WO2021111227A1 - 発光デバイス、発光装置、電子機器および照明装置 - Google Patents

発光デバイス、発光装置、電子機器および照明装置 Download PDF

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Publication number
WO2021111227A1
WO2021111227A1 PCT/IB2020/060831 IB2020060831W WO2021111227A1 WO 2021111227 A1 WO2021111227 A1 WO 2021111227A1 IB 2020060831 W IB2020060831 W IB 2020060831W WO 2021111227 A1 WO2021111227 A1 WO 2021111227A1
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Prior art keywords
layer
light emitting
electrode
emitting device
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English (en)
French (fr)
Japanese (ja)
Inventor
渡部剛吉
植田藍莉
大澤信晴
瀬尾哲史
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Priority to CN202080083525.XA priority Critical patent/CN114747295A/zh
Priority to JP2021562197A priority patent/JPWO2021111227A1/ja
Priority to KR1020227017251A priority patent/KR102931688B1/ko
Priority to US17/780,247 priority patent/US12364115B2/en
Publication of WO2021111227A1 publication Critical patent/WO2021111227A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/126—Shielding, e.g. light-blocking means over the TFTs
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L11/00—Machines for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L11/40—Parts or details of machines not provided for in groups A47L11/02 - A47L11/38, or not restricted to one of these groups, e.g. handles, arrangements of switches, skirts, buffers, levers
    • A47L11/4011—Regulation of the cleaning machine by electric means; Control systems and remote control systems therefor
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L11/00—Machines for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L11/40—Parts or details of machines not provided for in groups A47L11/02 - A47L11/38, or not restricted to one of these groups, e.g. handles, arrangements of switches, skirts, buffers, levers
    • A47L11/4061—Steering means; Means for avoiding obstacles; Details related to the place where the driver is accommodated
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L9/00—Details or accessories of suction cleaners, e.g. mechanical means for controlling the suction or for effecting pulsating action; Storing devices specially adapted to suction cleaners or parts thereof; Carrying-vehicles specially adapted for suction cleaners
    • A47L9/28—Installation of the electric equipment, e.g. adaptation or attachment to the suction cleaner; Controlling suction cleaners by electric means
    • A47L9/2805—Parameters or conditions being sensed
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L9/00—Details or accessories of suction cleaners, e.g. mechanical means for controlling the suction or for effecting pulsating action; Storing devices specially adapted to suction cleaners or parts thereof; Carrying-vehicles specially adapted for suction cleaners
    • A47L9/28—Installation of the electric equipment, e.g. adaptation or attachment to the suction cleaner; Controlling suction cleaners by electric means
    • A47L9/2805—Parameters or conditions being sensed
    • A47L9/2826—Parameters or conditions being sensed the condition of the floor
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L9/00—Details or accessories of suction cleaners, e.g. mechanical means for controlling the suction or for effecting pulsating action; Storing devices specially adapted to suction cleaners or parts thereof; Carrying-vehicles specially adapted for suction cleaners
    • A47L9/28—Installation of the electric equipment, e.g. adaptation or attachment to the suction cleaner; Controlling suction cleaners by electric means
    • A47L9/2857—User input or output elements for control, e.g. buttons, switches or displays
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L9/00—Details or accessories of suction cleaners, e.g. mechanical means for controlling the suction or for effecting pulsating action; Storing devices specially adapted to suction cleaners or parts thereof; Carrying-vehicles specially adapted for suction cleaners
    • A47L9/28—Installation of the electric equipment, e.g. adaptation or attachment to the suction cleaner; Controlling suction cleaners by electric means
    • A47L9/30—Arrangement of illuminating devices
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • 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
    • H05B33/02—Details
    • 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
    • H05B33/02—Details
    • H05B33/06—Electrode terminals
    • 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 [2D] radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • 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 [2D] radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional [2D] 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L2201/00—Robotic cleaning machines, i.e. with automatic control of the travelling movement or the cleaning operation
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L2201/00—Robotic cleaning machines, i.e. with automatic control of the travelling movement or the cleaning operation
    • A47L2201/04—Automatic control of the travelling movement; Automatic obstacle detection
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • 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
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
    • 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
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/32—Stacked devices having two or more layers, each emitting at different wavelengths
    • 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
    • H10K59/40—OLEDs integrated with touch screens
    • 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
    • H10K59/60—OLEDs integrated with inorganic light-sensitive elements, e.g. with inorganic solar cells or inorganic photodiodes
    • H10K59/65—OLEDs integrated with inorganic image sensors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • One aspect of the present invention relates to organic compounds, light emitting elements, light emitting devices, display modules, lighting modules, display devices, light emitting devices, electronic devices, lighting devices and electronic devices.
  • One aspect of the present invention is not limited to the above technical fields.
  • the technical field of one aspect of the invention disclosed in the present specification and the like relates to a product, a method, or a manufacturing method.
  • one aspect of the invention relates to a process, machine, manufacture, or composition of matter. Therefore, more specifically, the technical fields of one aspect of the present invention disclosed in the present specification include semiconductor devices, display devices, liquid crystal display devices, light emitting devices, lighting devices, power storage devices, storage devices, imaging devices, and the like.
  • the driving method or the manufacturing method thereof can be given as an example.
  • organic EL devices that utilize electroluminescence (EL) using organic compounds
  • EL layer organic compound layer
  • EL layer organic compound layer
  • Such a light emitting device can form a light emitting layer continuously in two dimensions, it is possible to obtain light emission in a planar manner. This is a feature that is difficult to obtain with a point light source represented by an incandescent lamp or an LED, or a line light source represented by a fluorescent lamp, and therefore has high utility value as a surface light source that can be applied to lighting or the like.
  • the organic EL device by manufacturing the organic EL device on a flexible substrate such as a plastic substrate, it is possible to use it as a flexible light source.
  • organic EL devices that emit light in the near-infrared region (780 nm to 1400 nm) having a long wavelength has been actively conducted. Since this wavelength region has high transmittance in water and hemoglobin, it can be used for sensing (biosensing) to a living body.
  • organic EL devices have the characteristics of being flexible and capable of surface light sources, and are easy to fit into the shape of living organisms. Therefore, organic EL devices that emit near-infrared light are said to be suitable for application to biosensing. There is.
  • the organic EL device that emits near-infrared light is a useful technique, but has a problem that the luminous efficiency is essentially lower than that of other emission colors. This is because it is affected by the bandgap law. Another reason is that when the host is doped with a near-infrared light emitting dopant in the light emitting layer, the HOMO-LUMO gap of the dopant is extremely narrow as compared with the host, so that a carrier trap is easily formed. This not only lowers the luminous efficiency, but may also adversely affect the device life. For this reason, there are very few research reports on organic EL devices that emit near-infrared light that have not only high luminous efficiency but also a sufficient life.
  • Patent Document 1 reports a phosphorescent dopant having an emission spectrum from deep red to near infrared.
  • one aspect of the present invention is to provide a near-infrared light emitting device having high luminous efficiency.
  • one aspect of the present invention is to provide a light emitting device, a light emitting device, an electronic device, a display device, and an electronic device having low power consumption.
  • the present invention shall solve any one of the above-mentioned problems.
  • One aspect of the present invention has a first electrode, a second electrode, and an EL layer, and the EL layer is located between the first electrode and the second electrode, and the EL
  • the layer exhibits light having a peak of the emission spectrum in the wavelength range of 750 nm or more and 1000 nm or less, and either one of the first electrode and the second electrode is used for light having a peak wavelength of the emission spectrum in the EL layer.
  • it is a transparent electrode, and the transparent electrode has a first layer in contact with the surface opposite to the surface on which the EL layer is formed with respect to the transparent electrode.
  • the first layer contains an organic compound, and the first layer is a light emitting device having an extinction coefficient k having a maximum value in the visible light region.
  • another aspect of the present invention has a first electrode, a second electrode, and an EL layer, and the EL layer is located between the first electrode and the second electrode.
  • the EL layer exhibits light having a peak emission spectrum in a wavelength range of 750 nm or more and 1000 nm or less, and either the first electrode or the second electrode has a peak emission spectrum in the EL layer.
  • An electrode that is transparent to light of a wavelength, and the transparent electrode is in contact with a surface opposite to the surface on which the EL layer is formed with respect to the transparent electrode.
  • the first layer is a light emitting device containing an organic compound and having an extinction coefficient k of 0.05 or more in the visible light region of the first layer.
  • another aspect of the present invention has a first electrode, a second electrode, and an EL layer, and the EL layer is located between the first electrode and the second electrode.
  • the EL layer exhibits light having a peak emission spectrum in a wavelength range of 750 nm or more and 1000 nm or less, and either the first electrode or the second electrode has a peak emission spectrum in the EL layer.
  • An electrode that is transparent to light of a wavelength, and the transparent electrode is in contact with a surface opposite to the surface on which the EL layer is formed with respect to the transparent electrode.
  • the first layer is a light emitting device containing an organic compound and having an extinction coefficient k of 0.2 or more in the visible light region of the first layer.
  • another aspect of the present invention is a light emitting device in which the refractive index n of the first layer is 1.9 or more at the peak wavelength of the light emission spectrum of the EL layer in the above configuration.
  • either one of the first electrode and the second electrode has transparency to light having a peak wavelength of the emission spectrum in the EL layer.
  • the electrode is a light emitting device, and the other is an electrode having reflectivity to light having a peak wavelength of the light emission spectrum in the EL layer.
  • the transmissive electrode is a semi-transmissive semi-reflective electrode that is more reflective of light having a peak wavelength in the emission spectrum of the EL layer. It is a device.
  • another aspect of the present invention is a light emitting device in which the second electrode is a transmissive electrode and the second electrode is a cathode in the above configuration.
  • another aspect of the present invention is a light emitting device in which the first electrode is a transmissive electrode and the first electrode is an anode in the above configuration.
  • another aspect of the present invention is a light emitting device in which the organic compound contained in the first layer is one kind in the above configuration.
  • another aspect of the present invention is a light emitting device in which the organic compound contained in the first layer is a substance that can be vapor-deposited by resistance heating in the above configuration.
  • another aspect of the present invention includes the light emitting device, a sensor, an operation button, a speaker, or a microphone. It is an electronic device having.
  • another aspect of the present invention is a light emitting device having the above light emitting device, a transistor, or a substrate.
  • another aspect of the present invention is a lighting device having the light emitting device and a housing.
  • the light emitting device in the present specification includes an image display device using the light emitting device. Further, a module in which a connector, for example, an anisotropic conductive film or TCP (Tape Carrier Package) is attached to the light emitting device, a module in which a printed wiring board is provided at the tip of TCP, or a COG (Chip On Glass) method in the light emitting device. A module in which an IC (integrated circuit) is directly mounted may also be included in the light emitting (display) device. Further, lighting equipment and the like may have a light emitting device.
  • a connector for example, an anisotropic conductive film or TCP (Tape Carrier Package) is attached to the light emitting device
  • a module in which a printed wiring board is provided at the tip of TCP or a COG (Chip On Glass) method in the light emitting device.
  • a module in which an IC (integrated circuit) is directly mounted may also be included in the light emitting (display) device. Further
  • a near-infrared light emitting device having high luminous efficiency can be provided.
  • a light emitting device, a light emitting device, an electronic device, a display device, and an electronic device having low power consumption can be provided.
  • 1A, 1B and 1C are schematic views of the light emitting device.
  • 2A and 2B are conceptual diagrams of an active matrix type light emitting device.
  • 3A and 3B are conceptual diagrams of a passive matrix type light emitting device.
  • 4A and 4B are diagrams showing a lighting device.
  • 5A, 5B1, 5B2 and 5C are diagrams representing electronic devices.
  • 6A, 6B and 6C are diagrams representing electronic devices.
  • FIG. 7 is an example of a block diagram of the authentication system.
  • FIG. 8 is an example of a diagram of a transparent vein recognition system.
  • FIG. 9 is an example of a diagram of a reflex type vein recognition system.
  • 10A and 10B are diagrams showing electronic devices.
  • 11A, 11B and 11C are diagrams representing electronic devices.
  • FIG. 12 shows the radiation divergence-current density characteristics of the light emitting device 1 and the comparative light emitting device 1.
  • FIG. 13 shows the radiant exitance-voltage characteristics of the light emitting device 1 and the comparative light emitting device 1.
  • FIG. 14 shows the radiant flux-current density characteristics of the light emitting device 1 and the comparative light emitting device 1.
  • FIG. 15 shows the current-voltage characteristics of the light emitting device 1 and the comparative light emitting device 1.
  • FIG. 16 shows the external quantum efficiency-current density characteristics of the light emitting device 1 and the comparative light emitting device 1.
  • FIG. 17 is an EL emission spectrum of the light emitting device 1 and the comparative light emitting device 1.
  • FIG. 18 is a graph showing the change in brightness with respect to the driving time of the light emitting device 1 and the comparative light emitting device 1.
  • FIG. 19 is a graph showing changes in external quantum efficiency with respect to the film thickness of the first layer in the light emitting devices 1-1 to 1-4 and the comparative light emitting devices 1-1 to 1-4.
  • 20A is a graph showing the refractive index n of DBP
  • FIG. 20B is a graph showing the refractive index n of DBT3P-II
  • 21A is a graph showing the extinction coefficient k of DBP
  • FIG. 21B is a graph showing the extinction coefficient k of DBT3P-II.
  • FIG. 22 is a graph showing the spectral radiance-wavelength characteristics of the light emitting device 1 and the comparative light emitting device 1.
  • FIG. 1A shows a diagram showing a light emitting device 150 according to an aspect of the present invention.
  • the light emitting device of the present invention has an organic EL device 130 formed on the insulating surface 100 and a first layer 140 provided in contact with the electrode on which the light is emitted.
  • the organic EL device 130 is an EL device that emits light by using an organic compound as a light emitting substance and passing an electric current between the electrodes. Further, the organic EL device according to one aspect of the present invention exhibits light emission having a peak in the emission spectrum in a wavelength range of 750 nm or more and 1000 nm or less.
  • the insulating surface 100 may be the surface of a substrate such as glass or quartz, or may be the surface of an insulating film provided on the surface of another element such as a transistor.
  • the electrodes of the organic EL device 130 are electrically connected to the transistor and other elements via wiring provided on the insulating surface 100 and a conductive layer provided on a part of the insulating surface 100. Shall be.
  • the first layer 140 is a layer containing an organic compound. Further, the first layer 140 is a layer in which the extinction coefficient k has a maximum value in the visible light region.
  • the step of the refractive index n between the electrode of the organic EL device 130 and the external atmosphere can be reduced, and the extraction efficiency is improved.
  • the first layer 140 has a maximum value of the extinction coefficient k in the visible light region, it has absorption in the visible light region, so that the light emitted from the light emitting device 150 in the visible light region is reduced. However, it can be used as a light source for near-infrared light that is difficult to see.
  • the first layer 140 can be produced by vapor deposition.
  • the first layer 140 can be manufactured without being separated from the vapor deposition process of the organic EL device 130, so that a light emitting device with improved extraction efficiency can be manufactured easily and inexpensively.
  • the maximum value of the extinction coefficient k in the visible light region of the first layer 140 is preferably 0.05 or more, and more preferably 0.2 or more.
  • the refractive index n of the first layer 140 is preferably higher at the peak wavelength in the emission spectrum of the organic EL device 130, and is preferably 1.9 or more.
  • Examples of the organic compound for forming such a first layer 140 include a phthalocyanine-based material such as copper phthalocyanine (abbreviation: CuPc), 5,10,15,20-tetraphenylbisbenzo [5,6] indeno [ 1,2,3-cd: 1', 2', 3'-lm] Perylene (abbreviation: DBP), 3,4,9,10-perylene Tetracarboxyl-bis-benzoimidazole (abbreviation: PTCBI) and other perylenes Derivatives, fullerene-based materials such as C60 and C70, and condensed aromatic hydrocarbons having four or more rings such as pyrene can be preferably used.
  • a phthalocyanine-based material such as copper phthalocyanine (abbreviation: CuPc), 5,10,15,20-tetraphenylbisbenzo [5,6] indeno [ 1,2,3-cd: 1', 2', 3'-l
  • the organic EL device 130 has an anode 101, a cathode 102, and an EL layer 103.
  • the EL layer 103 has a light emitting layer 113 using an organic compound as a light emitting material, and emits light having a peak in the light emitting spectrum in a wavelength range of 750 nm or more and 1000 nm or less.
  • One of the anode 101 and the cathode 102 is an electrode having transparency at the peak wavelength of the light emitted by the EL layer 103.
  • the first layer 140 is provided in contact with a surface opposite to the surface of the transparent electrode with respect to the EL layer 103.
  • the transmissive electrode is preferably a semi-transmissive semi-reflective electrode that also has reflectivity with respect to the peak wavelength of light emitted by the EL layer 103.
  • the electrode that is not the transparent electrode is preferably an electrode that is reflective to the peak wavelength of the light emitted by the EL layer 103.
  • the reflective electrode is a film having a reflectance of 40% to 100%, preferably 70% to 100%, and a resistivity of 1 ⁇ 10 ⁇ 2 ⁇ cm or less at the peak wavelength of the light emitted by the EL layer 103.
  • the semitransparent semireflective electrode has a reflectance of 20% to 80%, preferably 40% to 70% of the peak wavelength of the light emitted by the EL layer 103.
  • the film has a resistivity of 1 ⁇ 10 -2 ⁇ cm or less.
  • the light emitting device changes the optical distance (optical path length in the organic EL device 130) between the reflective electrode and the transflective semi-reflective electrode by changing the thickness of the transparent conductive film, the above-mentioned composite material, the carrier transport material, and the like. Can be done. As a result, it is possible to strengthen the light having a resonating wavelength and attenuate the light having a wavelength that does not resonate between the reflecting electrode and the transflective semi-reflective electrode.
  • the light reflected and returned by the reflecting electrode causes a large interference with the light directly incident on the semitransparent semi-reflecting electrode from the light emitting layer 113 (first incident light), and is therefore reflected.
  • the EL layer may have a structure having a plurality of light emitting layers or a structure having a single light emitting layer.
  • a tandem type light emitting device described later, one It may be applied to a configuration in which a plurality of EL layers are provided on one light emitting device with a charge generation layer interposed therebetween, and a single or a plurality of light emitting layers are formed on each EL layer.
  • the organic EL device 130 will be described with reference to FIGS. 1B and 1C.
  • the anode 101 is shown below
  • the cathode 102 is shown above
  • the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer are shown in this order from the bottom.
  • the stacking order of these may be upside down.
  • the transparent electrode may be either the anode 101 or the cathode 102.
  • the hole injection layer 111, the hole transport layer 112, the electron transport layer 114, and the electron injection layer 115 are shown on the EL layer 103 in FIG. 1B.
  • the configuration is not limited to these. It is not necessary to form any of these layers, or it may have a layer having another function.
  • the light emitting device of one aspect of the present invention has an EL layer 103 composed of a plurality of layers between the pair of electrodes of the anode 101 and the cathode 102.
  • the anode 101 is preferably formed by using a metal having a large work function (specifically, 4.0 eV or more), an alloy, a conductive compound, a mixture thereof, or the like.
  • a metal having a large work function specifically, 4.0 eV or more
  • an alloy e.g., aluminum, copper, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium
  • indium oxide-zinc oxide may be formed by a sputtering method using a target in which 1 to 20 wt% zinc oxide is added to indium oxide.
  • Indium oxide (IWZO) containing tungsten oxide and zinc oxide is formed by a sputtering method using a target containing 0.5 to 5 wt% of tungsten oxide and 0.1 to 1 wt% of zinc oxide with respect to indium oxide. You can also do it.
  • gold Au
  • platinum Pt
  • nickel Ni
  • tungsten W
  • Cr chromium
  • Mo molybdenum
  • iron Fe
  • Co cobalt
  • Cu copper
  • palladium Pd
  • a nitride of a metallic material for example, titanium nitride
  • Graphene can also be used.
  • the EL layer 103 preferably has a laminated structure, but the laminated structure is not particularly limited, and is a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a carrier block layer. , Exciton block layer, charge generation layer, and various other layer structures can be applied.
  • FIG. 1B a configuration having an electron transport layer 114 and an electron injection layer 115 in addition to the hole injection layer 111, the hole transport layer 112, and the light emitting layer 113 will be described.
  • the materials constituting each layer are specifically shown below.
  • the hole injection layer 111 is a layer containing a substance having an accepting property.
  • a substance having an accepting property both an organic compound and an inorganic compound can be used.
  • a compound having an electron-withdrawing group (halogen group or cyano group) can be used, and 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane.
  • F 4 -TCNQ chloranil, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (abbreviation: HAT-CN), 1, 3,4,5,7,8-Hexafluorotetracyano-naphthoquinodimethane (abbreviation: F6-TCNNQ), 2- (7-dicyanomethylene-1,3,4,5,6,8,9,10) ⁇ Octafluoro-7H-pyrene-2-ylidene) Malononitrile and the like can be mentioned.
  • a compound such as HAT-CN in which an electron-withdrawing group is bonded to a condensed aromatic ring having a plurality of complex atoms is thermally stable and preferable.
  • the [3] radialene derivative having an electron-withdrawing group is preferable because it has very high electron acceptability, and specifically, ⁇ , ⁇ ', ⁇ ''-.
  • 1,2,3-Cyclopropanetriylidentris [4-cyano-2,3,5,6-tetrafluorobenzenitrile], ⁇ , ⁇ ', ⁇ ''-1,2,3-cyclopropanetriiridentris [2,6-dichloro-3,5-difluoro-4- (trifluoromethyl) benzenenitrile acetonitrile], ⁇ , ⁇ ', ⁇ ''-1,2,3-cyclopropanthrylilidentris [2,3,4 , 5,6-Pentafluorobenzene acetonitrile] and the like.
  • molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, manganese oxide and the like can be used in addition to the organic compounds described above.
  • phthalocyanine (abbreviation: H 2 Pc) or copper phthalocyanine (CuPc) complex phthalocyanine-based compound such as 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) :
  • the hole injection layer 111 is also formed by an aromatic amine compound such as DNTPD) or a polymer such as poly (3,4-ethylenedioxythiophene) / poly (styrenes
  • a composite material in which the accepting substance is contained in a material having a hole transporting property can also be used.
  • a material forming an electrode can be selected regardless of the work function. That is, not only a material having a large work function but also a material having a small work function can be used as the anode 101.
  • the material having a hole transport property used for the composite material various organic compounds such as an aromatic amine compound, a carbazole derivative, an aromatic hydrocarbon, and a polymer compound (oligomer, dendrimer, polymer, etc.) can be used.
  • the hole-transporting material used for the composite material is preferably a substance having a hole mobility of 1 ⁇ 10-6 cm 2 / Vs or more. In the following, organic compounds that can be used as materials having hole transport properties in composite materials are specifically listed.
  • DTDPPA N'-di (p-tolyl) -N, N'-diphenyl-
  • carbazole derivative examples include 3- [N- (9-phenylcarbazole-3-yl) -N-phenylamino] -9-phenylcarbazole (abbreviation: PCzPCA1) and 3,6-bis [N- (9-Phenylcarbazole-3-yl) -9-phenylamino] -9-phenylcarbazole (abbreviation: PCzPCA2), 3- [N- (1-naphthyl) -N- (9-phenylcarbazole-3-yl) Amino] -9-phenylcarbazole (abbreviation: PCzPCN1), 4,4'-di (N-carbazolyl) biphenyl (abbreviation: CBP), 1,3,5-tris [4- (N-carbazolyl) phenyl] benzene ( Abbreviation: TCPB), 9- [4- (N-carbazolyl)] benzene ( Abbre
  • aromatic hydrocarbon examples include 2-tert-butyl-9,10-di (2-naphthyl) anthracene (abbreviation: t-BuDNA) and 2-tert-butyl-9,10-di (1-naphthyl).
  • pentacene, coronene and the like can also be used. It may have a vinyl skeleton.
  • aromatic hydrocarbons having a vinyl group include 4,4'-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi) and 9,10-bis [4- (2,2-2)].
  • poly (N-vinylcarbazole) (abbreviation: PVK), poly (4-vinyltriphenylamine) (abbreviation: PVTPA), poly [N- (4- ⁇ N'-[4- (4-diphenylamino)) Phenyl] phenyl-N'-phenylamino ⁇ phenyl) methacrylamide] (abbreviation: PTPDMA), poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) benzidine] (abbreviation: A polymer compound such as Poly-TPD) can also be used.
  • PVK poly (N-vinylcarbazole)
  • PVTPA poly (4-vinyltriphenylamine)
  • PTPDMA poly [N- (4- ⁇ N'-[4- (4-diphenylamino) Phenyl] phenyl-N'-phenylamino ⁇ phenyl) methacrylamide]
  • the hole-transporting material used for the composite material it is more preferable to have any one of a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton and an anthracene skeleton.
  • a carbazole skeleton a dibenzofuran skeleton, a dibenzothiophene skeleton and an anthracene skeleton.
  • an aromatic amine having a substituent containing a dibenzofuran ring or a dibenzothiophene ring an aromatic monoamine having a naphthalene ring, or an aromatic monoamine in which a 9-fluorenyl group is bonded to the nitrogen of the amine via an arylene group.
  • these second organic compounds are substances having an N, N-bis (4-biphenyl) amino group because a light emitting device having a good life can be produced.
  • Specific examples of the second organic compound as described above include N- (4-biphenyl) -6, N-diphenylbenzo [b] naphtho [1,2-d] furan-8-amine (abbreviation: abbreviation:).
  • BnfABP N, N-bis (4-biphenyl) -6-phenylbenzo [b] naphtho [1,2-d] furan-8-amine
  • BBABnf 4,4'-bis (6-phenyl) Benzo [b] naphtho [1,2-d] furan-8-yl) -4''-phenyltriphenylamine
  • BnfBB1BP 4,4'-bis (6-phenyl) Benzo [b] naphtho [1,2-d] furan-8-yl) -4''-phenyltriphenylamine
  • BnfBB1BP N, N-bis (4-biphenyl) benzo [b] naphtho [1] , 2-d] furan-6-amine
  • BBABnf N, N-bis (4-biphenyl) benzo [b] naphtho [1,2-d] furan-8-amine
  • BBABnf (8)
  • the hole-transporting material used for the composite material is more preferably a substance having a relatively deep HOMO level of ⁇ 5.7 eV or more and ⁇ 5.4 eV or less. Since the hole-transporting material used for the composite material has a relatively deep HOMO level, it is easy to inject holes into the hole-transporting layer 112, and a light-emitting device having a good life can be obtained. Becomes easier.
  • the refractive index of the layer can be lowered by further mixing fluoride of an alkali metal or an alkaline earth metal with the composite material (preferably, the atomic ratio of fluorine atoms in the layer is 20% or more). It can. This also makes it possible to form a layer having a low refractive index inside the EL layer 103, and improve the external quantum efficiency of the light emitting device.
  • the hole injection layer 111 By forming the hole injection layer 111, the hole injection property is improved, and a light emitting device having a small driving voltage can be obtained.
  • the organic compound having acceptability is a material that is easy to use because it is easier to deposit and form a film than the above-mentioned metal and the fluoride of the metal. Examples of such organic compounds include N, N-bis (4-cyclohexylphenyl) -N- (9,9-dimethyl-9H-fluoren-2yl) amine (abbreviation: dcPAF) and N- (4-cyclohexylphenyl).
  • the hole transport layer 112 is formed containing a material having a hole transport property.
  • the material having hole transportability it is preferable that the material has a hole mobility of 1 ⁇ 10-6 cm 2 / Vs or more.
  • the material having hole transporting property include 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPB) and N, N'-bis (3-methylphenyl).
  • Tri (dibenzothiophene) (abbreviation: DBT3P-II), 2,8-diphenyl-4- [4- (9-phenyl-9H-fluoren-9-yl) phenyl] dibenzothiophene (abbreviation: DBTFLP-III), 4- [4- (9-Phenyl-9H-Fluoren-9-yl) Phenyl] -6-Phenyldibenzoti Compounds with a thiophene skeleton such as offen (abbreviation: DBTFLP-IV) and 4,4', 4''- (benzene-1,3,5-triyl) tri (dibenzofuran) (abbreviation: DBF3P-II), 4 Examples thereof include compounds having a furan skeleton such as ⁇ ⁇ 3- [3- (9-phenyl-9H-fluorene-9-yl) phenyl] phenyl ⁇ dibenzofuran (abbre
  • compounds having an aromatic amine skeleton and compounds having a carbazole skeleton are preferable because they have good reliability, high hole transportability, and contribute to reduction of driving voltage.
  • the substance mentioned as the material having hole transportability used for the composite material of the hole injection layer 111 can also be suitably used as the material constituting the hole transport layer 112.
  • a material having a low refractive index mentioned as a material having hole transportability used for the composite material of the hole injection layer 111 can also be used, and by using the material for the hole transport layer 112, it can be taken out. The efficiency is improved, and it becomes possible to provide a light emitting device having high light emitting efficiency.
  • the light emitting layer 113 has a light emitting substance and a host material.
  • the light emitting layer 113 may contain other materials at the same time. Further, two layers having different compositions may be laminated.
  • the luminescent substance may be a fluorescent luminescent substance, a phosphorescent luminescent substance, a substance exhibiting thermal activated delayed fluorescence (TADF), or another luminescent substance.
  • TADF thermal activated delayed fluorescence
  • the light emitting layer when light having a light emitting peak in the wavelength range of 750 nm or more and 1000 nm or less is exhibited from the EL layer, the light emitting layer emits light in the wavelength range of 750 nm or more and 1000 nm or less. It is preferable to use an organic compound having a peak (organic metal complex or the like).
  • a phthalocyanine compound central metal: aluminum, zinc, etc.
  • a naphthalocyanine compound central metal: nickel
  • a quinone compound central metal: nickel
  • a diimonium compound an azo compound, or the like
  • organometallic complex having an emission peak in the wavelength range of 750 nm or more and 1000 nm or less
  • an organometallic complex represented by the following general formula (G1) can be mentioned.
  • R 1 to R 11 independently represent hydrogen or an alkyl group having 1 or more and 6 or less carbon atoms, and at least two of R 1 to R 4 have 1 or more and 6 or less carbon atoms.
  • X represents a substituted or unsubstituted benzene ring or a naphthalene ring
  • n represents 2 or 3 and L represents a monoanionic ligand.
  • examples of the alkyl group having 1 or more and 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, and a pentyl group.
  • the substituent when the benzene ring or the naphthalene ring has a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms. As the alkyl group having 1 or more and 6 or less carbon atoms, the above description can be incorporated.
  • Examples of the monoanionic ligand include a monoanionic bidentate chelate ligand having a ⁇ -diketone structure, a monoanionic bidentate chelate ligand having a carboxyl group, and a monoanionic monoanionic ligand having a phenolic hydroxyl group.
  • Bidentate chelate ligands, monoanionic bidentate chelate ligands in which the two coordinating elements are both nitrogen, bidentate ligands that form a metal-carbon bond with iridium by cyclometallation, etc. Can be mentioned.
  • the monoanionic ligand is preferably any one of the general formulas (L1) to (L8).
  • R 51 to R 89 are independently hydrogen or substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, halogeno group, vinyl group, substituted or unsubstituted carbon.
  • a 1 to A 13 each independently represent an sp 2 hybrid carbon that binds to nitrogen and hydrogen, or an sp 2 hybrid carbon that has a substituent, and the substituent is an alkyl group having 1 to 6 carbon atoms. , A halogeno group, a haloalkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • organometallic complex represented by the general formula (G1) include the organometallic complexes represented by the structural formulas (100) to (107). However, the present invention is not limited to these.
  • the material that can be used as the fluorescent luminescent material in the light emitting layer 113 is, for example, 5,6-bis [4- (10-phenyl-9-).
  • Anthryl) phenyl] -2,2'-bipyridine abbreviation: PAP2BPy
  • PAP2BPy 5,6-bis [4'-(10-phenyl-9-anthril) biphenyl-4-yl] -2,2'-bipyridine
  • PAPP2BPy 5,6-bis [4'-(10-phenyl-9-anthril) biphenyl-4-yl] -2,2'-bipyridine
  • N, N'-diphenyl-N N'-bis [4- (9-phenyl-9H-fluoren-9-yl) phenyl] pyrene-1,6-diamine
  • 1,6FLPAPrn N, N'-bis (3-methylphenyl) -N, N'-bis [3- (9-phen
  • condensed aromatic diamine compounds typified by pyrenediamine compounds such as 1,6FLPAPrn, 1,6mmemFLPARn, and 1,6BnfAPrn-03 are preferable because they have high hole trapping properties and are excellent in luminous efficiency and reliability. Further, other fluorescent light emitting substances can also be used.
  • a phosphorescent luminescent substance is used as the luminescent substance in the light emitting layer 113, as a material that can be used, for example, Tris ⁇ 2- [5- (2-methylphenyl) -4- (2,6-dimethylphenyl) -4- (2,6-dimethylphenyl) ) -4H-1,2,4-triazol-3-yl- ⁇ N2] Phenyl- ⁇ C ⁇ Iridium (III) (abbreviation: [Ir (mpptz-dmp) 3 ]), Tris (5-methyl-3,4- Diphenyl-4H-1,2,4-triazolate) Iridium (III) (abbreviation: [Ir (Mptz) 3 ]), Tris [4- (3-biphenyl) -5-isopropyl-3-phenyl-4H-1, Organic metal iridium complex having a 4H-triazole skeleton such as 2,4-triazolate] iridium (III)
  • organometallic iridium complex having a pyrimidine skeleton is particularly preferable because it is remarkably excellent in reliability and luminous efficiency.
  • organometallic iridium complex having a pyrazine skeleton can obtain red light emission with good chromaticity.
  • a known phosphorescent luminescent substance may be selected and used.
  • TADF material fullerene and its derivative, acridine and its derivative, eosin derivative and the like can be used.
  • metal-containing porphyrin include a protoporphyrin-tin fluoride complex (SnF 2 (Proto IX)), a mesoporphyrin-tin fluoride complex (SnF 2 (Meso IX)), and hematoporphyrin represented by the following structural formulas.
  • 2- (biphenyl-4-yl) -4,6-bis (12-phenylindro [2,3-a] carbazole-11-yl) -1,3,5-l shown in the following structural formula Triazine (abbreviation: PIC-TRZ) and 9- (4,6-diphenyl-1,3,5-triazine-2-yl) -9'-phenyl-9H, 9'H-3,3'-bicarbazole (Abbreviation: PCCzTzn), 2- ⁇ 4- [3- (N-phenyl-9H-carbazole-3-yl) -9H-carbazole-9-yl] phenyl ⁇ -4,6-diphenyl-1,3,5 -Triazine (abbreviation: PCCzPTzn), 2- [4- (10H-phenoxazine-10-yl) phenyl] -4,6-diphenyl-1,3,5-triazine (abbreviation: PIC-
  • Heterocyclic compounds having one or both rings can also be used. Since the heterocyclic compound has a ⁇ -electron excess type heteroaromatic ring and a ⁇ -electron deficiency type heteroaromatic ring, both electron transportability and hole transportability are high, which is preferable.
  • the pyridine skeleton, the diazine skeleton (pyrimidine skeleton, pyrazine skeleton, pyridazine skeleton), and triazine skeleton are preferable because they are stable and have good reliability.
  • the benzoflopyrimidine skeleton, the benzothienopyrimidine skeleton, the benzoflopyrazine skeleton, and the benzothienopyrazine skeleton are preferable because they have high acceptability and good reliability.
  • the acrydin skeleton, the phenoxazine skeleton, the phenothiazine skeleton, the furan skeleton, the thiophene skeleton, and the pyrrole skeleton are stable and have good reliability, and therefore at least one of the skeletons. It is preferable to have.
  • the furan skeleton is preferably a dibenzofuran skeleton
  • the thiophene skeleton is preferably a dibenzothiophene skeleton.
  • an indole skeleton, a carbazole skeleton, an indolecarbazole skeleton, a bicarbazole skeleton, and a 3- (9-phenyl-9H-carbazole-3-yl) -9H-carbazole skeleton are particularly preferable.
  • the substance in which the ⁇ -electron-rich heteroaromatic ring and the ⁇ -electron-deficient heteroaromatic ring are directly bonded has both the electron donating property of the ⁇ -electron-rich heteroaromatic ring and the electron acceptability of the ⁇ -electron-deficient heteroaromatic ring.
  • an aromatic ring to which an electron-withdrawing group such as a cyano group is bonded may be used.
  • an aromatic amine skeleton, a phenazine skeleton, or the like can be used as the ⁇ -electron excess type skeleton.
  • An aromatic ring having a group or a cyano group, a heteroaromatic ring, a carbonyl skeleton such as benzophenone, a phosphine oxide skeleton, a sulfone skeleton and the like can be used.
  • a ⁇ -electron-deficient skeleton and a ⁇ -electron-rich skeleton can be used in place of at least one of the ⁇ -electron-deficient heteroaromatic ring and the ⁇ -electron-rich heteroaromatic ring.
  • the TADF material is a material having a small difference between the S1 level and the T1 level and having a function of converting energy from triplet excitation energy to singlet excitation energy by intersystem crossing. Therefore, the triplet excited energy can be up-converted to the singlet excited energy by a small amount of heat energy (intersystem crossing), and the singlet excited state can be efficiently generated. In addition, triplet excitation energy can be converted into light emission.
  • an excited complex also referred to as an exciplex, an exciplex or an Exciplex
  • the difference between the S1 level and the T1 level is extremely small, and the triplet excitation energy is the singlet excitation energy. It has a function as a TADF material that can be converted into.
  • a phosphorescent spectrum observed at a low temperature may be used.
  • a TADF material a tangent line is drawn at the hem on the short wavelength side of the fluorescence spectrum, the energy of the wavelength of the extraline is set to the S1 level, and a tangent line is drawn at the hem on the short wavelength side of the phosphorescent spectrum, and the extrapolation thereof is performed.
  • the difference between S1 and T1 is preferably 0.3 eV or less, and more preferably 0.2 eV or less.
  • the S1 level of the host material is preferably higher than the S1 level of the TADF material. Further, when the TADF material is used as a light emitting substance, the T1 level of the host material is preferably higher than the T1 level of the TADF material.
  • various carrier transport materials such as a material having an electron transport property, a material having a hole transport property, and the TADF material can be used.
  • an organic compound having an amine skeleton or a ⁇ -electron excess type complex aromatic ring skeleton is preferable.
  • NPB 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl
  • TPD 1,1'-biphenyl] -4,4'-diamine
  • BSPB 4,4'-bis [N- (spiro-9,9'-bifluoren-2-yl) -N-phenylamino] biphenyl
  • BSPB 4-Phenyl-4'-(9-Phenylfluoren-9-yl) Triphenylamine
  • BPAFLP 4-Phenyl-3'-(9-Phenylfluoren-9-yl) Tri Pheny
  • compounds having an aromatic amine skeleton and compounds having a carbazole skeleton are preferable because they have good reliability, high hole transportability, and contribute to reduction of driving voltage. Further, a material having a hole transporting property, which is mentioned as a material that can be used for the composite material, can also be used.
  • electron-transporting material examples include bis (10-hydroxybenzo [h] quinolinato) berylium (II) (abbreviation: BeBq 2 ) and 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) and organic compounds having a ⁇ -electron-deficient heteroaromatic ring skeleton are preferable.
  • Examples of the organic compound having a ⁇ -electron-deficient heterocyclic skeleton include 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD).
  • the heterocyclic compound having a diazine skeleton and the heterocyclic compound having a pyridine skeleton are preferable because they have good reliability.
  • a heterocyclic compound having a diazine (pyrimidine or pyrazine) skeleton has high electron transport property and contributes to reduction of driving voltage.
  • the TADF material that can be used as the host material
  • those listed above as the TADF material can also be used in the same manner.
  • the triplet excitation energy generated by the TADF material is converted to singlet excitation energy by inverse intersystem crossing, and the energy is further transferred to the luminescent material, thereby increasing the emission efficiency of the light emitting device. be able to.
  • the TADF material functions as an energy donor, and the luminescent material functions as an energy acceptor.
  • the S1 level of the TADF material is preferably higher than the S1 level of the fluorescent light emitting substance.
  • the T1 level of the TADF material is preferably higher than the S1 level of the fluorescent light emitting substance. Therefore, the T1 level of the TADF material is preferably higher than the T1 level of the fluorescent substance.
  • a TADF material that emits light so as to overlap the wavelength of the absorption band on the lowest energy side of the fluorescent light emitting substance.
  • the fluorescent substance preferably has a protecting group around the chromophore (skeleton that causes light emission) of the fluorescent substance.
  • a protecting group a substituent having no ⁇ bond is preferable, a saturated hydrocarbon is preferable, specifically, an alkyl group having 3 or more and 10 or less carbon atoms, and a substituted or unsubstituted cyclo having 3 or more and 10 or less carbon atoms.
  • Examples thereof include an alkyl group and a trialkylsilyl group having 3 or more and 10 or less carbon atoms, and it is more preferable that there are a plurality of protecting groups.
  • Substituents that do not have a ⁇ bond have a poor function of transporting carriers, so that the distance between the TADF material and the chromophore of the fluorescent luminescent material can be increased with almost no effect on carrier transport or carrier recombination. ..
  • the chromophore refers to an atomic group (skeleton) that causes light emission in a fluorescent luminescent substance.
  • the chromophore preferably has a skeleton having a ⁇ bond, preferably contains an aromatic ring, and preferably has a condensed aromatic ring or a condensed heteroaromatic ring.
  • the condensed aromatic ring or the condensed heteroaromatic ring include a phenanthrene skeleton, a stilbene skeleton, an acridone skeleton, a phenoxazine skeleton, and a phenothiazine skeleton.
  • a fluorescent substance having a naphthalene skeleton, anthracene skeleton, fluorene skeleton, chrysene skeleton, triphenylene skeleton, tetracene skeleton, pyrene skeleton, perylene skeleton, coumarin skeleton, quinacridone skeleton, and naphthobisbenzofuran skeleton is preferable because of its high fluorescence quantum yield.
  • a material having an anthracene skeleton is suitable as the host material.
  • a substance having an anthracene skeleton is used as a host material for a fluorescent light emitting substance, it is possible to realize a light emitting layer having good luminous efficiency and durability.
  • a substance having an anthracene skeleton used as the host material a substance having a diphenylanthracene skeleton, particularly a substance having a 9,10-diphenylanthracene skeleton is preferable because it is chemically stable.
  • the host material has a carbazole skeleton
  • the injection / transportability of holes is enhanced, but when the host material contains a benzocarbazole skeleton in which a benzene ring is further condensed with carbazole, the HOMO is about 0.1 eV shallower than that of carbazole.
  • the HOMO is about 0.1 eV shallower than that of carbazole, holes are easily entered, and the hole transport property is excellent and the heat resistance is high, which is preferable. ..
  • a substance having a 9,10-diphenylanthracene skeleton and a carbazole skeleton (or a benzocarbazole skeleton or a dibenzocarbazole skeleton) at the same time is further preferable as a host material.
  • a benzofluorene skeleton or a dibenzofluorene skeleton may be used instead of the carbazole skeleton.
  • examples of such substances are 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] Fran (abbreviation: 2mBnfPPA), 9-Phenyl-10- ⁇ 4- (9-phenyl-9H-fluoren-9-yl) biphenyl-4'-yl ⁇ anthracene (abbreviation: FLPPA), 9- Examples thereof include (1-naphthyl) -10- [4- (2
  • the host material may be a material obtained by mixing a plurality of kinds of substances, and when a mixed host material is used, it is preferable to mix a material having an electron transporting property and a material having a hole transporting property. ..
  • a material having an electron transporting property and a material having a hole transporting property By mixing the material having electron transportability and the material having hole transportability, the transportability of the light emitting layer 113 can be easily adjusted, and the recombination region can be easily controlled.
  • the electron-transporting material and the hole-transporting material may be mixed by co-depositing or by depositing a premixed (premixed) sample.
  • a phosphorescent light emitting substance can be used as a part of the mixed materials.
  • the phosphorescent luminescent material can be used as an energy donor that provides excitation energy to the fluorescent luminescent material when the fluorescent luminescent material is used as the luminescent material.
  • At least one of the materials forming the excitation complex may be a phosphorescent substance.
  • the HOMO level of the material having hole transportability is equal to or higher than the HOMO level of the material having electron transportability.
  • the LUMO level of the material having hole transportability is equal to or higher than the LUMO level of the material having electron transportability.
  • the LUMO level and HOMO level of the material can be derived from the electrochemical properties (reduction potential and oxidation potential) of the material measured by cyclic voltammetry (CV) measurement.
  • the emission spectrum of the material having hole transporting property, the emission spectrum of the material having electron transporting property, and the emission spectrum of the mixed film in which these materials are mixed are compared, and the emission spectrum of the mixed film is compared.
  • the transient photoluminescence (PL) of the material having hole transportability, the transient PL of the material having electron transportability, and the transient PL of the mixed membrane in which these materials are mixed are compared, and the transient PL lifetime of the mixed membrane is determined.
  • transient PL may be read as transient electroluminescence (EL). That is, by comparing the transient EL of the material having hole transportability, the transient EL of the material having electron transportability, and the transient EL of the mixed membrane of these, and observing the difference in the transient response, the formation of the excited complex can be formed. You can check.
  • EL transient electroluminescence
  • the electron transport layer 114 is a layer containing a substance having an electron transport property.
  • substance having electron transportability those listed as the substance having electron transportability that can be used for the host material can be used.
  • the electron transport layer 114 preferably has an electron mobility of 1 ⁇ 10-7 cm 2 / Vs or more and 5 ⁇ 10-5 cm 2 / Vs or less when the square root of the electric field strength [V / cm] is 600. By reducing the electron transportability of the electron transport layer 114, the amount of electrons injected into the light emitting layer can be controlled, and the light emitting layer can be prevented from being in a state of excess electrons. Further, the electron transport layer preferably contains a material having an electron transport property and a simple substance, a compound or a complex of an alkali metal or an alkaline earth metal.
  • the hole injection layer is formed as a composite material
  • the HOMO level of the material having hole transportability in the composite material is -5.7 eV or more and -5.4 eV or less, which is a relatively deep HOMO level. It is particularly preferable that the substance has a good life. At this time, it is preferable that the HOMO level of the material having electron transportability is ⁇ 6.0 eV or more.
  • the material having electron transport property is preferably an organic compound having an anthracene skeleton, and more preferably an organic compound containing both an anthracene skeleton and a heterocyclic skeleton.
  • the heterocyclic skeleton is preferably a nitrogen-containing 5-membered ring skeleton or a nitrogen-containing 6-membered ring skeleton, and these heterocyclic skeletons include pyrazole ring, imidazole ring, oxazole ring, thiazole ring, pyrazine ring, pyrimidine ring, and pyridazine ring. It is particularly preferable to have a nitrogen-containing 5-membered ring skeleton or a nitrogen-containing 6-membered ring skeleton containing two heteroatoms in the ring. Further, the simple substance, compound or complex of the alkali metal or alkaline earth metal preferably contains an 8-hydroxyquinolinato structure.
  • 8-hydroxyquinolinato-lithium abbreviation: Liq
  • 8-hydroxyquinolinato-sodium abbreviation: Naq
  • a monovalent metal ion complex particularly a lithium complex
  • Liq is more preferable.
  • it contains an 8-hydroxyquinolinato structure its methyl-substituted product (for example, 2-methyl-substituted product or 5-methyl-substituted product) can also be used.
  • a simple substance, a compound or a complex of an alkali metal or an alkaline earth metal has a concentration difference (including the case where it is 0) in the thickness direction thereof.
  • lithium fluoride LiF
  • cesium fluoride CsF
  • calcium fluoride CaF 2
  • 8-hydroxyquinolinato-lithium abbreviation::
  • a layer containing an alkali metal or alkaline earth metal such as Liq or a compound thereof may be provided.
  • an alkali metal, an alkaline earth metal, or a compound thereof contained in a layer made of a substance having an electron transporting property, or an electride may be used. Examples of the electride include a substance in which a high concentration of electrons is added to a mixed oxide of calcium and aluminum.
  • the electron-injected layer 115 contains an electron-transporting substance (preferably an organic compound having a bipyridine skeleton) containing fluoride of the above-mentioned alkali metal or alkaline earth metal in a concentration or more (50 wt% or more) of being in a microcrystalline state. It is also possible to use an alkaline layer. Since the layer has a low refractive index, it is possible to provide a light emitting device having better external quantum efficiency.
  • an electron-transporting substance preferably an organic compound having a bipyridine skeleton
  • fluoride of the above-mentioned alkali metal or alkaline earth metal in a concentration or more (50 wt% or more) of being in a microcrystalline state. It is also possible to use an alkaline layer. Since the layer has a low refractive index, it is possible to provide a light emitting device having better external quantum efficiency.
  • a charge generation layer may be provided instead of the electron injection layer 115.
  • the charge generation layer is a layer capable of injecting holes into the layer in contact with the cathode side and electrons into the layer in contact with the anode side by applying an electric potential.
  • the charge generation layer includes at least a P-type layer.
  • the P-type layer is preferably formed by using the composite material mentioned as a material capable of forming the hole injection layer described above. Further, the P-type layer may be formed by laminating a film containing the above-mentioned acceptor material and a film containing a hole transport material as a material constituting the composite material. By applying an electric potential to the P-type layer, electrons are injected into the electron transport layer and holes are injected into the cathode 102, which is a cathode, and the light emitting device operates.
  • the charge generation layer preferably has one or both of an electron relay layer and an electron injection buffer layer in addition to the P-type layer.
  • the electron relay layer contains at least a substance having electron transportability, and has a function of preventing interaction between the electron injection buffer layer and the P-type layer and smoothly transferring electrons.
  • the LUMO levels of the electron-transporting substance contained in the electron relay layer are the LUMO level of the accepting substance in the P-type layer and the LUMO level of the substance contained in the layer in contact with the charge generation layer 116 in the electron-transporting layer. It is preferable that it is between.
  • the specific energy level of the LUMO level in the electron-transporting material used for the electron relay layer is preferably -5.0 eV or more, preferably -5.0 eV or more and -3.0 eV or less.
  • As the electron-transporting substance used for the electron relay layer it is preferable to use a phthalocyanine-based material or a metal complex having a metal-oxygen bond and an aromatic ligand.
  • the electron injection buffer layer 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). It is possible to use substances with high electron injection properties such as alkaline earth metal compounds (including oxides, halides and carbonates) or rare earth metal compounds (including oxides, halides and carbonates). is there.
  • the donor substance includes an alkali metal, an alkaline earth metal, a rare earth metal, and a compound thereof (alkali).
  • Metal compounds including oxides such as lithium oxide, halides, carbonates such as lithium carbonate and cesium carbonate), alkaline earth metal compounds (including oxides, halides and carbonates), or rare earth metal compounds (including oxides, halides and carbonates) (Including oxides, halides, and carbonates)), organic compounds such as tetrathianaphthalene (abbreviation: TTN), nickerosen, and decamethyl nickerosen can also be used.
  • TTN tetrathianaphthalene
  • nickerosen nickerosen
  • decamethyl nickerosen can also be used.
  • the material having electron transportability it can be formed by using the same material as the material constituting the electron transport layer 114 described above.
  • a metal having a small work function (specifically, 3.8 eV or less), an alloy, an electrically conductive compound, a mixture thereof, or the like
  • a cathode material include alkali metals such as lithium (Li) and cesium (Cs), and Group 1 of the periodic table of elements such as magnesium (Mg), calcium (Ca), and strontium (Sr).
  • alkali metals such as lithium (Li) and cesium (Cs)
  • Group 1 of the periodic table of elements such as magnesium (Mg), calcium (Ca), and strontium (Sr).
  • Examples include elements belonging to Group 2, rare earth metals such as alloys containing them (MgAg, AlLi), europium (Eu), ytterbium (Yb), and alloys containing these.
  • a conductive material can be used as the cathode 102.
  • These conductive materials can be formed into a film by using a dry method such as a vacuum deposition method or a sputtering method, an inkjet method, a spin coating method, or the like. Further, it may be formed by a wet method using a sol-gel method, or may be formed by a wet method using a paste of a metal material.
  • a method for forming the EL layer 103 various methods can be used regardless of a dry method or a wet method.
  • a vacuum deposition 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 by using a different film forming method.
  • the structure of the layer provided between the anode 101 and the cathode 102 is not limited to the above. However, a light emitting region in which holes and electrons recombine in a portion away from the anode 101 and the cathode 102 so that quenching caused by the proximity of the light emitting region to the metal used for the electrode or carrier injection layer is suppressed. Is preferable.
  • the hole transport layer and the electron transport layer in contact with the light emitting layer 113 suppresses the energy transfer from the excitons generated in the light emitting layer, so that the band gap thereof.
  • a light emitting device also referred to as a laminated element or a tandem type element having a configuration in which a plurality of light emitting units are laminated
  • This light emitting device is a light emitting device having a plurality of light emitting units between the anode and the cathode.
  • One light emitting unit has substantially the same configuration as the EL layer 103 shown in FIG. 1B. That is, it can be said that the light emitting device shown in FIG. 1C is a light emitting device having a plurality of light emitting units, and the light emitting device shown in FIG. 1B is a light emitting device having one light emitting unit.
  • a first light emitting unit 511 and a second light emitting unit 512 are laminated between the anode 501 and the cathode 502, and between the first light emitting unit 511 and the second light emitting unit 512. Is provided with a charge generation layer 513.
  • the anode 501 and the cathode 502 correspond to the anode 101 and the cathode 102 in FIG. 1B, respectively, and the same ones described in the description of FIG. 1B can be applied.
  • the first light emitting unit 511 and the second light emitting unit 512 may have the same configuration or different configurations.
  • the charge generation layer 513 has a function of injecting electrons into one light emitting unit and injecting holes into the other light emitting unit when a voltage is applied to the anode 501 and the cathode 502. That is, in FIG. 1C, when a voltage is applied so that the potential of the anode is higher than the potential of the cathode, the charge generation layer 513 injects electrons into the first light emitting unit 511 and the second light emitting unit. Anything that injects holes into 512 may be used.
  • the charge generation layer 513 is preferably formed with the same configuration as the charge generation layer described with reference to FIG. 1B. Since the composite material of the organic compound and the metal oxide is excellent in carrier injection property and carrier transport property, low voltage drive and low current drive can be realized. When the surface of the light emitting unit on the anode side is in contact with the charge generating layer 513, the charge generating layer 513 can also serve as the hole injection layer of the light emitting unit, so that the light emitting unit uses the hole injection layer. It does not have to be provided.
  • the electron injection buffer layer plays the role of the electron injection layer in the light emitting unit on the anode side, so that the electron injection layer is not necessarily formed in the light emitting unit on the anode side. No need.
  • FIG. 1C a light emitting device having two light emitting units has been described, but the same can be applied to a light emitting device in which three or more light emitting units are stacked.
  • a light emitting device in which three or more light emitting units are stacked.
  • each light emitting unit by making the emission color of each light emitting unit different, it is possible to obtain light emission of a desired color as the entire light emitting device. For example, in a light emitting device having two light emitting units, the first light emitting unit obtains near-infrared light and the second light emitting unit obtains blue light to simultaneously emit light for display and sensing. It is also possible to get a device.
  • each layer or electrode such as the EL layer 103, the first light emitting unit 511, the second light emitting unit 512, and the charge generation layer can be, for example, a vapor deposition method (including a vacuum deposition method) or a droplet ejection method (inkjet). It can be formed by using a method such as a method), a coating method, or a gravure printing method. They may also include low molecular weight materials, medium molecular weight materials (including oligomers, dendrimers), or high molecular weight materials.
  • FIG. 2A is a top view showing the light emitting device
  • FIG. 2B is a cross-sectional view of FIG. 2A cut by AB and CD.
  • This light emitting device includes a drive circuit unit (source line drive circuit) 601, a pixel unit 602, and a drive circuit unit (gate line drive circuit) 603 shown by dotted lines to control the light emission of the light emitting device.
  • 604 is a sealing substrate
  • 605 is a sealing material
  • the inside surrounded by the sealing material 605 is a space 607.
  • the routing wiring 608 is a wiring for transmitting signals input to the source line drive circuit 601 and the gate line drive circuit 603, and is a video signal, a clock signal, and a video signal and a clock signal from the FPC (flexible print circuit) 609 which is an external input terminal. Receives start signal, reset signal, etc. Although only the FPC is shown 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 PWB is attached to the light emitting device main body.
  • a drive circuit unit and a pixel unit are formed on the element substrate 610, and here, a source line drive circuit 601 which is a drive circuit unit and one pixel in the pixel unit 602 are shown.
  • the element substrate 610 is manufactured by using a substrate made of glass, quartz, organic resin, metal, alloy, semiconductor, etc., as well as a plastic substrate made of FRP (Fiber Reinforced Plastics), PVF (polyvinyl fluoride), polyester, acrylic resin, etc. do it.
  • FRP Fiber Reinforced Plastics
  • PVF polyvinyl fluoride
  • the structure of the transistor used for the pixel and the drive circuit is not particularly limited. For example, it may be an inverted stagger type transistor or a stagger type transistor. Further, a top gate type transistor or a bottom gate type transistor may be used.
  • the semiconductor material used for the transistor is not particularly limited, and for example, silicon, germanium, silicon carbide, gallium nitride and the like can be used. Alternatively, 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, and either an amorphous semiconductor or a semiconductor having crystallinity (a microcrystalline semiconductor, a polycrystalline semiconductor, a single crystal semiconductor, or a semiconductor having a partially crystalline region). May be used. It is preferable to use a semiconductor having crystallinity because deterioration of transistor characteristics can be suppressed.
  • an oxide semiconductor in addition to the transistors provided in the pixels and the drive circuit, it is preferable to apply an oxide semiconductor to a semiconductor device such as a transistor used in a touch sensor or the like. In particular, it is preferable to apply an oxide semiconductor having a bandgap wider than that of silicon. By using an oxide semiconductor having a bandgap wider than that of silicon, the current in the off state of the transistor can be reduced.
  • the oxide semiconductor preferably contains at least indium (In) or zinc (Zn). Further, the oxide semiconductor contains an oxide represented by an In—M—Zn-based oxide (M is a metal such as Al, Ti, Ga, Ge, Y, Zr, Sn, La, Ce or Hf). Is more preferable.
  • M is a metal such as Al, Ti, Ga, Ge, Y, Zr, Sn, La, Ce or Hf. Is more preferable.
  • the semiconductor layer has a plurality of crystal portions, and the c-axis of the crystal portion is oriented perpendicular to the surface to be formed of the semiconductor layer or the upper surface of the semiconductor layer, and grain boundaries are formed between adjacent crystal portions. It is preferable to use an oxide semiconductor film that does not have.
  • the transistor having the above-mentioned semiconductor layer can retain the electric charge accumulated in the capacitance through the transistor for a long period of time due to its low off current.
  • the transistor having the above-mentioned semiconductor layer can retain the electric charge accumulated in the capacitance through the transistor for a long period of time due to its low off current.
  • a base film for stabilizing the characteristics of the transistor As the base film, an inorganic insulating film such as a silicon oxide film, a silicon nitride film, a silicon oxide film, or a silicon nitride film can be used, and can be produced as a single layer or laminated.
  • the base film is formed by using a sputtering method, a CVD (Chemical Vapor Deposition) method (plasma CVD method, thermal CVD method, MOCVD (Metal Organic CVD) method, etc.), ALD (Atomic Layer Deposition) method, coating method, printing method, etc. it can.
  • the base film may not be provided if it is not necessary.
  • the FET 623 represents one of the transistors formed in the drive circuit unit 601.
  • the drive circuit may be formed of various CMOS circuits, epitaxial circuits or NMOS circuits.
  • the driver integrated type in which the drive circuit is formed on the substrate is shown, but it is not always necessary, and the drive circuit can be formed on the outside instead of on the substrate.
  • the pixel unit 602 is formed by a plurality of pixels including a switching FET 611, a current control FET 612, and a first electrode 613 electrically connected to the drain thereof, but the pixel portion 602 is not limited to 3
  • a pixel unit may be a combination of two or more FETs and a capacitive element.
  • An insulator 614 is formed so as to cover the end portion of the first electrode 613.
  • it can be formed by using a positive type photosensitive acrylic resin film.
  • a curved surface having a curvature is formed at the upper end portion or the lower end portion of the insulator 614.
  • a positive photosensitive acrylic resin is used as the material of the insulator 614
  • a negative type photosensitive resin or a positive type photosensitive resin can be used as the insulator 614.
  • An EL layer 616 and a second electrode 617 are formed on the first electrode 613, respectively.
  • the material used for the first electrode 613 that functions as an anode it is desirable to use a material having a large work function.
  • a laminated structure 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.
  • the resistance as wiring is low, good ohmic contact can be obtained, and the structure can further function as an anode.
  • the EL layer 616 is formed by various methods such as a thin-film deposition method using a thin-film deposition mask, an inkjet method, and a spin coating method.
  • the EL layer 616 includes a configuration as described in the first embodiment.
  • the other material constituting the EL layer 616 may be a low molecular weight compound or a high molecular weight compound (including an oligomer and a dendrimer).
  • the material used for the second electrode 617 formed on the EL layer 616 and functioning as a cathode a material having a small work function (Al, Mg, Li, Ca, or an alloy or compound thereof (MgAg, MgIn, etc.) It is preferable to use AlLi etc.)).
  • the second electrode 617 is a thin metal thin film and a transparent conductive film (ITO, 2 to 20 wt% oxidation). It is preferable to use a laminate with indium oxide containing zinc, indium tin oxide containing silicon, zinc oxide (ZnO), etc.).
  • a light emitting device is formed by the first electrode 613, the EL layer 616, and the second electrode 617.
  • the light emitting device is the light emitting device according to the first embodiment. Although a plurality of light emitting devices are formed in the pixel portion, in the light emitting device according to the present embodiment, both the light emitting device according to the first embodiment and the light emitting device having other configurations are mixed. You may be doing it.
  • the sealing substrate 604 by bonding the sealing substrate 604 to the element substrate 610 with the sealing material 605, the light emitting device 618 is provided in the space 607 surrounded by the element substrate 610, the sealing substrate 604, and the sealing material 605.
  • the space 607 is filled with a filler, which may be filled with an inert gas (nitrogen, argon, etc.) or a sealing material.
  • an epoxy resin or glass frit for the sealing material 605. Further, it is desirable that these materials are materials that do not allow moisture or oxygen to permeate as much as possible. Further, as a material used for the sealing substrate 604, in addition to a glass substrate and a quartz substrate, a plastic substrate made of FRP (Fiber Reinforced Plastics), PVF (polyvinyl fluoride), polyester, acrylic resin or the like can be used.
  • FRP Fiber Reinforced Plastics
  • PVF polyvinyl fluoride
  • polyester acrylic resin or the like
  • a protective film may be provided on the second electrode.
  • the protective film may be formed of an organic resin film or an inorganic insulating film. Further, a protective film may be formed so as to cover the exposed portion of the sealing material 605. Further, the protective film can be provided so as to cover the surface and side surfaces of the pair of substrates, the sealing layer, the insulating layer, and the exposed side surfaces.
  • the protective film a material that does not easily allow impurities such as water to permeate can be used. Therefore, it is possible to effectively prevent impurities such as water from diffusing from the outside to the inside.
  • oxides, nitrides, fluorides, sulfides, ternary compounds, metals, polymers and the like can be used, and for example, aluminum oxide, hafnium oxide, hafnium silicate, lanthanum oxide and oxidation can be used.
  • the protective film is preferably formed by using a film forming method having good step coverage (step coverage).
  • a film forming method having good step coverage is the atomic layer deposition (ALD) method.
  • ALD atomic layer deposition
  • ALD method it is possible to form a protective film having a dense, reduced defects such as cracks and pinholes, or a uniform thickness.
  • damage to the processed member when forming the protective film can be reduced.
  • the protective film by using the ALD method, it is possible to form a protective film having a complicated uneven shape and a uniform and few defects on the upper surface, the side surface and the back surface of the touch panel.
  • a light emitting device manufactured by using the light emitting device according to the first embodiment can be obtained.
  • the light emitting device according to the present embodiment uses the light emitting device according to the first embodiment, it is possible to obtain a light emitting device having good characteristics. Specifically, since the light emitting device according to the first embodiment has good luminous efficiency, it can be a light emitting device having low power consumption.
  • FIG. 3 shows a passive matrix type light emitting device manufactured by applying the present invention.
  • 3A is a perspective view showing the light emitting device
  • FIG. 3B is a cross-sectional view of FIG. 3A cut by XY.
  • an EL layer 955 is provided between the electrodes 952 and the electrodes 956 on the substrate 951.
  • the end of the electrode 952 is covered with an insulating layer 953.
  • a partition layer 954 is provided on the insulating layer 953.
  • the side wall of the partition wall layer 954 has an inclination such that the distance between one side wall and the other side wall becomes narrower as it gets closer to the substrate surface. That is, the cross section in the short side direction of the partition wall layer 954 is trapezoidal, and the bottom side (the side facing the same direction as the surface direction of the insulating layer 953 and in contact with the insulating layer 953) is the upper side (the surface of the insulating layer 953). It faces in the same direction as the direction, and is shorter than the side that does not contact the insulating layer 953).
  • the passive matrix type light emitting device also uses the light emitting device according to the first embodiment, and can be a light emitting device having low power consumption or a light emitting device having good reliability.
  • FIG. 4B is a top view of the lighting device
  • FIG. 4A is a sectional view taken along line ef in FIG. 4B.
  • the anode 401 is formed on the translucent substrate 400, which is a support.
  • the anode 401 corresponds to the anode 101 in the first embodiment.
  • the anode 401 is formed of a translucent material.
  • a pad 412 for supplying a voltage to the cathode 404 is formed on the substrate 400.
  • An EL layer 403 is formed on the anode 401.
  • the EL layer 403 corresponds to the configuration of the EL layer 103 in the first embodiment, or the configuration in which the light emitting units 511 and 512 and the charge generation layer 513 are combined. Please refer to the description for these configurations.
  • a cathode 404 is formed by covering the EL layer 403.
  • the cathode 404 corresponds to the cathode 102 in the first embodiment.
  • the cathode 404 is formed of a highly reflective material.
  • a voltage is supplied to the cathode 404 by connecting it to the pad 412.
  • the lighting device showing the light emitting device having the anode 401, the EL layer 403, and the cathode 404 in the present embodiment has. Since the light emitting device is a light emitting device having high luminous efficiency, the lighting device in the present embodiment can be a lighting device having low power consumption.
  • the illumination device is completed by fixing the substrate 400 on which the light emitting device having the above configuration is formed and the sealing substrate 407 using the sealing materials 405 and 406 and sealing them. Either one of the sealing materials 405 and 406 may be used. Further, a desiccant can be mixed with the inner sealing material 406 (not shown in FIG. 4B), whereby moisture can be adsorbed, which leads to improvement in reliability.
  • an IC chip 420 or the like on which a converter or the like is mounted may be provided on the IC chip 420.
  • the lighting device according to the present embodiment uses the light emitting device according to the first embodiment for the EL element, and can be a lighting device having low power consumption.
  • the user who authenticates inputs information (for example, a user number) that identifies himself / herself from the input unit 6.
  • the user presents the finger 1 to the input device 2.
  • a light emitting device 3 which is a light source is installed in the input device 2, and the finger 1 is irradiated with infrared light.
  • the light emitting device of one aspect of the present invention can be applied as a light emitting device 3.
  • the image pickup device 4 installed in the input device 2 inputs the image obtained by the image pickup to the CPU 8 via the image input unit 5.
  • the CPU 8 stores the input image in the memory 7, and extracts feature data from the image stored in the memory 7.
  • the CPU 8 acquires personal authentication data stored in the database 9 based on the information input in advance. Subsequently, the CPU 8 stores the acquired authentication data in the memory 7, collates it with the extracted feature data, and identifies the person who presented the finger 1 to the input device 2. As described above, the authentication system of the present embodiment can authenticate the user.
  • FIG. 8 shows a diagram of a portion corresponding to an input device of the transparent vein authentication device.
  • the user's finger 1 is presented so as to close the groove formed in the guide 11.
  • a CMOS camera can be used as the image pickup device 4, and by using the near infrared ray transmission filter 12 in front of the image pickup device 4, a clearer image can be obtained without being affected by visible light or the like.
  • the cover 10 is made of a material that does not transmit both visible light and infrared light because it acts as a support for blocking external light and supporting the light emitting device 3.
  • the guide 11 is also made of a material that does not transmit both visible light and infrared light.
  • the light emitting device of one aspect of the present invention can form a light emitting region in a plane and can be made flexible, the light source portion can be compactly formed even in a transmissive vein authentication device. be able to. Further, since the luminous efficiency is good, the power consumption can be reduced.
  • FIG. 9 is a diagram showing a reflex type vein recognition device.
  • the reflective vein recognition device is excellent in miniaturization and is also applied to mobile devices such as smartphones and smart watches.
  • mobile devices such as smartphones and smart watches.
  • the light emitting device according to one aspect of the present invention can be formed very thin, further miniaturization can be realized.
  • the luminous efficiency is good, the power consumption can be reduced, which is more suitable for application to mobile devices.
  • the light emitting device of one aspect of the present invention is not limited to the vein recognition system, and uses near-infrared light such as a sugar content sensor, cerebral blood flow measurement, pulse measurement, electrocardiogram measurement, and oxygen concentration measurement in blood flow. It can be applied to all devices and systems. Since it can be made flexible, a light emitting region can be obtained in a planar shape, and the light emitting device itself can be made extremely thin, it greatly contributes to miniaturization and the degree of freedom in device design. Further, since the luminous efficiency is good, the power consumption can be reduced.
  • the light emitting device according to the first embodiment is a light emitting device having good luminous efficiency and low power consumption.
  • the electronic device described in the present embodiment can be an electronic device having a light emitting unit having low power consumption.
  • Examples of electronic devices to which the above light emitting device is applied include television devices (also referred to as televisions or television receivers), monitors for computers, digital cameras, digital video cameras, digital photo frames, mobile phones (mobile phones, etc.). (Also referred to as a mobile phone device), a portable game machine, a mobile information terminal, a smart watch, a sound reproduction device, a large game machine such as a pachinko machine, and the like. Specific examples of these electronic devices are shown below.
  • FIG. 5A shows an example of a television device.
  • the display unit 7103 is incorporated in the housing 7101. Further, here, a configuration in which the housing 7101 is supported by the stand 7105 is shown. An image can be displayed by the display unit 7103, and the display unit 7103 is configured by arranging the light emitting devices according to the first embodiment in a matrix.
  • the operation of the television device can be performed by an operation switch provided in the housing 7101 or a separate remote control operation device 7110.
  • the operation keys 7109 included in the remote controller 7110 can be used to control the channel and volume, and the image displayed on the display unit 7103 can be operated.
  • the remote controller 7110 may be provided with a display unit 7107 for displaying information output from the remote controller 7110.
  • the television device is configured to include a receiver, a modem, and the like.
  • the receiver can receive general television broadcasts, and by connecting to a wired or wireless communication network via a modem, it can be unidirectional (sender to receiver) or bidirectional (sender and receiver). It is also possible to perform information communication between (or between recipients, etc.).
  • FIG. 5B1 is a computer, which includes a main body 7201, a housing 7202, a display unit 7203, a keyboard 7204, an external connection port 7205, a pointing device 7206, and the like.
  • This computer is manufactured by arranging the light emitting devices according to the first embodiment in a matrix and using the light emitting devices in the display unit 7203.
  • the computer of FIG. 5B1 may have a form as shown in FIG. 5B2.
  • the computer of FIG. 5B2 is provided with a second display unit 7210 instead of the keyboard 7204 and the pointing device 7206.
  • the second display unit 7210 is a touch panel type, and input can be performed by operating the input display displayed on the second display unit 7210 with a finger or a dedicated pen.
  • the second display unit 7210 can display not only the input display but also other images. Further, the display unit 7203 may also be a touch panel. By connecting the two screens with a hinge, it is possible to prevent troubles such as damage or damage to the screens during storage or transportation.
  • FIG. 5C shows an example of a mobile terminal.
  • the mobile phone includes an operation button 7403, an external connection port 7404, a speaker 7405, a microphone 7406, and the like, in addition to the display unit 7402 incorporated in the housing 7401.
  • the mobile phone may have a display unit 7402 produced by arranging the light emitting devices according to the first embodiment in a matrix.
  • the mobile terminal shown in FIG. 5C may be configured so that information can be input by touching the display unit 7402 with a finger or the like. In this case, operations such as making a phone call or composing an e-mail can be performed by touching the display unit 7402 with a finger or the like.
  • the screen of the display unit 7402 mainly has three modes. The first is a display mode mainly for displaying an image, and the second is an input mode mainly for inputting information such as characters. The third is a display + input mode in which two modes, a display mode and an input mode, are mixed.
  • the display unit 7402 may be set to a character input mode mainly for inputting characters, and the characters displayed on the screen may be input. In this case, it is preferable to display the keyboard or the number button on most of the screen of the display unit 7402.
  • the orientation (vertical or horizontal) of the mobile terminal is determined, and the screen display of the display unit 7402 is automatically displayed. Can be switched.
  • the screen mode can be switched by touching the display unit 7402 or by operating the operation button 7403 of the housing 7401. It is also possible to switch depending on the type of image displayed on the display unit 7402. For example, if the image signal displayed on the display unit is moving image data, the display mode is switched, and if the image signal is text data, the input mode is switched.
  • the input mode the signal detected by the optical sensor of the display unit 7402 is detected, and when there is no input by the touch operation of the display unit 7402 for a certain period of time, the screen mode is switched from the input mode to the display mode. You may control it.
  • the display unit 7402 can also function as an image sensor.
  • the person can be authenticated by touching the display unit 7402 with a palm or a finger and imaging a palm print, a fingerprint, or the like.
  • the light emitting device according to the first embodiment is mounted on the display unit, it is possible to take an image of a finger vein, a palm vein, or the like.
  • FIG. 6A is a schematic view showing an example of a cleaning robot.
  • the cleaning robot 5100 has a display 5101 arranged on the upper surface, a plurality of cameras 5102 arranged on the side surface, a brush 5103, and an operation button 5104. Although not shown, the lower surface of the cleaning robot 5100 is provided with tires, suction ports, and the like.
  • the cleaning robot 5100 also includes various sensors such as an infrared sensor, an ultrasonic sensor, an acceleration sensor, a piezo sensor, an optical sensor, and a gyro sensor. Further, the cleaning robot 5100 is provided with wireless communication means.
  • the light emitting device of one aspect of the present invention may be mounted as the sensor or communication means.
  • the cleaning robot 5100 is self-propelled, can detect dust 5120, and can suck dust from a suction port provided on the lower surface.
  • the cleaning robot 5100 can analyze the image taken by the camera 5102 and determine the presence or absence of obstacles such as walls, furniture, and steps. Further, when an object such as wiring that is likely to be entangled with the brush 5103 is detected by image analysis, the rotation of the brush 5103 can be stopped.
  • the display 5101 can display the remaining amount of the battery, the amount of dust sucked, and the like.
  • the route traveled by the cleaning robot 5100 may be displayed on the display 5101. Further, the display 5101 may be a touch panel, and the operation buttons 5104 may be provided on the display 5101.
  • the cleaning robot 5100 can communicate with a portable electronic device 5140 such as a smartphone.
  • the image taken 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 when he / she is out. Further, the display of the display 5101 can be confirmed by a portable electronic device such as a smartphone.
  • the light emitting device of one aspect of the present invention may be used for the display 5101.
  • the robot 2100 shown in FIG. 6B includes a computing device 2110, an illuminance sensor 2101, a microphone 2102, an upper camera 2103, a speaker 2104, a display 2105, a lower camera 2106, an obstacle sensor 2107, and a moving mechanism 2108.
  • the microphone 2102 has a function of detecting a user's voice, environmental sound, and the like. Further, the speaker 2104 has a function of emitting sound.
  • the robot 2100 can communicate with the user using the microphone 2102 and the speaker 2104.
  • the display 2105 has a function of displaying various information.
  • the robot 2100 can display the information desired by the user on the display 2105.
  • the display 2105 may be equipped with a touch panel. Further, the display 2105 may be a removable information terminal, and by installing the display 2105 at a fixed position of the robot 2100, charging and data transfer are possible.
  • the upper camera 2103 and the lower camera 2106 have a function of photographing the surroundings of the robot 2100. Further, the obstacle sensor 2107 can detect the presence or absence of an obstacle in the traveling direction when the robot 2100 advances by using the moving 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.
  • the light emitting device of one aspect of the present invention can be used for an obstacle sensor 2107 and a display 2105.
  • FIG. 6C is a diagram showing an example of a goggle type display.
  • the goggle type display includes, for example, a housing 5000, a display unit 5001, a speaker 5003, an LED lamp 5004, a connection terminal 5006, and a sensor 5007 (force, displacement, position, speed, acceleration, angular velocity, rotation speed, distance, light, liquid, etc. Includes functions to measure magnetism, temperature, chemicals, voice, time, hardness, electric field, current, voltage, power, radiation, flow rate, humidity, gradient, vibration, odor, or infrared rays), microphone 5008, display 5002 , Support portion 5012, earphone 5013, and the like.
  • the light emitting device of one aspect of the present invention can be used for the sensor 5007, the display unit 5001 and the display unit 5002.
  • FIGS. 10A and 10B show a foldable portable information terminal 5150.
  • the foldable personal digital assistant 5150 has a housing 5151, a display area 5152, and a bent portion 5153.
  • FIG. 10A shows the mobile information terminal 5150 in the expanded state.
  • FIG. 10B shows a mobile information terminal 5150 in a folded state.
  • the portable information terminal 5150 has a large display area 5152, it is compact and excellent in portability when folded.
  • the display area 5152 can be folded in half by the bent portion 5153.
  • the bent portion 5153 is composed of a stretchable member and a plurality of support members. When folded, the stretchable member is stretched, and the bent portion 5153 is folded with a radius of curvature of 2 mm or more, preferably 3 mm or more. Is done.
  • the display area 5152 may be a touch panel (input / output device) equipped with a touch sensor (input device).
  • the light emitting device of one aspect of the present invention can be used in the display area 5152.
  • FIGS. 11A to 11C show a foldable mobile information terminal 9310.
  • FIG. 11A shows the mobile information terminal 9310 in the expanded state.
  • FIG. 11B shows a mobile information terminal 9310 in a state of being changed from one of the expanded state or the folded state to the other.
  • FIG. 11C shows a mobile information terminal 9310 in a folded state.
  • the mobile information terminal 9310 is excellent in portability in the folded state, and is excellent in display listability due to a wide seamless display area in the unfolded state.
  • 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) equipped with a sensor (input device, authentication device) using the light emitting device of one aspect of the present invention. Further, the display panel 9311 can be reversibly deformed from the unfolded state to the folded state of the portable information terminal 9310 by bending between the two housings 9315 via the hinge 9313.
  • the light emitting device of one aspect of the present invention can be used for the display panel 9311.
  • the configurations shown in the present embodiment can be used by appropriately combining the configurations shown in the first to third embodiments.
  • the range of application of the light emitting device provided with the light emitting device according to the first embodiment is extremely wide, and this light emitting device can be applied to electronic devices in all fields.
  • an electronic device having low power consumption can be obtained.
  • the light emitting device 1 which is the light emitting device of one aspect of the present invention and the comparative light emitting device 1 in the comparative light emitting device will be described.
  • the structural formulas of the organic compounds used in the light emitting device 1 and the comparative light emitting device 1 are shown below.
  • an alloy film (Ag-Pd-Cu (APC) film) of silver (Ag), palladium (Pd) and copper (Cu) is formed on a glass substrate as a reflective electrode with a thickness of 100 nm by a sputtering method.
  • indium tin oxide (ITSO) containing silicon oxide was formed as a transparent electrode by a sputtering method to a thickness of 10 nm to form an anode 101.
  • the electrode area was 4 mm 2 (2 mm ⁇ 2 mm).
  • the surface of the substrate was washed with water, fired at 200 ° C. for 1 hour, and then UV ozone treatment was performed for 370 seconds.
  • the substrate was introduced into a vacuum deposition apparatus whose internal pressure was reduced to about 10-4 Pa, vacuum-baked at 170 ° C. for 30 minutes in a heating chamber inside the vacuum deposition apparatus, and then the substrate was released for about 30 minutes. It was chilled.
  • N- (4-cyclohexylphenyl) -N- (3 ′′, 5 ′′ -ditercious butyl-1,1 ′′ -biphenyl-4-yl) -N represented by the above structural formula (i) by the method.
  • mmtBuBichPAF -(9,9-dimethyl-9H-fluoren-2yl) amine
  • ALD-MP001Q Analytical Studio Co., Ltd., material serial number: 1S20170124
  • mmtBuBichPAF is deposited on the hole injection layer 111 as the first hole transport layer so as to have a diameter of 55 nm, and then the second hole transport layer is represented by the above structural formula (ii).
  • the second hole transport layer also functions as an electron block layer.
  • 9mDBtBPNfpr as a first electron transport layer is deposited on the light emitting layer 113 so as to have a film thickness of 20 nm, and then as a second electron transport layer 2, 9- represented by the above structural formula (v).
  • LiF is vapor-deposited to a film thickness of 1 nm to form an electron injection layer 115, and the volume ratio of silver (Ag) and magnesium (Mg) is 1: 0.1.
  • the cathode 102 was formed by vapor deposition so as to have a thickness of 30 nm.
  • the 5,10,15,20-tetraphenylbisbenzo [5,6] indeno [1,2,3-cd: 1', 2' which is in contact with the cathode 102 and is represented by the above structural formula (vi).
  • DBP 3'-lm] Perylene
  • the cathode 102 is a semi-transmissive / semi-reflective electrode having a function of reflecting light and a function of transmitting light
  • the light emitting device 1 of this embodiment is a top emission element that extracts light from the cathode 102.
  • the first layer of the light emitting device 1 is formed by forming the first layer of the light emitting device 1 with 4,4', 4''- (benzene-1,3,5-triyl) tri (dibenzothiophene) represented by the above structural formula (vii). ) (Abbreviation: DBT3P-II) was formed by vapor deposition so as to have a diameter of 115 nm, and was produced in the same manner as in the light emitting device 1.
  • the radiation divergence-current density characteristics of the light emitting device 1 and the comparative light emitting device 1 are shown in FIG. 12, the radiation divergence-voltage characteristics are shown in FIG. 13, the radiation bundle-current density characteristics are shown in FIG. 14, and the current-voltage characteristics are shown in FIG.
  • the external quantum efficiency-current density characteristic is shown in FIG. 16, and the EL emission spectrum when a current is passed at a current density of 10 mA / cm 2 is shown in FIG. Table 2 shows the main characteristics of the light emitting device 1 and the comparative light emitting device 1 in the vicinity of the current density of 10 mA / cm 2.
  • the radiant exitance, radiant flux, and external quantum efficiency were calculated using a near-infrared spectroradiometer (SR-NIR, manufactured by Topcon), assuming that the light distribution characteristics of the device were Lambersian type.
  • the light emitting device 1 and the comparative light emitting device 1 were near-infrared light emitting devices having good characteristics, but the light emitting device 1 was in contact with the cathode 102 and was a layer of DBP. It was found that the external quantum efficiency was improved by providing.
  • FIG. 18 shows a graph showing the change in luminance with respect to the driving time when the luminance at a current density of 75 mA / cm 2 is standardized by the initial luminance.
  • the light emitting device 1 and the comparative light emitting device 1 maintain a brightness of 95% or more of the initial brightness even after 450 hours have elapsed, and the decrease in brightness due to the accumulation of the driving time is particularly small and has a very long life. It turned out to be a good light emitting device.
  • the light emitting devices 1-1 to 1-4 in which the film thickness of the first layer in the light emitting device 1 is changed, and the comparative light emitting device 1- in which the film thickness of the first layer in the comparative light emitting device is changed, respectively. 1 to 1-4 were prepared.
  • the film thickness of the first layer in each light emitting device is summarized in Table 3.
  • FIG. 19 shows a graph in which the external quantum efficiency when a current is passed through these light emitting devices at a current density of 5 mA / cm 2 is plotted against the film thickness of the first layer.
  • the maximum external quantum efficiency of the light emitting device of one aspect of the present invention in FIG. 19 is 15.5%, which is about 1.05 times that of 14.7% of the maximum external quantum efficiency of the comparative light emitting device. It was. Since it is considered that the light emitting device of one aspect of the present invention leaves room for further extension of the external quantum efficiency by making the film thickness of the first layer thinner than 100 nm, the light emitting device of the present invention is described. It can be said that an efficiency of at least 1.05 times or more that of a comparative light emitting device can be realized.
  • the above-mentioned external quantum efficiency is an efficiency assuming that the light distribution characteristic of the device is a Lambersian type. When the light distribution characteristics of the light emitting device according to one aspect of the present invention were measured, the light distribution Lambersian ratio was 46.2%. From this, the maximum value of the true external quantum efficiency of the light emitting device of one aspect of the present invention was 7.2%.
  • the results of measuring the refractive index n and the extinction coefficient k of ⁇ II are shown in FIGS. 20A, 20B, 21A, and 21B.
  • the refractive index n and the extinction coefficient k were measured using a spectroscopic ellipsometer (M-2000U, manufactured by JA Woolam Japan Co., Ltd.). For the measurement, a film obtained by forming a material on a quartz substrate by a vacuum deposition method at about 50 nm was used.
  • FIGS. 20 and 21 A shows the result of DBP, and B shows the result of DBT3P-II. Further, in FIGS. 20 and 21, the solid line represents the refractive index n or the extinction coefficient k in the normal light ray, and the dotted line represents the refractive index n or the extinction coefficient k in the abnormal light ray.
  • the refractive index of DBP is higher than that of DBT3P-II in the wavelength range of 700 nm to 1000 nm, and it is possible to extract light emitted from the EL layer more efficiently.
  • DBP has a large extinction coefficient in the wavelength range of visible light and absorbs a large amount in the visible light region.
  • DBT3P-II has a very small extinction coefficient value in the visible light region and very small absorption in the visible light region.
  • FIG. 22 is a graph showing the spectral radiance-wavelength characteristics when a voltage of 5 V is applied to the light emitting device 1 and the comparative light emitting device 1.
  • the wavelength range of 380 to 780 nm is measured using a spectroradiometer (SR-UL1R manufactured by Topcon), and the wavelength range of 781 to 1030 nm is measured using a near infrared spectroradiometer (SR-NIR manufactured by Topcon). did.
  • the light emitting device 1 uses DBP having a large extinction coefficient k in the visible light range in the first layer, comparative light emission using DBT3P-II having no large extinction coefficient k in the visible light range. It can be seen that the light emission in the visible light region is smaller than that of the device 1.
  • the luminance (cd / m 2) is the light-emitting device 1 when a voltage is 3.6V applied 0.598cd / m 2, the comparative light-emitting devices 1 was 1.14cd / m 2. Since the brightness (cd / m 2 ) is a unit related to the luminosity factor, it can be seen that the light emission in the visible light region of the light emitting device 1 is sufficiently smaller than that of the comparative light emitting device 1.
  • the radiance in the same condition (W / sr / m 2) the light emitting device 1, 10.2W / sr / m 2, was compared emitting device 1, 9.87W / sr / m 2.
  • Radiance (W / sr / m 2 ) is a physical quantity that represents a radiant flux emitted in a certain direction from a point on the surface of the radiation source, and luminosity factor is irrelevant. From this, it was found that the energy radiated from the light emitting device 1 was larger than that of the comparative light emitting device 1 by making the first layer DBP.
  • the light emitting device of one aspect of the present invention is a near infrared light emitting device that is very efficient and difficult to see.
  • this light emitting device is a near infrared light emitting device having extremely high reliability and good characteristics.
  • step 1 3', 5'-ditercious butyl-4-chloro-1,1'-biphenyl> 13.5 g (50 mmol) of 3,5-ditershally butyl-1-bromobenzene, 8.2 g (52.5 mmol) of 4-chlorophenylboronic acid, 21.8 g (158 mmol) of potassium carbonate, 125 mL of toluene, 31 mL of ethanol in a three-necked flask. , 40 mL of water was added, and after degassing under reduced pressure, the inside of the flask was replaced with nitrogen.
  • step 1 The synthesis scheme of step 1 is shown in the following equation.
  • Step 2 Synthesis of N- (4-cyclohexylphenyl) -N- (9,9-dimethyl-9H-fluorene-2yl) amine>
  • 10.5 g (50 mmol) of 9,9-dimethyl-9H-fluorene-2-amine, 12.0 g (50 mmol) of 4-cyclohexyl-1-bromobenzene, 14.4 g (150 mmol) of sodium-tert-butoxide, 250 mL of xylene was added and degassed under reduced pressure, and then the inside of the flask was replaced with nitrogen. The mixture was heated and stirred to about 50 ° C.
  • allyl palladium chloride dimer (II) (abbreviation: (AllylPdCl) 2 ) 183 mg (0.50 mmol), di-tert-butyl (1-methyl-2,2-diphenylcyclopropyl) phosphine (abbreviation: cBRIDP). (Registered Trademark)) 821 mg (2.0 mmol) was added, and the mixture was heated at 90 ° C. for about 6 hours. Then, the temperature of the flask was lowered to about 60 ° C., about 4 mL of water was added, and the precipitated solid was filtered off. The filtrate was concentrated and the resulting solution was purified by silica gel column chromatography.
  • step 1 The synthesis scheme of step 1 is shown in the following equation.
  • Step 3 N- (4-Cyclohexylphenyl) -N- (3', 5'-ditercious butyl-1,1'-biphenyl-4-yl) -N- (9,9-dimethyl-9H-fluorene) -Synthesis of -2 yl) amine (abbreviation: mmtBuBichPAF)> 3.2 g (10.6 mmol) of 3', 5'-ditercious butyl-4-chloro-1,1'-biphenyl obtained in step 1 and N- (4-cyclohexyl) obtained in step 2 in a three-necked flask.
  • allyl palladium chloride dimer (II) (abbreviation: (AllylPdCl) 2 ) 39 mg (0.11 mmol), di-tert-butyl (1-methyl-2,2-diphenylcyclopropyl) phosphine (abbreviation: cBRIDP). (Registered Trademark)) 150 mg (0.42 mmol) was added, and the mixture was heated at 120 ° C. for about 3 hours. Then, the temperature of the flask was returned to about 60 ° C., and about 1 mL of water was added to precipitate a solid. The precipitated solid was filtered off. The filtrate was concentrated and the resulting solution was purified by silica gel column chromatography.
  • II allyl palladium chloride dimer
  • cBRIDP di-tert-butyl (1-methyl-2,2-diphenylcyclopropyl) phosphine
  • step 3 The synthesis scheme of step 3 is shown in the following equation.
  • Step 1 Synthesis of 2,3-bis- (3,5-dimethylphenyl) -2-benzo [g] quinoxaline (abbreviation: Hdmdpbq)> 3.20 g of 3,3', 5,5'-tetramethylbenzyl, 1.97 g of 2,3-diaminonaphthalene, and 60 mL of ethanol were placed in a three-necked flask equipped with a reflux tube, and the inside was replaced with nitrogen, and then 90 ° C. Was stirred for 7 and a half hours. After a lapse of a predetermined time, the solvent was distilled off. Then, the product was purified by silica gel column chromatography using toluene as a developing solvent to obtain the desired product (yellow solid, yield 3.73 g, yield 79%).
  • the synthesis scheme of step 1 is shown below.
  • step 2 The synthesis scheme of step 2 is shown below.
  • the obtained solid was purified by silica gel column chromatography using dichloromethane as a developing solvent, and then recrystallized from a mixed solvent of dichloromethane and methanol to obtain the desired product (dark green solid, yield 0.42 g, 21% yield). 0.41 g of the obtained dark green solid was sublimated and purified by the train sublimation method.
  • the sublimation purification conditions were such that the dark green solid was heated at 300 ° C. while flowing an argon gas at a pressure of 2.7 Pa and a flow rate of 10.5 mL / min. After sublimation purification, a dark green solid was obtained in a yield of 78%.
  • the synthesis scheme of step 3 is shown below.

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