MTDATA and molybdenum oxide (4: 0.5: 1)
  • sample 4 is a co-deposited film of potassium fluoride, m-MTDATA and molybdenum oxide (4: 0.5: 1)
  • sample 5 is lithium fluoride
  • sample 6 is a co-deposited film of calcium fluoride, m-MTDATA and molybdenum oxide (5: 0.5: 1)
  • sample 7 is magnesium fluoride and m- A co-deposited film (5: 0.5: 1) of MTDATA and molybdenum oxide.
  • the mixing ratio is represented by weight.
  • the spin density showed the highest value in sample 2 which is a conventional composite material not containing the first substance.
  • the value of the spin density largely changes depending on the type of the first substance contained.
  • Samples 5 to 7 are films having the same composition as the layers used for the hole injection layers of the light-emitting elements 1 to 3.
  • the spin density of each of the films used for the light emitting element with good characteristics is 1 ⁇ 10 18 spins / cm 3 or more.
  • the spin density of the film (Sample 3 and Sample 4) containing sodium fluoride or potassium fluoride as the first substance is immeasurable or less than 1 ⁇ 10 17 spins / cm 3, as can be seen from Table 5.
  • the These materials were found to have a significantly lower spin density than the other materials.
  • a light emitting element in which a film having the same composition as these films is used for a hole transporting layer has a significant deterioration in characteristics and hardly functions as a light emitting element.
  • a novel composite material having a spin concentration of 1.0 ⁇ 10 18 spins / cm 3 or more measured by ESR method has good driving characteristics and It turned out that it is possible to make luminous efficiency compatible.
  • the absorbance ⁇ was calculated based on the following equation by measuring the transmittance T (%) and the reflectance R (%) of the sample.
  • the absorption of quartz used as the substrate is also measured in an overlapping manner.
  • the absorptions having peaks at around 450 nm and at around 1200 nm are absorptions from the charge transfer complex of the hole transport material which is the second substance and the molybdenum oxide which is the third substance. It can be seen that Sample 1, Sample 3 and Sample 4 do not show these absorptions, and Sample 2 and Samples 5 to 7 show these absorptions.
  • the lithium fluoride used in sample 5 may be used in the electron injection layer.
  • fluorides of these alkali metals or alkaline earth metals may be used in the light emitting element as substances exhibiting an electron donating property.
  • molybdenum oxide or the like is an electron accepting substance, and these substances have opposite properties.
  • the new composite material has a smaller absorption due to the formation of the charge transfer complex than the conventional composite material using the same second and third substances, so that the visible light It turned out that absorption becomes small and it becomes a highly transparent material. That is, the loss due to absorption in the hole injection layer is reduced, which also contributes to the improvement of the efficiency of the light emitting device.
  • Fluorides of alkali metals or alkaline earth metals are insulators in the first place, and they are employed as an extremely thin film of about 1 nm even when used for the electron injection layer.
  • the fluoride layer is a relatively thick film of about 30 nm, and the fluoride is about four times the weight ratio of the amount of molybdenum oxide, and about three quarters of the entire material. Is also used as the main component of the membrane. That is, the novel composite material used in one aspect of the present invention is characterized in that the insulating material, which is a fluoride, is a main component, and functions normally as a hole injection layer even if it is a relatively thick film. It is.
  • the light-emitting element 4 and the light-emitting element 5 which are light-emitting elements of one embodiment of the present invention described in Embodiment will be described.
  • Comparative Light-emitting Element 3 and Comparative Light-emitting Element 4 were also produced. Structural formulas of organic compounds used in the light-emitting element 4 and the light-emitting element 5, the comparative light-emitting element 3, and the comparative light-emitting element 4 are shown below.
  • indium tin oxide (ITSO) containing silicon oxide was deposited over a glass substrate by a sputtering method to form a first electrode 101.
  • the film thickness was 70 nm, and the electrode area was 2 mm ⁇ 2 mm.
  • the substrate surface was washed with water and baked at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
  • the substrate is introduced into a vacuum deposition apparatus whose inside is depressurized to about 10 -4 Pa, and vacuum baking is performed at 170 ° C. for 30 minutes in a heating chamber in the vacuum deposition apparatus, and then the substrate is released for about 30 minutes. It was cold.
  • the substrate on which the first electrode 101 is formed is fixed to a substrate holder provided in a vacuum evaporation apparatus so that the surface on which the first electrode 101 is formed is downward, and the first electrode 101 is formed.
  • Calcium fluoride (CaF 2 ) and N- (1,1′-biphenyl-4-yl) -9,9- represented by the above structural formula (vii) are deposited thereon by vapor deposition using resistance heating.
  • PCBBiF Dimethyl-N- [4- (9-phenyl-9H-carbazol-3-yl) phenyl] -9H-fluoren-2-amine
  • VI molybdenum oxide
  • PCBBiF was vapor-deposited to a film thickness of 15 nm to form a hole transport layer 112.
  • 2mDBTBPDBq-II is vapor deposited on the light emitting layer 113 to a film thickness of 25 nm, and then bathophenanthroline (abbreviation: BPhen) represented by the above structural formula (vi) is vapor deposited to a film thickness of 10 nm. , And the electron transport layer 114 were formed.
  • BPhen bathophenanthroline
  • lithium fluoride (LiF) is evaporated to a film thickness of 1 nm to form an electron injection layer 115, and subsequently, aluminum is evaporated to a film thickness of 200 nm.
  • the two electrodes 102 were formed to fabricate a light emitting element 4 of this example.
  • the light emitting element 4 was formed in the same manner as the light emitting element 4 except that it was formed by vapor deposition.
  • the light emitting element 4 was formed in the same manner as the light emitting element 4 except that it was formed by vapor deposition.
  • the element structures of the light emitting element 4, the light emitting element 5, the comparative light emitting element 3 and the comparative light emitting element 4 are summarized in the following table.
  • the luminance-current density characteristics of the light-emitting element 4, the light-emitting element 5, the comparative light-emitting element 3 and the comparative light-emitting element 4 are shown in FIG. 21, current efficiency-luminance characteristics are shown in FIG. 22, luminance-voltage characteristics are shown in FIG. The characteristics are shown in FIG. 24, the external quantum efficiency-luminance characteristics in FIG. 25, and the emission spectrum in FIG. Further, main characteristics of each light emitting element in the vicinity of 1000 cd / m 2 are shown in Table 7.
  • the light-emitting element 4 and the light-emitting element 5 which are one embodiment of the present invention can be a light-emitting element whose external quantum efficiency is as high as 35% to 36%. it can.
  • the external quantum efficiency of the comparative light emitting element 3 and the comparative light emitting element 4 is about 32%, and this is also a light emitting element showing very good light emitting efficiency, but by using the configuration of the present invention, the light emitting efficiency is further improved. Can be obtained.
  • the light-emitting element 6 of one embodiment of the present invention described in Embodiment 1 and the comparative light-emitting element 5 are described.
  • Structural formulas of organic compounds used in the light-emitting element 6 and the comparative light-emitting element 5 are shown below.
  • indium tin oxide (ITSO) containing silicon oxide was deposited over a glass substrate by a sputtering method to form a first electrode 101.
  • the film thickness was 70 nm, and the electrode area was 2 mm ⁇ 2 mm.
  • the substrate surface was washed with water and baked at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
  • the substrate is introduced into a vacuum deposition apparatus whose inside is depressurized to about 10 -4 Pa, and vacuum baking is performed at 170 ° C. for 30 minutes in a heating chamber in the vacuum deposition apparatus, and then the substrate is released for about 30 minutes. It was cold.
  • the substrate on which the first electrode 101 is formed is fixed to a substrate holder provided in a vacuum evaporation apparatus so that the surface on which the first electrode 101 is formed is downward, and the first electrode 101 is formed.
  • Calcium fluoride (CaF 2 ) and N- (1,1′-biphenyl-4-yl) -9,9- represented by the above structural formula (vii) are deposited thereon by vapor deposition using resistance heating.
  • PCBBiF Dimethyl-N- [4- (9-phenyl-9H-carbazol-3-yl) phenyl] -9H-fluoren-2-amine
  • VI molybdenum oxide
  • PCBBiF was vapor-deposited to a film thickness of 15 nm to form a hole transport layer 112.
  • 2mDBTBPDBq-II is vapor deposited on the light emitting layer 113 to a film thickness of 25 nm, and then bathophenanthroline (abbreviation: BPhen) represented by the above structural formula (vi) is vapor deposited to a film thickness of 10 nm. , And the electron transport layer 114 were formed.
  • BPhen bathophenanthroline
  • lithium fluoride (LiF) is evaporated to a film thickness of 1 nm to form an electron injection layer 115, and subsequently, aluminum is evaporated to a film thickness of 200 nm.
  • the electrode 102 of No. 2 was formed, and the light emitting element 6 of this example was manufactured.
  • CaF 2 calcium fluoride
  • PCBBiF molybdenum oxide
  • the luminance-current density characteristics of the light-emitting element 6 and the comparative light-emitting element 5 are shown in FIG. 27, the current efficiency-luminance characteristic is shown in FIG. 28, the luminance-voltage characteristic is shown in FIG. 29, the current-voltage characteristic is shown in FIG. The luminance characteristics are shown in FIG. 31, and the emission spectrum is shown in FIG. Further, main characteristics of each light emitting element in the vicinity of 1000 cd / m 2 are shown in Table 9.
  • the hole injection layer is alkali such as calcium fluoride
  • Light emitting element 6 comprising three materials of an earth metal fluoride or an alkali metal fluoride, a hole transporting material, and an electron accepting material such as molybdenum oxide, has a very good performance It turned out that it was.
  • the light-emitting element 7 of one embodiment of the present invention described in Embodiment 1 and the comparative light-emitting element 6 are described.
  • Structural formulas of organic compounds used in the light-emitting element 7 and the comparative light-emitting element 6 are shown below.
  • indium tin oxide (ITSO) containing silicon oxide was deposited over a glass substrate by a sputtering method to form a first electrode 101.
  • the film thickness was 70 nm, and the electrode area was 2 mm ⁇ 2 mm.
  • the substrate surface was washed with water and baked at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
  • the substrate is introduced into a vacuum deposition apparatus whose inside is depressurized to about 10 -4 Pa, and vacuum baking is performed at 170 ° C. for 30 minutes in a heating chamber in the vacuum deposition apparatus, and then the substrate is released for about 30 minutes. It was cold.
  • the substrate on which the first electrode 101 is formed is fixed to a substrate holder provided in a vacuum evaporation apparatus so that the surface on which the first electrode 101 is formed is downward, and the first electrode 101 is formed.
  • 1,1-bis- (4-bis (4-methyl-phenyl) -amino-phenyl) -cyclohexane (abbreviation: TAPC) represented by the above structural formula (x) by vapor deposition using resistance heating.
  • Phenyl-9H-carbazol-3-yl) phenyl] -9H-fluoren-2-amine (abbreviation: PCBBiF) was deposited to a film thickness of 15 nm to form a hole transporting layer 112.
  • 2mDBTBPDBq-II is vapor deposited on the light emitting layer 113 to a film thickness of 25 nm, and then 2,9-bis (naphthalene-2-yl) -4,7- represented by the above structural formula (xii) Diphenyl-1,10-phenanthroline (abbreviation: NBPhen) was vapor-deposited to a film thickness of 15 nm to form an electron transporting layer 114.
  • lithium fluoride (LiF) is evaporated to a film thickness of 1 nm to form an electron injection layer 115, and subsequently, aluminum is evaporated to a film thickness of 200 nm.
  • the two electrodes 102 were formed to fabricate a light emitting element 7 of this example.
  • the luminance-current density characteristics of the light emitting element 7 and the comparative light emitting element 6 are shown in FIG. 33, the current efficiency-luminance characteristic is shown in FIG. 34, the luminance-voltage characteristic is shown in FIG. 35, and the current-voltage characteristic is shown in FIG.
  • the luminance characteristics are shown in FIG. 37, and the emission spectrum is shown in FIG. Further, main characteristics of each light emitting element in the vicinity of 1000 cd / m 2 are shown in Table 11.
  • a film co-deposited with TAPC C 24 F 50 : molybdenum oxide at 1: 1: 0.5 (weight ratio) and a film co-evaporated with TAPC: molybdenum oxide at 2: 0.5 (weight ratio)
  • a graph showing the change of the refractive index in the visible light region of the film is shown in FIG. From FIG. 39, it was found that the film mixed with C 24 F 50 has a refractive index lowered by about 0.2 to 0.3 in the entire wavelength region. That is, although the light emitting element 7 has substantially the same structure as the comparative light emitting element 6, a part of the layer has a small refractive index in the EL layer.

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne un nouveau élément électroluminescent. L'invention concerne en outre un élément électroluminescent ayant une longévité favorable. L'invention concerne également un élément électroluminescent qui a une efficacité d'émission favorable. L'invention concerne également un dispositif électronique qui a une première électrode, une seconde électrode et une première couche qui est prise en sandwich entre la première électrode et la seconde électrode. La première couche comprend au moins une seconde couche et une troisième couche. La seconde couche est positionnée entre la troisième couche et la première électrode. La seconde couche comprend une première substance, une seconde substance et une troisième substance. La première substance est un composé qui comprend du fluor. La seconde substance est un composé organique qui a des propriétés de transport de trous. La troisième substance peut accepter des électrons provenant de la seconde substance.
PCT/IB2018/056298 2017-09-01 2018-08-21 Dispositif électronique, élément électroluminescent, batterie solaire, dispositif électroluminescent, appareil électronique et dispositif d'éclairage WO2019043501A1 (fr)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
JP2007141736A (ja) * 2005-11-21 2007-06-07 Fujifilm Corp 有機電界発光素子
JP2010123716A (ja) * 2008-11-19 2010-06-03 Fujifilm Corp 有機電界発光素子
JP2010147338A (ja) * 2008-12-19 2010-07-01 Panasonic Electric Works Co Ltd 有機エレクトロルミネッセンス素子
JP2012049159A (ja) * 2010-08-24 2012-03-08 Toray Ind Inc 発光素子
JP2012204022A (ja) * 2011-03-23 2012-10-22 Panasonic Corp 透明導電膜、透明導電膜付き基材、及びそれを用いた有機エレクトロルミネッセンス素子
JP2013179248A (ja) * 2011-08-12 2013-09-09 Canon Inc 有機ｅｌ素子、及びこれを用いた発光装置、画像形成装置、表示装置、撮像装置
JP2016153400A (ja) * 2015-02-18 2016-08-25 株式会社半導体エネルギー研究所 有機化合物、発光素子、ディスプレイモジュール、照明モジュール、発光装置、表示装置、電子機器及び照明装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007141736A (ja) * 2005-11-21 2007-06-07 Fujifilm Corp 有機電界発光素子
JP2010123716A (ja) * 2008-11-19 2010-06-03 Fujifilm Corp 有機電界発光素子
JP2010147338A (ja) * 2008-12-19 2010-07-01 Panasonic Electric Works Co Ltd 有機エレクトロルミネッセンス素子
JP2012049159A (ja) * 2010-08-24 2012-03-08 Toray Ind Inc 発光素子
JP2012204022A (ja) * 2011-03-23 2012-10-22 Panasonic Corp 透明導電膜、透明導電膜付き基材、及びそれを用いた有機エレクトロルミネッセンス素子
JP2013179248A (ja) * 2011-08-12 2013-09-09 Canon Inc 有機ｅｌ素子、及びこれを用いた発光装置、画像形成装置、表示装置、撮像装置
JP2016153400A (ja) * 2015-02-18 2016-08-25 株式会社半導体エネルギー研究所 有機化合物、発光素子、ディスプレイモジュール、照明モジュール、発光装置、表示装置、電子機器及び照明装置

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