WO2020212799A1 - 表示装置、表示モジュール、及び電子機器 - Google Patents
表示装置、表示モジュール、及び電子機器 Download PDFInfo
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- WO2020212799A1 WO2020212799A1 PCT/IB2020/053289 IB2020053289W WO2020212799A1 WO 2020212799 A1 WO2020212799 A1 WO 2020212799A1 IB 2020053289 W IB2020053289 W IB 2020053289W WO 2020212799 A1 WO2020212799 A1 WO 2020212799A1
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- light emitting
- layer
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- compound
- emitting device
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- 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
Definitions
- One aspect of the present invention relates to display devices, display modules, and electronic devices.
- One aspect of the present invention is not limited to the above technical fields.
- the technical fields of one aspect of the present invention include semiconductor devices, display devices, light emitting devices, power storage devices, storage devices, electronic devices, lighting devices, input devices (for example, touch sensors), input / output devices (for example, touch panels, etc.). ), Their driving method, or their manufacturing method can be given as an example.
- display devices are expected to be applied to various applications.
- applications of a large display device include a home television device (also referred to as a television or television receiver), digital signage (electronic signboard), PID (Public Information Display), and the like.
- a home television device also referred to as a television or television receiver
- digital signage electronic signboard
- PID Public Information Display
- smartphones and tablet terminals equipped with a touch panel are being developed.
- a light emitting device having a light emitting device has been developed.
- a light emitting device also referred to as an EL device or EL element
- EL electroluminescence
- Patent Document 1 discloses a flexible light emitting device to which an organic EL device (also referred to as an organic EL element) is applied.
- One aspect of the present invention is to provide a display device having a long life.
- One aspect of the present invention is to provide a highly reliable display device.
- One aspect of the present invention is to provide a large-sized display device.
- One aspect of the present invention is to provide a highly productive display device.
- One aspect of the present invention is to provide a display device having high display quality.
- One aspect of the present invention is a display device having a first light emitting device and a second light emitting device.
- the first light emitting device has a first electrode and a common electrode.
- the second light emitting device has a second electrode and a common electrode.
- the first light emitting device has a first light emitting layer and an electron transporting layer in this order from the electrode side of the first electrode and the common electrode that functions as an anode.
- the second light emitting device has a second light emitting layer between the second electrode and the common electrode.
- the first light emitting layer has a first organic compound that emits light of a first color.
- the second light emitting layer has a second organic compound that emits light of a second color.
- the electron transport layer has a third organic compound and a first substance.
- the third organic compound is an electron transporting material.
- the first substance is a metal, metal salt, metal oxide, or organometallic salt.
- the electron transport layer has a first region and a second region. The concentration of the first substance is different from each other in the first region and the second region.
- the first region When the first region is located closer to the first light emitting layer than the second region, the first region preferably has a higher concentration of the first substance than the second region.
- the second light emitting device preferably has a layer common to that of the first light emitting device between the second electrode and the common electrode.
- the third organic compound is HOMO level -6.0eV above, and the electric field intensity electron mobility in the square root 600 [V / cm] is 1 ⁇ 10 -7 cm 2 / Vs or more 5 ⁇ 10 - It is preferably 5 cm 2 / Vs or less.
- the second light emitting layer preferably further contains a fourth organic compound and a fifth organic compound.
- the fourth organic compound and the fifth organic compound are preferably a combination that forms an excitation complex.
- the first light emitting device preferably further has a hole injection layer.
- the hole injection layer is preferably in contact with an electrode that functions as an anode among the first electrode and the common electrode.
- the hole injection layer preferably has a first compound and a second compound.
- the first compound preferably has electron acceptability for the second compound.
- the HOMO level of the second compound is preferably -5.7 eV or more and -5.4 eV or less.
- the first light emitting device preferably further has a first hole transport layer.
- the first hole transport layer is preferably located between the hole injection layer and the first light emitting layer.
- the first hole transport layer preferably has a third compound.
- the HOMO level of the third compound is preferably a value equal to or lower than the HOMO level of the second compound.
- the difference between the HOMO level of the third compound and the HOMO level of the second compound is preferably within 0.2 eV.
- the second compound and the third compound preferably have at least one of a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, and an anthracene skeleton, respectively.
- the first light emitting device preferably further has a second hole transport layer.
- the second hole transport layer is preferably located between the first hole transport layer and the first light emitting layer.
- the second hole transport layer preferably has a fourth compound.
- the HOMO level of the fourth compound is preferably lower than the HOMO level of the third compound.
- the second compound, the third compound, and the fourth compound preferably have at least one of a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, and an anthracene skeleton, respectively.
- the first organic compound is preferably a fluorescent luminescent substance.
- the first color is preferably blue.
- the second color is preferably red or green.
- the first substance is preferably an organometallic complex having an alkali metal or an alkaline earth metal.
- the first substance is preferably an organometallic complex having a ligand having nitrogen and oxygen and an alkali metal or an alkaline earth metal.
- the first substance is preferably an organometallic complex having a quinolinol ligand and an alkali metal or alkaline earth metal.
- One aspect of the present invention is a display module having a display device having any of the above configurations and to which a connector such as a flexible printed circuit board (hereinafter referred to as FPC) or TCP (Tape Carrier Package) is attached.
- a display module such as a display module in which an integrated circuit (IC) is mounted by a COG (Chip On Glass) method, a COF (Chip On Film) method, or the like.
- One aspect of the present invention is an electronic device having the above display module and at least one of an antenna, a battery, a housing, a camera, a speaker, a microphone, and an operation button.
- a display device having a long life can be provided.
- a highly reliable display device can be provided.
- a large display device can be provided.
- a highly productive display device can be provided.
- a display device having high display quality can be provided.
- FIG. 1A and 1B are cross-sectional views showing an example of a display device.
- 2A and 2B are cross-sectional views showing an example of a display device.
- FIG. 3 is a cross-sectional view showing an example of the display device.
- 4A to 4C are cross-sectional views showing an example of a light emitting device.
- 5A to 5C are conceptual diagrams illustrating a light emitting model of the light emitting device.
- FIG. 5D is a diagram illustrating the normalized brightness of the light emitting device over time.
- 6A-6D are diagrams illustrating the concentration of the first substance in the electron transport layer.
- FIG. 7 is a perspective view showing an example of the display device.
- 8A and 8B are cross-sectional views showing an example of a display device.
- FIG. 9A is a cross-sectional view showing an example of the display device.
- FIG. 9B is a cross-sectional view showing an example of a transistor.
- FIG. 10A is a block diagram showing an example of pixels.
- FIG. 10B is a circuit diagram showing an example of a pixel circuit.
- FIG. 11A is a diagram illustrating classification of the crystal structure of IGZO.
- FIG. 11B is a diagram illustrating an XRD spectrum of a quartz glass substrate.
- FIG. 11C is a diagram illustrating an XRD spectrum of a crystalline IGZO film.
- FIG. 11D is a diagram illustrating a microelectron diffraction pattern of a quartz glass substrate.
- FIG. 11A is a cross-sectional view showing an example of the display device.
- FIG. 9B is a cross-sectional view showing an example of a transistor.
- FIG. 10A is a block diagram showing an example of pixels.
- FIG. 10B is
- 11E is a diagram for explaining the microelectron diffraction pattern of the crystalline IGZO film.
- 12A and 12B are diagrams showing an example of an electronic device.
- 13A to 13C are diagrams showing an example of an electronic device.
- 14A and 14B are diagrams showing an example of an electronic device.
- 15A to 15D are diagrams showing an example of an electronic device.
- 16A to 16D are diagrams showing an example of an electronic device.
- 17A to 17F are diagrams showing an example of an electronic device.
- FIG. 18A is a diagram showing the structure of an electron-only device.
- FIG. 18B is a diagram showing the structure of the light emitting device of the embodiment.
- FIG. 19 is a diagram showing the current density-voltage characteristics of the electron-only device.
- FIG. 18A is a diagram showing the structure of an electron-only device.
- FIG. 18B is a diagram showing the structure of the light emitting device of the embodiment.
- FIG. 19 is a
- FIG. 20 is a diagram showing the frequency characteristics of the calculated capacitance C of ZADN: Liq (1: 1) at a DC power supply of 7.0 V.
- FIG. 21 is a diagram showing a frequency characteristic of ⁇ B of ZADN: Liq (1: 1) at a DC voltage of 7.0 V.
- FIG. 22 is a diagram showing electric field strength-dependent characteristics of electron mobility in each organic compound.
- FIG. 23 is a diagram showing the luminance-current density characteristics.
- FIG. 24 is a diagram showing the luminance-voltage characteristics.
- FIG. 25 is a diagram showing current efficiency-luminance characteristics.
- FIG. 26 is a diagram showing a current density-voltage characteristic.
- FIG. 27 is a diagram showing an emission spectrum.
- FIG. 28 is a diagram showing the luminance-current density characteristics.
- FIG. 29 is a diagram showing a luminance-voltage characteristic.
- FIG. 30 is a diagram showing current efficiency-luminance characteristics.
- FIG. 31 is a diagram showing a current density-voltage characteristic.
- FIG. 32 is a diagram showing an emission spectrum.
- FIG. 33 is a diagram showing the luminance-current density characteristics.
- FIG. 34 is a diagram showing the luminance-voltage characteristic.
- FIG. 35 is a diagram showing the current efficiency-luminance characteristic.
- FIG. 36 is a diagram showing a current density-voltage characteristic.
- FIG. 37 is a diagram showing an emission spectrum.
- FIG. 38 is a diagram showing the results of the reliability test.
- FIG. 39 is a diagram showing the results of the reliability test.
- FIG. 40 is a diagram showing the results of the reliability test.
- FIG. 41 is a diagram showing the results of the reliability test.
- membrane and the word “layer” can be interchanged with each other in some cases or depending on the situation.
- conductive layer can be changed to the term “conductive layer”.
- insulating film can be changed to the term “insulating layer”.
- the display device of the present embodiment has a light emitting device in the display unit, and the display unit can display an image.
- an EL device such as an OLED (Organic Light Emitting Diode) or a QLED (Quantum-dot Light Emitting Diode).
- the luminescent substances possessed by the EL device include substances that emit fluorescence (fluorescent luminescent substances), substances that emit phosphorescence (phosphorescent luminescent substances), inorganic compounds (quantum dot materials, etc.), and substances that exhibit delayed fluorescence (thermal activation). Delayed fluorescence (Thermally Activated Fluorescence (TADF) material) and the like can be mentioned.
- TADF Thermally Activated Fluorescence
- a color-coding method is applied to the colorization method of the display device of the present embodiment.
- the color-coding method is used for a small display device, it is preferable because the matching accuracy of the metal mask can be improved and the yield of coloring can be increased. Further, since a large display device can have a relatively low definition, it is advantageous in that a separate painting type light emitting device is adopted.
- the light emitting devices included in the sub-pixels of each color have different light emitting layers.
- the light emitting layers of each light emitting device are preferably separated from each other.
- the light emitting layers of each light emitting device may have a portion overlapping with each other.
- the display device of the present embodiment has a top emission type that emits light in the direction opposite to the substrate on which the light emitting device is formed, a bottom emission type that emits light on the substrate side on which the light emitting device is formed, and both sides. It may be any of the dual emission type that emits light.
- micro-optical resonator microcavity
- the EL layer in addition to the light emitting layer, another layer (for example, a hole transport layer) is painted separately with a light emitting device of each color, and other layers are used.
- the layer is preferably a common layer for the light emitting devices of each color.
- the display device of the present embodiment has a light emitting device having a configuration in which holes are easily injected into the light emitting layer and electrons are hard to be injected.
- a light emitting device having a configuration in which holes are easily injected into the light emitting layer and electrons are hard to be injected.
- FIGS. 1 to 3 show a configuration example of a display device.
- the configuration of the light emitting device illustrated in FIGS. 4 to 6 is applied to at least one light emitting device.
- FIG. 1A shows a cross-sectional view of the display device 10A.
- the display device 10A includes a light emitting device 190R exhibiting red light 21R, a light emitting device 190G exhibiting green light 21G, and a light emitting device 190B exhibiting blue light 21B.
- the light emitting device 190R has a pixel electrode 191 and an optical adjustment layer 199R, a buffer layer 192R, a light emitting layer 193R, a buffer layer 194R, and a common electrode 115.
- the light emitting layer 193R has an organic compound that emits red light.
- the light emitting device 190G has a pixel electrode 191 and an optical adjustment layer 199G, a buffer layer 192G, a light emitting layer 193G, a buffer layer 194G, and a common electrode 115.
- the light emitting layer 193G has an organic compound that emits green light.
- the light emitting device 190B has a pixel electrode 191 and an optical adjustment layer 199B, a buffer layer 192B, a light emitting layer 193B, a buffer layer 194B, and a common electrode 115.
- the light emitting layer 193B has an organic compound that emits blue light.
- an organic compound that emits blue light may be referred to as a first organic compound, and an organic compound that emits red light or an organic compound that emits green light may be referred to as a second organic compound. ..
- the configuration of the light emitting device illustrated in FIGS. 4 to 6 is applied to at least one of the light emitting device 190R, the light emitting device 190G, and the light emitting device 190B.
- the pixel electrode 191 functions as an anode and the common electrode 115 functions as a cathode will be described as an example.
- the buffer layer 194B, and the common electrode 115 may have a single-layer structure or a laminated structure, respectively.
- the pixel electrode 191 is located on the insulating layer 214. The end of the pixel electrode 191 is covered with a partition wall 216. Each pixel electrode 191 is electrically insulated from each other (also referred to as being electrically separated) by a partition wall 216.
- An organic insulating film is suitable as the partition wall 216.
- Examples of the material that can be used for the organic insulating film include acrylic resin, polyimide resin, epoxy resin, polyamide resin, polyimideamide resin, siloxane resin, benzocyclobutene resin, phenol resin, and precursors of these resins. ..
- the buffer layer 192 is located on the pixel electrode 191.
- the light emitting layer 193 overlaps with the pixel electrode 191 via the buffer layer 192.
- the buffer layer 194 is located on the light emitting layer 193.
- the light emitting layer 193 overlaps with the common electrode 115 via the buffer layer 194.
- the buffer layer 192 can have one or both of the hole injection layer and the hole transport layer.
- the buffer layer 194 can have one or both of an electron injection layer and an electron transport layer.
- the common electrode 115 is a layer commonly used for the light emitting device 190 of each color.
- the display device 10A has a light emitting device 190, a transistor 42, and the like between the pair of substrates (the substrate 151 and the substrate 152).
- the buffer layer 192, the light emitting layer 193, and the buffer layer 194 located between the pixel electrode 191 and the common electrode 115 can also be referred to as EL layers.
- the pixel electrode 191 preferably has a function of reflecting visible light.
- the common electrode 115 has a function of transmitting visible light.
- one of the pair of electrodes of the light emitting device preferably has an electrode having transparency and reflection to visible light (semi-transmissive / semi-reflective electrode), and the other has an electrode having reflection to visible light (semi-transmissive / semi-reflective electrode). It is preferable to have a reflective electrode).
- the light emitting device has a microcavity structure, the light emitted from the light emitting layer can be resonated between both electrodes, and the light emitted from the light emitting device can be strengthened.
- the semi-transmissive / semi-reflective electrode can have a laminated structure of a reflective electrode and an electrode having transparency to visible light (also referred to as a transparent electrode).
- the reflective electrode which functions as a part of the semitransmissive / semi-reflective electrode, may be referred to as a pixel electrode or a common electrode
- the transparent electrode may be referred to as an optical adjustment layer.
- the layer can also be said to have a function as a pixel electrode or a common electrode.
- the light transmittance of the transparent electrode shall be 40% or more.
- an electrode having a transmittance of 40% or more for visible light (light having a wavelength of 400 nm or more and less than 750 nm) and near-infrared light (light having a wavelength of 750 nm or more and 1300 nm or less) as the light emitting device.
- the reflectance of each of the visible light and the near-infrared light of the semi-transmissive / semi-reflective electrode is 10% or more and 95% or less, preferably 30% or more and 80% or less.
- the reflectance of visible light and near-infrared light of the reflecting electrode is 40% or more and 100% or less, preferably 70% or more and 100% or less.
- the resistivity of these electrodes is preferably 1 ⁇ 10 -2 ⁇ cm or less.
- the optical adjustment layer 199 is provided on the pixel electrode 191
- the optical adjustment layer 199 may not be provided.
- the buffer layer 192 or the buffer layer 194 may have a function as an optical adjustment layer.
- the film thickness of the buffer layer 192 or the buffer layer 194 it is possible to intensify and extract light of a specific color in each light emitting device.
- the semi-transmissive / semi-reflective electrode has a laminated structure of a reflective electrode and a transparent electrode, the optical distance between the pair of electrodes indicates the optical distance between the pair of reflective electrodes.
- the light emitting device 190 has a function of emitting visible light. Specifically, the light emitting device 190 is an electroluminescent device that emits light to the substrate 152 side by applying a voltage between the pixel electrode 191 and the common electrode 115.
- the pixel electrode 191 is electrically connected to the source or drain of the transistor 42 through an opening provided in the insulating layer 214.
- the transistor 42 has a function of controlling the drive of the light emitting device 190.
- each of the light emitting devices 190 is covered with a protective layer 195.
- the protective layer 195 is provided in contact with the common electrode 115.
- the protective layer 195 it is possible to prevent impurities such as water from entering the light emitting device 190 and improve the reliability of the light emitting device 190.
- the protective layer 195 and the substrate 152 are bonded to each other by the adhesive layer 142.
- the light-shielding layer BM a material that blocks light emission from the light-emitting device can be used.
- the light-shielding layer BM preferably absorbs visible light.
- a metal material or a resin material containing a pigment (carbon black or the like) or a dye can be used to form a black matrix.
- the light-shielding layer BM may have a laminated structure of a red color filter, a green color filter, and a blue color filter.
- the light emitting layer 193R preferably has a phosphorescent substance as an organic compound that emits red light.
- the light emitting layer 193G preferably has a phosphorescent substance as an organic compound that emits green light.
- an excited complex is formed on the light emitting layer 193R by applying a voltage between the pixel electrode 191 and the common electrode 115.
- an excited complex is formed in the light emitting layer 193G by applying a voltage between the pixel electrode 191 and the common electrode 115.
- the light emitting layer 193R and the light emitting layer 193G each have two kinds of organic compounds in addition to the light emitting substance.
- the two organic compounds are preferably substances that form an excitation complex. It can be said that the two organic compounds are a combination that forms an excited complex.
- the two kinds of organic compounds can also be referred to as a host material and an assist material, or a first host material and a second host material.
- the host material contained in each of the light emitting layer 193R and the light emitting layer 193G is a mixed material of two kinds of organic compounds.
- Each of the two kinds of organic compounds contained in the light emitting layer 193R may be the same material as each of the two kinds of organic compounds contained in the light emitting layer 193G, or may be different materials.
- two kinds of organic compounds may be described as a 4th organic compound and a 5th organic compound.
- the configuration of the light emitting layer capable of forming the excited complex will be described later.
- the light emitting layer 193B preferably has a fluorescent light emitting substance as an organic compound that emits blue light.
- FIG. 1B shows a cross-sectional view of the display device 10B.
- the description of the same configuration as the display device described above may be omitted.
- the display device 10B is different from the display device 10A in that the red light emitting device 190R and the green light emitting device 190G have a common layer 182 and a common layer 184.
- the red light emitting device 190R the green light emitting device 190G, and the blue light emitting device 190B
- at least two color light emitting devices preferably have one or more commonly used layers (common layers).
- the display device can be manufactured with a small number of manufacturing steps.
- FIG. 1B shows an example in which the light emitting device 190R and the light emitting device 190G have the common layer 182 and the common layer 184, but in the display device of one aspect of the present invention, the light emitting device 190R and the light emitting device 190G have only the common layer 182, or , The configuration may have only the common layer 184.
- the common layer 182 is located between the pixel electrode 191 and the light emitting layer 193R, and between the pixel electrode 191 and the light emitting layer 193G.
- the common layer 184 is located between the light emitting layer 193R and the common electrode 115, and between the light emitting layer 193G and the common electrode 115.
- the common layer 182 and the common layer 184 may have a single-layer structure or a laminated structure, respectively.
- the common layer 182 for example, one or both of the hole injection layer and the hole transport layer can be formed.
- the common layer 184 for example, one or both of the electron injection layer and the electron transport layer can be formed.
- the light emitting device 190R and the light emitting device 190G are used between the pixel electrode 191 and the common layer 182, between the common layer 182 and the light emitting layer, between the light emitting layer and the common layer 184, and between the common layer 184 and the common electrode.
- a buffer layer may be provided in at least one of 115.
- As the buffer layer for example, at least one of a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer can be formed.
- the configuration of the light emitting device illustrated in FIGS. 4 to 6 is applied to the light emitting device 190B.
- the configuration of the light emitting device illustrated in FIGS. 4 to 6 may be applied to both the light emitting device 190R and the light emitting device 190G.
- the configuration of the light emitting device illustrated in FIGS. 4 to 6 is applied to one of the light emitting device 190R or the light emitting device 190G and the light emitting device 190B, one of the light emitting device 190R or the light emitting device 190G It is preferable that the light emitting device 190B and the light emitting device 190B have a common layer 182 and a common layer 184. At this time, it is preferable that the configurations of the light emitting devices illustrated in FIGS. 4 to 6 are applied to the configurations of the common layer 182 and the common layer 184.
- FIG. 2A shows a cross-sectional view of the display device 10C.
- the display device 10C differs from the display device 10A in that the red light emitting device 190R, the green light emitting device 190G, and the blue light emitting device 190B have a common layer 112 and a common layer 114.
- the red light emitting device 190R, the green light emitting device 190G, and the blue light emitting device 190B preferably have one or more layers (common layers) that are commonly used. As a result, the display device can be manufactured with a small number of manufacturing steps.
- FIG. 2A shows an example in which the light emitting device of each color has the common layer 112 and the common layer 114, but in the display device of one aspect of the present invention, the light emitting device of each color has only the common layer 112 or only the common layer 114. It may have a structure.
- the common layer 112 is located between the pixel electrode 191 and the light emitting layer of each color.
- the common layer 114 is located between the light emitting layer of each color and the common electrode 115.
- the common layer 112 and the common layer 114 may have a single-layer structure or a laminated structure, respectively.
- the common layer 112 for example, one or both of the hole injection layer and the hole transport layer can be formed.
- the common layer 114 for example, one or both of the electron injection layer and the electron transport layer can be formed.
- Each light emitting device is located between the pixel electrode 191 and the common layer 112, between the common layer 112 and the light emitting layer, between the light emitting layer and the common layer 114, and between the common layer 114 and the common electrode 115.
- a buffer layer may be provided in at least one of them.
- the buffer layer for example, at least one of a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer can be formed.
- FIG. 2B shows a cross-sectional view of the display device 10D.
- the display device 10D differs from the display device 10C in that it does not have the substrate 151 and the substrate 152, but has the substrate 153, the substrate 154, the adhesive layer 155, and the insulating layer 212.
- the substrate 153 and the insulating layer 212 are bonded to each other by an adhesive layer 155.
- the substrate 154 and the protective layer 195 are bonded to each other by an adhesive layer 142.
- the display device 10D has a configuration in which the insulating layer 212, the transistor 42, the light emitting device of each color, and the like formed on the manufactured substrate are transposed on the substrate 153. It is preferable that the substrate 153 and the substrate 154 each have flexibility. Thereby, the flexibility of the display device 10D can be increased. For example, it is preferable to use a resin for the substrate 153 and the substrate 154, respectively.
- the substrates 153 and 154 include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyacrylonitrile resins, acrylic resins, polyimide resins, polymethyl methacrylate resins, polycarbonate (PC) resins, and polyethers, respectively.
- polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyacrylonitrile resins, acrylic resins, polyimide resins, polymethyl methacrylate resins, polycarbonate (PC) resins, and polyethers, respectively.
- Sulfonate (PES) resin polyamide resin (nylon, aramid, etc.), polysiloxane resin, cycloolefin resin, polystyrene resin, polyamideimide resin, polyurethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, polypropylene resin, polytetrafluoroethylene (PTFE) resin, ABS resin, cellulose nanofibers and the like can be used.
- PES Sulfonate
- polyamide resin nylon, aramid, etc.
- polysiloxane resin cycloolefin resin
- polystyrene resin polyamideimide resin
- polyurethane resin polyvinyl chloride resin
- polyvinylidene chloride resin polypropylene resin
- PTFE polytetrafluoroethylene
- ABS resin cellulose nanofibers and the like
- a film having high optical isotropic properties may be used for the substrate included in the display device of the present embodiment.
- the film having high optical isotropic properties include a triacetyl cellulose (TAC, also referred to as cellulose triacetate) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer (COC) film, and an acrylic film.
- TAC triacetyl cellulose
- COP cycloolefin polymer
- COC cycloolefin copolymer
- FIG. 3 shows a cross-sectional view of the display device 10E.
- the display device 10E is different from the display device 10C in that it is a bottom emission type.
- the pixel electrode 191 has a function of transmitting visible light.
- the common electrode 115 preferably has a function of reflecting visible light.
- the transistor 42 is provided at a position that does not overlap with the light emitting region of the light emitting device.
- the substrate 152 is provided on the protective layer 195 via the adhesive layer 142 is shown, but the adhesive layer 142 and the substrate 152 may not be provided.
- [Light emitting device] 4A to 4C show an example of a light emitting device that can be used in the display device of this embodiment.
- the light emitting device shown in FIG. 4A has an anode 101, an EL layer 103, and a cathode 102.
- the EL layer 103 has a hole injection layer 121, a hole transport layer 122, a light emitting layer 123, an electron transport layer 124, and an electron injection layer 125 from the anode 101 side.
- the light emitting device may have an optical adjustment layer.
- the anode 101, the cathode 102, the hole injection layer 121, the hole transport layer 122, the light emitting layer 123, the electron transport layer 124, and the electron injection layer 125 may have a single layer structure or a laminated structure, respectively. Good.
- the hole transport layer 122 included in the light emitting device shown in FIGS. 4B and 4C has a two-layer structure consisting of a hole transport layer 122a on the hole injection layer 121 side and a hole transport layer 122b on the light emitting layer 123 side. is there.
- the electron transport layer 124 included in the light emitting device shown in FIG. 4C has a two-layer structure consisting of an electron transport layer 124a on the light emitting layer 123 side and an electron transport layer 124b on the electron injection layer 125 side.
- a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like can be appropriately used. Specific examples thereof include In—Sn oxide (also referred to as ITO), In—Si—Sn oxide (also referred to as ITSO), In—Zn oxide, and In—W—Zn oxide.
- ITO In—Sn oxide
- ITSO In—Si—Sn oxide
- Zn oxide In—W—Zn oxide.
- Ni Indium (In), Tin (Sn), Molybdenum (Mo), Tantal (Ta), Tungsten (W), Palladium (Pd), Gold (Au), Platinum (Pt), Silver (Ag), Ittrium (Y) ), Neodymium (Nd) and other metals, and alloys containing these in appropriate combinations can also be used.
- Other elements belonging to Group 1 or Group 2 of the Periodic Table of Elements eg, Lithium (Li), Cesium (Cs), Calcium (Ca), Strontium (Sr)), Europium (Eu), Ytterbium Rare earth metals such as (Yb) and alloys containing them in appropriate combinations, graphene and the like can be used.
- a reflective electrode and a semi-transmissive / semi-reflective electrode are used. Therefore, it can be formed in a single layer or laminated by using one or more desired conductive materials.
- a sputtering method or a vacuum vapor deposition method can be used for producing the electrodes.
- the hole injection layer 121 preferably has a first compound and a second compound.
- the first compound is an electron acceptor material (acceptor material) and has electron acceptability for the second compound.
- the second compound is a hole transporting material.
- Hole-transporting materials have higher hole-transporting properties than electrons.
- the highest occupied orbital level (HOMO level) of the second compound is preferably relatively low (deep). Specifically, the HOMO level of the second compound is preferably -5.7 eV or more and -5.4 eV or less. The relatively low HOMO level of the second compound facilitates the injection of holes into the hole transport layer 122, which is preferable.
- an organic compound having an electron-withdrawing group (particularly a halogen group such as a fluoro group or a cyano group) can be used.
- an organic acceptor such as a quinodimethane derivative, a chloranil derivative, or a hexaazatriphenylene derivative
- a quinodimethane derivative such as a chloranil derivative, or a hexaazatriphenylene derivative
- F 4 -TCNQ 7,7,8,8-(abbreviation: F 4 -TCNQ)
- chloranil 2,3,6,7,10,11 -Hexacyano-1,4,5,8,9,12-Hexaazatriphenylene
- HAT-CN 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane
- F6-TCNNQ 2- (7-dicyanomethylene-1,3,4,5,6,8,9,10-octafluoro-7H-pyrene-2-ylidene
- 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 (particularly a halogen group such as a fluoro group or a cyano group) is preferable because it has very high electron acceptability.
- Examples of the [3] radialene derivative having an electron-withdrawing group include ⁇ , ⁇ ', ⁇ ''-1,2,3-cyclopropanetriylidentris [4-cyano-2,3,5,6-tetrafluoro].
- Benzene acetonitrile ⁇ , ⁇ ', ⁇ ''-1,2,3-cyclopropanetriylidentris [2,6-dichloro-3,5-difluoro-4- (trifluoromethyl) benzene acetonitrile], ⁇ , Examples thereof include ⁇ ', ⁇ ''-1,2,3-cyclopropanetriylidentris [2,3,4,5,6-pentafluorobenzene acetonitrile].
- the second compound preferably has a hole-transporting skeleton.
- a hole transporting skeleton a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, and an anthracene skeleton, in which the HOMO level of the hole transporting material does not become too high (shallow), are preferable.
- the second compound preferably has at least one of a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, and an anthracene skeleton.
- the hole transporting material is an aromatic amine having a substituent containing a dibenzofuran ring or a dibenzothiophene ring, an aromatic monoamine having a naphthalene ring, or an aromatic in which a 9-fluorenyl group is bonded to the nitrogen of the amine via an arylene group. It may be a monoamine.
- the second compound has an N, N-bis (4-biphenyl) amino group because a long-life light emitting device can be produced.
- Examples of the second compound include N- (4-biphenyl) -6, N-diphenylbenzo [b] naphtho [1,2-d] furan-8-amine (abbreviation: BnfABP), N, N-bis. (4-Biphenyl) -6-phenylbenzo [b] naphtho [1,2-d] furan-8-amine (abbreviation: BBABnf), 4,4'-bis (6-phenylbenzo [b] naphtho [1, 2-d] furan-8-yl-4''-phenyltriphenylamine (abbreviation: BnfBB1BP), N, N-bis (4-biphenyl) benzo [b] naphtho [1,2-d] furan-6- Amin (abbreviation: BBABnf (6)), N, N-bis (4-biphenyl) benzo [b] naphtho [1,2-d] furan-8-amine (abbreviation: BBABnf (8)
- the hole transport layer 122 is a layer that transports the holes injected by the hole injection layer 121 to the light emitting layer 123.
- the hole transport layer 122 preferably has a third compound.
- the third compound is a hole transporting material.
- a hole-transporting material that can be used for the second compound can be used.
- the HOMO level of the third compound is preferably a value equal to or lower than the HOMO level of the second compound.
- the difference between the HOMO level of the third compound and the HOMO level of the second compound is preferably within 0.2 eV.
- the second compound and the third compound preferably have at least one of a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, and an anthracene skeleton, respectively.
- the second compound and the third compound have the same hole-transporting skeleton (particularly a dibenzofuran skeleton) because the hole injection becomes smooth.
- the second compound and the third compound are the same because the injection of holes becomes smooth.
- each layer constituting the hole transport layer 122 is a layer that transports holes to the light emitting layer 123.
- the hole transport layer 122a in FIGS. 4B and 4C can have the same configuration as the hole transport layer 122 in FIG. 4A.
- the hole transport layer 122b in FIGS. 4B and 4C (that is, the layer of the hole transport layer 122 located closest to the light emitting layer 123) preferably has a function as an electron block layer.
- the hole transport layer 122b preferably has a fourth compound.
- the fourth compound is a hole transporting material.
- a hole-transporting material that can be used for the second compound can be used.
- the HOMO level of the fourth compound is preferably lower than the HOMO level of the third compound.
- the difference between the HOMO level of the fourth compound and the HOMO level of the third compound is preferably within 0.2 eV.
- the second compound, the third compound, and the fourth compound preferably have at least one of a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, and an anthracene skeleton, respectively.
- the second compound, the third compound, and the fourth compound have the same hole-transporting skeleton (particularly a dibenzofuran skeleton) because the hole injection becomes smooth.
- the hole transporting materials used for the hole injection layer 121, the hole transport layer 122a, and the hole transport layer 122b have the above relationship, the hole injection into each layer is smoothly performed, and the drive voltage rises. And the hole in the light emitting layer 123 can be prevented from being insufficient.
- the light emitting layer is a layer containing a light emitting substance.
- the light emitting layer can have one or more kinds of light emitting substances.
- a substance exhibiting a luminescent color such as blue, purple, bluish purple, green, yellowish green, yellow, orange, and red is appropriately used.
- a substance that emits near infrared light can also be used.
- the light emitting layer may have one or more kinds of organic compounds (host material, assist material, etc.) in addition to the light emitting substance (guest material).
- organic compounds host material, assist material, etc.
- guest material the one or more kinds of organic compounds
- one or both of the hole transporting material and the electron transporting material described in this embodiment can be used.
- a bipolar material may be used as one or more kinds of organic compounds.
- the luminescent material that can be used for the light emitting layer is not particularly limited, and is a luminescent material that converts singlet excitation energy into light emission in the visible light region or near infrared light region, or triplet excitation energy in the visible light region or near infrared region.
- a luminescent substance that changes light emission in the light region can be used.
- the luminescent substance that converts the single-term excitation energy into luminescence examples include a fluorescent substance, for example, a pyrene derivative, an anthracene derivative, a triphenylene derivative, a fluorene derivative, a carbazole derivative, a dibenzothiophene derivative, a dibenzofuran derivative, a dibenzoquinoxaline derivative, and a quinoxalin derivative.
- a fluorescent substance for example, a pyrene derivative, an anthracene derivative, a triphenylene derivative, a fluorene derivative, a carbazole derivative, a dibenzothiophene derivative, a dibenzofuran derivative, a dibenzoquinoxaline derivative, and a quinoxalin derivative.
- the pyrene derivative is preferable because it has a high emission quantum yield.
- pyrene derivative examples include N, N'-bis (3-methylphenyl) -N, N'-bis [3- (9-phenyl-9H-fluoren-9-yl) phenyl] pyrene-1,6. -Diamine (abbreviation: 1,6 mM FLPAPrn), N, N'-diphenyl-N, N'-bis [4- (9-phenyl-9H-fluoren-9-yl) phenyl] pyrene-1,6-diamine (abbreviation) : 1,6FLPAPrn), N, N'-bis (dibenzofuran-2-yl) -N, N'-diphenylpyrene-1,6-diamine (abbreviation: 1,6FrAPrn), N, N'-bis (dibenzothiophene) -2-yl) -N, N'-diphenylpyrene-1,6-diamine (abbreviation: 1,6
- condensed aromatic diamine compounds typified by pyrenediamine compounds such as 1,6FLPAPrn, 1,6 mMFLPAPrn, and 1,6BnfAPrn-03 have high hole trapping properties and are excellent in luminous efficiency and reliability. preferable.
- Examples of the luminescent material that converts triplet excitation energy into luminescence include a phosphorescent luminescent material and a heat-activated delayed fluorescence (TADF) material exhibiting heat-activated delayed fluorescence.
- TADF heat-activated delayed fluorescence
- Examples of the phosphorescent substance include an organic metal complex having a 4H-triazole skeleton, a 1H-triazole skeleton, an imidazole skeleton, a pyrimidine skeleton, a pyrazine skeleton, or a pyridine skeleton (particularly an iridium complex), and a phenylpyridine derivative having an electron-withdrawing group.
- Examples thereof include an organic metal complex (particularly an iridium complex) as a ligand, a platinum complex, and a rare earth metal complex.
- Examples of the phosphorescent substance having a blue or green color and a peak wavelength of the emission spectrum of 450 nm or more and 570 nm or less include the following substances.
- Examples of the phosphorescent substance having a green or yellow color and a peak wavelength of 495 nm or more and 590 nm or less in the emission spectrum include the following substances.
- tris (4-methyl-6-phenylpyrimidinato) iridium (III) (abbreviation: [Ir (mppm) 3 ]
- tris (4-t-butyl-6-phenylpyrimidinato) iridium (III) (abbreviation: [Ir (mppm) 3 ])
- tris (4-t-butyl-6-phenylpyrimidinato) iridium (III) tris (4-t-butyl-6-phenylpyrimidinato) iridium (III).
- Examples of the phosphorescent substance having a yellow or red color and a peak wavelength of 570 nm or more and 750 nm or less in the emission spectrum include the following substances.
- the organic compound (host material, assist material, etc.) used for the light emitting layer one or a plurality of substances having an energy gap larger than the energy gap of the light emitting substance can be selected and used.
- organic compound used in combination with the fluorescent substance it is preferable to use an organic compound having a large energy level in the singlet excited state and a small energy level in the triplet excited state.
- organic compound that can be used in combination with the fluorescent substance examples include condensed polycyclic aromatic compounds such as anthracene derivative, tetracene derivative, phenanthrene derivative, pyrene derivative, chrysene derivative, and dibenzo [g, p] chrysene derivative.
- organic compound (host material) used in combination with the fluorescent luminescent material examples include 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole (abbreviation: PCzPA), 3 , 6-Diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole (abbreviation: DPCzPA), 3- [4- (1-naphthyl) -phenyl] -9-phenyl-9H -Carbazole (abbreviation: PCPN), 9,10-diphenylanthracene (abbreviation: DPAnth), N, N-diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl] -9H-carbazole-3-amine (Abbreviation: CzA1PA), 4- (10-phenyl-9-anthril) triphenylamine (abbreviation:
- an organic compound having a larger triplet excitation energy than the triplet excitation energy (energy difference between the base state and the triplet excited state) of the luminescent substance may be selected.
- the plurality of organic compounds are phosphorescent. It is preferably used by mixing with a luminescent substance (particularly an organic metal complex).
- ExTET Extra-Triplet Energy Transfer
- a compound that easily forms an excitation complex is preferable, and a compound that easily receives holes (hole transporting material) and a compound that easily receives electrons (electron transporting material) are combined. Is particularly preferred.
- hole transporting material the materials shown in the present embodiment can be used. With this configuration, high efficiency, low voltage drive, and long life of the light emitting device can be realized at the same time.
- the HOMO level of the hole-transporting material is equal to or higher than the HOMO level of the electron-transporting material.
- the LUMO level (lowest empty orbital level) of the hole transporting material is equal to or higher than the LUMO level of the electron transporting material.
- the LUMO and HOMO levels of the material can be derived from the electrochemical properties (reduction potential and oxidation potential) of the material as measured by cyclic voltammetry (CV) measurements.
- the emission spectrum of the hole transporting material, the emission spectrum of the electron transporting material, 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 the emission spectrum of each material. It can be confirmed by observing the phenomenon of shifting to the longer wavelength side (or having a new peak on the longer wavelength side) than the spectrum.
- the transient photoluminescence (PL) of the hole-transporting material, the transient PL of the electron-transporting material, 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 the transient of each material.
- transient PL may be read as transient electroluminescence (EL). That is, the formation of the excited complex can be confirmed by comparing the transient EL of the hole transporting material, the transient EL of the electron transporting material, and the transient EL of the mixed film thereof and observing the difference in the transient response. Can be done.
- EL transient electroluminescence
- Organic compounds that can be used in combination with phosphorescent substances include aromatic amines (compounds having an aromatic amine skeleton), carbazole derivatives (compounds having a carbazole skeleton), dibenzothiophene derivatives (thiophene derivatives), and dibenzofuran derivatives (furans). Derivatives), zinc and aluminum-based metal complexes, oxadiazole derivatives, triazole derivatives, benzoimidazole derivatives, quinoxalin derivatives, dibenzoquinoxalin derivatives, pyrimidine derivatives, triazine derivatives, pyridine derivatives, bipyridine derivatives, phenanthroline derivatives and the like.
- aromatic amine carbazole derivative, dibenzothiophene derivative, and dibenzofuran derivative, which are organic compounds having high hole transport properties, include the following substances.
- carbazole derivative examples include a bicarbazole derivative (for example, a 3,3'-bicarbazole derivative), an aromatic amine having a carbazolyl group, and the like.
- bicarbazole derivative for example, 3,3'-bicarbazole derivative
- PCCP 3,3'-bis (9-phenyl-9H-carbazole)
- 9,9'-bis (1,1'-biphenyl-4-yl) -3,3'-bi-9H-carbazole
- 9,9'-bis (1,1'-biphenyl-3-yl) -3,3'-bi- 9H-carbazole
- 9- (2-naphthyl) -9'-phenyl-9H, 9'H-3,3'-bicarbazole abbreviation: ⁇ NCCP
- aromatic amine having a carbazolyl group examples include PCBA1BP, N- (4-biphenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazole.
- PCBiF -3-Amin
- PCBBiF 4-phenyldiphenyl- (9-phenyl-9H-carbazole-3-yl) amine
- PCA1BP N, N'-bis (abbreviation: PCA1BP) 9-Phenylcarbazole-3-yl) -N, N'-diphenylbenzene-1,3-diamine
- PCA2B N, N', N''-triphenyl-N, N', N''- Tris (9-phenylcarbazole-3-yl) benzene-1,3,5-triamine
- PCA3B 9,9-dimethyl-N-phenyl-N- [4- (9-phenyl-9H-carbazole-) 3-Il) phenyl] Fluoren-2-amine
- PCBAF 4-phenyldiphenyl- (9-phenyl-9H-carbazole-3-yl) amine
- PCA1BP N, N'
- carbazole derivatives include 3- [4- (9-phenanthryl) -phenyl] -9-phenyl-9H-carbazole (abbreviation: PCPPn), PCPN, 1,3-bis (N-carbazolyl) benzene.
- PCPPn 3- [4- (9-phenanthryl) -phenyl] -9-phenyl-9H-carbazole
- PCPN 1,3-bis (N-carbazolyl) benzene.
- mCP 4,4'-di (N-carbazolyl) biphenyl
- CzTP 3,6-bis (3,5-diphenylphenyl) -9-phenylcarbazole
- TCPB 3,5-tris [4- (N-carbazolyl) phenyl] benzene
- CzPA 3,5-tris [4- (N-carbazolyl) phenyl] benzene
- thiophene derivative compound having a thiophene skeleton
- furan derivative compound having a furan skeleton
- aromatic amine examples include 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPB or ⁇ -NPD) and N, N'-bis (3).
- organic compounds having high hole transport properties include poly (N-vinylcarbazole) (abbreviation: PVK), poly (4-vinyltriphenylamine) (abbreviation: PVTPA), and poly [N- (4- ⁇ N'-). [4- (4-Diphenylamino) phenyl] phenyl-N'-phenylamino ⁇ phenyl) methacrylamide] (abbreviation: PTPDMA), poly [N, N'-bis (4-butylphenyl) -N, N'- A high molecular compound such as bis (phenyl) benzidine] (abbreviation: Poly-TPD) can also be used.
- PVK poly (N-vinylcarbazole)
- PVTPA poly (4-vinyltriphenylamine)
- PTPDMA poly [N- (4- ⁇ N'-).
- PTPDMA poly [N, N'-bis (4-butylphenyl) -N, N
- zinc and aluminum-based metal complexes that are organic compounds with high electron transport properties include tris (8-quinolinolato) aluminum (III) (abbreviation: Alq) and tris (4-methyl-8-quinolinolato) aluminum.
- III) abbreviation: Almq 3
- bis (10-hydroxybenzo [h] quinolinato) berylium (II) abbreviation: BeBq 2
- metal complexes having a quinoline skeleton or a benzoquinoline skeleton such as (III) (abbreviation: BAlq) and bis (8-quinolinolato) zinc (II) (abbreviation: Znq).
- oxazoles such as bis [2- (2-benzothazolyl) phenolato] zinc (II) (abbreviation: ZnPBO) and bis [2- (2-benzothiazolyl) phenolato] zinc (II) (abbreviation: ZnBTZ)
- ZnPBO bis [2- (2-benzothazolyl) phenolato] zinc
- ZnBTZ bis [2- (2-benzothiazolyl) phenolato] zinc
- oxadiazole derivative triazole derivative, benzimidazole derivative, quinoxalin derivative, dibenzoquinoxalin derivative, and phenylanthrolin derivative, which are organic compounds having high electron transport properties, are 2- (4-biphenylyl) -5- (4-).
- tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5- (p-tert-butylphenyl) -1,3,4-oxadiazol-2- Il] benzene (abbreviation: OXD-7), 9- [4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenyl] -9H-carbazole (abbreviation: CO11), 3-( 4-Biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazol (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethyl) Phenyl) -5- (4-biphenylyl) -1,2,4-triazol (abbreviation: p-EtTAZ), 2- ⁇ 4- [9,10-di (naphthalen
- heterocyclic compound having a diazine skeleton the heterocyclic compound having a triazine skeleton, and the heterocyclic compound having a pyridine skeleton, which are organic compounds having high electron transport properties, are 4,6-bis [3- (phenanthrene-).
- organic compounds having high electron transport properties examples include poly (2,5-pyridinediyl) (abbreviation: PPy) and poly [(9,9-dihexylfluorene-2,7-diyl) -co- (pyridine-3,5). -Diyl)] (abbreviation: PF-Py), poly [(9,9-dioctylfluorene-2,7-diyl) -co- (2,2'-bipyridine-6,6'-diyl)] (abbreviation: Polymer compounds such as PF-BPy) can also be used.
- PPy poly (2,5-pyridinediyl)
- PF-Py poly [(9,9-dihexylfluorene-2,7-diyl) -co- (pyridine-3,5).
- PF-Py poly [(9,9-dioctylfluorene-2,7-di
- the TADF material S 1 level position small difference (singlet energy level of excited state) and T 1 level position and (energy level of a triplet excited state), the triplet excitation energy by reverse intersystem crossing It is a material having a function of converting energy into singlet excitation energy. 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.
- the conditions for thermally activated delayed fluorescence is efficiently obtained, the energy difference between the S 1 level and T 1 level position is 0eV than 0.2eV or less, preferably not more than 0.1eV than 0eV. Further, the delayed fluorescence in the TADF material refers to light emission having a spectrum similar to that of normal fluorescence but having a remarkably long life. Its life is 10-6 seconds or longer, preferably 10-3 seconds or longer.
- An excited complex that forms an excited state with two types of substances has an extremely small difference between the S 1 level and the T 1 level, and can be used as a TADF material capable of converting triplet excitation energy into singlet excitation energy. Has a function.
- a phosphorescence spectrum observed at a low temperature may be used as an index of the T 1 level.
- the TADF material drawing a tangential line at the short wavelength side of the hem of the fluorescence spectrum, the energy of the wavelength of the extrapolation and S 1 levels, drawing a tangential line at the short wavelength side of the hem of the phosphorescence spectrum, its extrapolation
- the difference between S 1 and T 1 is preferably 0.3 eV or less, and more preferably 0.2 eV or less.
- the TADF material may be used as a guest material or as a host material.
- Examples of the TADF material include fullerenes and derivatives thereof, acridine derivatives such as proflavine, and eosin.
- Examples thereof include metal-containing porphyrins containing magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), palladium (Pd) and the like.
- Examples of the metal-containing porphyrin include protoporphyrin-tin fluoride complex (abbreviation: SnF 2 (Proto IX)), mesoporphyrin-tin fluoride complex (abbreviation: SnF 2 (Meso IX)), and hematoporphyrin-tin fluoride.
- the heterocyclic compound has a ⁇ -electron excess type heteroaromatic ring and a ⁇ -electron deficiency type heterocyclic ring, both electron transportability and hole transportability are high, which is preferable.
- an aromatic ring to which an electron-withdrawing group such as a cyano group is bonded may be used.
- a ⁇ -electron-deficient skeleton can be used instead of the ⁇ -electron-deficient heteroaromatic ring.
- a ⁇ -electron-rich backbone can be used instead of the ⁇ -electron-rich heteroaromatic ring.
- 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 electron acceptability and good reliability.
- the acridine skeleton, the phenoxazine skeleton, the phenothiazine skeleton, the furan skeleton, the thiophene skeleton, and the pyrrole skeleton are stable and have good reliability. It is preferable to have.
- a dibenzofuran skeleton, a dibenzothiophene skeleton, an indole skeleton, a carbazole skeleton, an indolocarbazole skeleton, a bicarbazole skeleton, and a 3- (9-phenyl-9H-carbazole-3-yl) -9H-carbazole skeleton are preferable.
- both the donor property of the ⁇ -electron-rich heteroaromatic ring and the acceptability of the ⁇ -electron-deficient heteroaromatic ring become stronger.
- an aromatic amine skeleton, a phenazine skeleton, or the like can be used.
- An aromatic ring having 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 TADF material When a TADF material is used as the luminescent substance, it can also be used in combination with other organic compounds. In particular, it can be combined with the above-mentioned host materials (hole transporting material, electron transporting material).
- S 1 level of the host material is preferably higher than S 1 level of TADF material.
- T 1 level of the host material is preferably higher than the T 1 level of the TADF material.
- the TADF material may be used as the host material and the fluorescent substance may be used as the guest material.
- the triplet excitation energy generated by the TADF material is converted into singlet excitation energy by the inverse intersystem crossing, and the energy is further transferred to the luminescent material to improve the luminescence efficiency of the luminescent device. be able to.
- the TADF material functions as an energy donor, and the luminescent material functions as an energy acceptor. Therefore, using a TADF material as the host material is very effective when using a fluorescent substance as the guest material.
- S 1 level of TADF material is preferably higher than S 1 level of fluorescence emission substance.
- the T 1 level of the TADF material is preferably higher than the S 1 level of the fluorescent substance. Therefore, T 1 level of the TADF material is preferably higher than the T 1 level of the fluorescence 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 luminescent group (skeleton that causes light emission) of the fluorescent substance.
- a protecting group a substituent having no ⁇ bond is preferable, a saturated hydrocarbon is preferable, and specifically, an alkyl group having 3 or more and 10 or less carbon atoms, or a substituted or unsubstituted cyclo having 3 or more and 10 carbon atoms or less.
- the luminescent group refers to an atomic group (skeleton) that causes light emission in a fluorescent luminescent substance.
- the luminescent group 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.
- the electron transport layer 124 is a layer that transports the electrons injected from the cathode 102 to the light emitting layer 123.
- the electron transport layer 124 has a third organic compound and a first substance.
- the third organic compound is an electron transporting material. Electron-transporting materials have higher electron-transporting properties than holes.
- the third organic compound preferably has a maximum occupied orbital level (HOMO level) of ⁇ 6.0 eV or higher.
- the third organic compound preferably has an electron mobility of 1 ⁇ 10-7 cm 2 / Vs or more and 1 ⁇ 10-5 cm 2 / Vs or less when the square root of the electric field strength [V / cm] is 600. It is more preferably 1 ⁇ 10 -7 cm 2 / Vs or more and 5 ⁇ 10 -5 cm 2 / Vs or less.
- the square root of the electric field strength [V / cm] of the third organic compound is smaller than the electron mobility at 600 in the square root of the electric field strength [V / cm] of the host material of the light emitting layer 123. ..
- the amount of electrons injected into the light emitting layer 123 can be controlled, and the light emitting layer 123 can be prevented from being in a state of excess electrons.
- the third organic compound preferably has an anthracene skeleton, and more preferably has an anthracene skeleton and a heterocyclic skeleton.
- a nitrogen-containing 5-membered ring skeleton is preferable.
- the nitrogen-containing 5-membered ring skeleton it is particularly preferable to have a nitrogen-containing 5-membered ring skeleton containing two complex atoms in the ring, such as a pyrazole ring, an imidazole ring, an oxazole ring, and a thiazole ring.
- the electron transporting material that can be used as the host material and the substance listed as the material that can be used as the host material in combination with the fluorescent light emitting substance can be used for the electron transporting layer 124. it can.
- Examples of the third organic compound include 2- ⁇ 4- [9,10-di (naphthalen-2-yl) -2-anthril] phenyl ⁇ -1-phenyl-1H-benzoimidazole (abbreviation: ZADN), 9- (1-naphthyl) -10- [4- (2-naphthyl) phenyl] anthracene (abbreviation: ⁇ N- ⁇ NPAnth), 9- [4- (10-phenyl-9-anthracenyl) phenyl] -9H-carbazole ( Abbreviation: CzPA), 7- [4- (10-phenyl-9-anthril) phenyl] -7H-dibenzo [c, g] carbazole (abbreviation: cgDBCzPA) and the like.
- ZADN 9- (1-naphthyl) -10- [4- (2-naphthyl) phen
- an electron transporting material that can be used for the light emitting layer an organic compound (host material) that can be used in combination with a fluorescent light emitting substance, and the like can be used.
- the first substance is a metal, metal salt, metal oxide, or organometallic salt.
- the metal examples include alkali metals, alkaline earth metals, and rare earth metals. Specific examples thereof include Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.
- the metal salt examples include a halide of the metal and a carbonate of the metal.
- LiF, NaF, KF, RbF, CsF, MgF 2 , CaF 2 , SrF 2 , BaF 2 LiCl, NaCl, KCl, RbCl, CsCl, MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , Li.
- Examples thereof include 2 CO 3 and Cs 2 CO 3 .
- metal oxide examples include the oxides of the above metals. Specific examples thereof include Li 2 O, Na 2 O, Cs 2 O, MgO, and CaO.
- organometallic salt examples include an organometallic complex.
- the first substance is preferably an organometallic complex having an alkali metal or an alkaline earth metal.
- the first substance is preferably an organometallic complex having a ligand having nitrogen and oxygen and an alkali metal or an alkaline earth metal.
- the first substance is preferably an organometallic complex having a quinolinol ligand and an alkali metal or alkaline earth metal.
- organic metal complex examples include 8- (quinolinolato) lithium (abbreviation: Liq), 8- (quinolinolato) sodium (abbreviation: Naq), 8- (quinolinolato) potassium (abbreviation: Kq), and (8-quinolinolato) magnesium ( Abbreviation: Mgq 2 ), (8-kinokirinorato) zinc (abbreviation: Znq 2 ) and the like can be mentioned.
- Liq is particularly preferable.
- the electron transport layer 124 may have an electron transport layer 124a on the light emitting layer 123 side and an electron transport layer 124b on the cathode 102 side. It is preferable that the electron transport layer 124a and the electron transport layer 124b have different concentration ratios of the third organic compound and the first substance. For example, the electron transport layer 124a preferably has a higher concentration of the first substance than the electron transport layer 124b.
- the electron injection layer 125 is a layer that enhances the efficiency of electron injection from the cathode 102.
- the difference between the work function value of the material of the cathode 102 and the LUMO level value of the material used for the electron injection layer 125 is preferably small (within 0.5 eV).
- the electron injection layer 125 includes lithium, cesium, lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF 2 ), 8- (quinolinolato) lithium (abbreviation: Liq), 2- (2- (2-). Pyridyl) phenolatrithium (abbreviation: LiPP), 2- (2-pyridyl) -3-pyridinolatolithium (abbreviation: LiPPy), 4-phenyl-2- (2-pyridyl) phenolatrithium (abbreviation: LiPPP), Alkali metals such as lithium oxide (LiO x ), cesium carbonate and the like, alkaline earth metals, or compounds thereof can be used.
- rare earth metal compounds such as erbium fluoride (ErF 3 ) can be used.
- an electlide may be used for the electron injection layer.
- the electride include a substance in which a high concentration of electrons is added to a mixed oxide of calcium and aluminum. It should be noted that the substance constituting the electron transport layer described above can also be used.
- a composite material containing an electron transporting material and a donor material may be used for the electron injection layer.
- a composite material is excellent in electron injection property and electron transport property because electrons are generated in the organic compound by the electron donor.
- the organic compound is preferably a material excellent in transporting generated electrons, and specifically, for example, the above-mentioned electron transporting material (metal complex, complex aromatic compound, etc.) can be used. ..
- the electron donor may be any substance that exhibits electron donating property to the organic compound. Specifically, alkali metals, alkaline earth metals and rare earth metals are preferable, and lithium, cesium, magnesium, calcium, erbium, ytterbium and the like can be mentioned.
- alkali metal oxides and alkaline earth metal oxides are preferable, and lithium oxides, calcium oxides, barium oxides and the like can be mentioned.
- a Lewis base such as magnesium oxide can also be used.
- an organic compound such as tetrathiafulvalene (abbreviation: TTF) can also be used.
- a vacuum process such as a vapor deposition method or a solution process such as a spin coating method or an inkjet method can be used to fabricate the light emitting device according to one aspect of the present invention.
- a physical vapor deposition method such as a sputtering method, an ion plating method, an ion beam vapor deposition method, a molecular beam deposition method, or a vacuum vapor deposition method, or a chemical vapor deposition method (CVD method) is used.
- PVD method physical vapor deposition method
- CVD method chemical vapor deposition method
- a vapor deposition method vacuum vapor deposition method, etc.
- a coating method dip coating method, die coating
- bar coating method spin coating method, spray coating method, etc.
- printing method inkprint method, screen (stencil printing) method, offset (flat printing) method, flexo (letter printing) method, gravure method, microcontact method, etc.
- Etc. can be formed.
- the material of the functional layer constituting the light emitting device is not limited to the above-mentioned materials.
- a high molecular compound oligoform, dendrimer, polymer, etc.
- a medium molecular compound compound in the intermediate region between low molecular weight and high molecular weight: molecular weight 400 to 4000
- an inorganic compound quantum dot material, etc.
- a colloidal quantum dot material an alloy type quantum dot material, a core / shell type quantum dot material, a core type quantum dot material, or the like can be used.
- Light emission model in light emitting device A light emitting model in a light emitting device that can be used in the display device of the present embodiment will be described.
- a light emitting model of the light emitting device will be described using the hole transport layer 122, the light emitting layer 123, and the electron transport layer 124 shown in FIG. 4A.
- the light emitting device is not limited to the configuration shown in FIG. 4A, and the light emitting model can be applied to other configurations.
- a light emitting region 123-1 is formed in a local region in the light emitting layer 123 as shown in FIG. 5A.
- the width of the light emitting region 123-1 in the light emitting layer 123 is narrow. Therefore, in the local region of the light emitting layer 123, the electrons (e ⁇ ) and the holes (h + ) are intensively recombined, and the deterioration is promoted. Further, the electrons that could not be recombined in the light emitting layer 123 may pass through the light emitting layer 123, so that the life or the luminous efficiency may be lowered.
- the width of the light emitting region 123-1 in the light emitting layer 123 can be widened by lowering the electron transporting property in the electron transport layer 124 (FIGS. 5B and 5C). ..
- the recombination region of the electron and the ball in the light emitting layer 123 can be dispersed. Therefore, it is possible to provide a light emitting device having a long life and good luminous efficiency.
- the recombination region may extend to the electron transport layer 124 side at the initial stage of driving.
- the recombination region in the electron transport layer 124 is shown as region 124-1.
- the hole injection barrier is small at the initial stage of driving, and the electron transporting property of the electron transporting layer 124 is relatively low, so that the light emitting region 123-1 (that is, that is) A recombination region) may be formed in the entire light emitting layer 123, and a recombination region may also be formed in the electron transport layer 124.
- the HOMO level of the third organic compound contained in the electron transport layer 124 is relatively high at ⁇ 6.0 eV or higher, some of the holes reach the electron transport layer 124, and the electron transport layer 124 also reappears. Bonding may occur. This phenomenon may also occur when the difference in HOMO level between the host material (or assist material) contained in the light emitting layer 123 and the third organic compound is within 0.2 eV.
- the carrier balance changes as the drive time elapses, and recombination at the electron transport layer 124 is less likely to occur.
- the energy of the recombined carriers can be effectively contributed to light emission. Therefore, the brightness can be increased as compared with the initial stage of driving.
- the so-called initial deterioration it is possible to provide a light emitting device having a small initial deterioration and a long driving life.
- the above-mentioned light emitting device may be referred to as a Recombination-Site Tailoring Injection structure (ReSTI structure).
- the thick solid line and the thick alternate long and short dash line are the deterioration curves of the standardized luminance of the light emitting device of the present embodiment
- the thick broken line is the deterioration curve of the normalized luminance of the light emitting device for comparison.
- the light emitting device of the present embodiment and the light emitting device for comparison have different slopes of the deterioration curve of the normalized luminance. Specifically, the slope ⁇ 2 of the deterioration curve of the light emitting device of the present embodiment is smaller than the slope ⁇ 1 of the deterioration curve of the light emitting device for comparison.
- the light emitting device of one aspect of the present invention may have a maximum value in the brightness deterioration curve obtained by the drive test under the condition of constant current density (thick solid line). That is, the light emitting device of one aspect of the present invention may exhibit a behavior in which the brightness increases with the passage of time. This behavior can offset the rapid deterioration at the initial stage of driving (so-called initial deterioration).
- the light emitting device of one aspect of the present invention is not limited to the above, and does not have a maximum value of brightness as shown by a thick alternate long and short dash line in FIG. 5D, in other words, does not cause an increase in brightness.
- the slope of the deterioration curve can be reduced. Therefore, by configuring the light emitting device to exhibit the behavior, the initial deterioration of the light emitting device can be reduced and the drive life can be made very long.
- a light emitting device having a portion where the derivative of the deterioration curve becomes 0 can be rephrased as the light emitting device of one aspect of the present invention.
- the electron transport layer 124 preferably has a portion in which the mixing ratio (concentration) of the third organic compound and the first substance is different in the thickness direction. Specifically, it is preferable to have a portion in which the mixing ratio (concentration) of the electron-transporting material and the metal, metal salt, metal oxide, or organometallic salt is different.
- the concentration of the first substance in the electron transport layer 124 can be inferred from the amount of atoms and molecules detected by time-of-flight secondary ion mass spectrometry (ToF-SIMS: Time-of-flight second day mass spectrometry).
- ToF-SIMS Time-of-flight second day mass spectrometry
- the magnitude of the value detected by the ToF-SIMS analysis corresponds to the magnitude of the abundance of the atom or molecule of interest. Therefore, the magnitude of the mixing ratio can be estimated by comparing the detected amounts of the electron-transporting material and the organometallic complex.
- the content of the first substance in the electron transport layer 124 is preferably smaller on the cathode 102 side than on the anode 101 side. That is, it is preferable that the electron transport layer 124 is formed so that the concentration of the first substance increases from the cathode 102 side toward the anode 101 side. That is, the electron transport layer 124 has a portion having a lower concentration of the third organic compound on the light emitting layer 123 side than a portion having a higher concentration of the third organic compound. In other words, the electron transport layer 124 has a portion having a higher concentration of the first substance on the light emitting layer 123 side than a portion having a lower concentration of the first substance.
- the electron mobility in the portion where the concentration of the third organic compound is high is 1 ⁇ 10 -7 when the square root of the electric field strength [V / cm] is 600. It is preferably cm 2 / Vs or more and 5 ⁇ 10 -5 cm 2 / Vs or less.
- the content (concentration) of the first substance in the electron transport layer 124 can be configured as shown in FIGS. 6A to 6D.
- 6A and 6B show the case where there is no clear boundary in the electron transport layer 124
- FIGS. 6C and 6D show the case where there is a clear boundary in the electron transport layer 124.
- the concentration of the third organic compound and the first substance changes continuously as shown in FIGS. 6A and 6B. Further, when there is a clear boundary in the electron transport layer 124, the concentration of the third organic compound and the first substance changes stepwise as shown in FIGS. 6C and 6D.
- the electron transport layer 124 is composed of a plurality of layers.
- FIG. 6C shows a case where the electron transport layer 124 has a two-layer laminated structure
- FIG. 6D shows a case where the electron transport layer 124 has a three-layer laminated structure.
- the broken line represents the boundary region of a plurality of layers.
- the change in the carrier balance in the light emitting device of one aspect of the present invention is brought about by the change in the electron mobility of the electron transport layer 124.
- the electron transport layer 124 has a region having a high concentration of the first substance between the region having a low concentration of the first substance and the light emitting layer 123. That is, the region where the concentration of the first substance is low is located closer to the cathode 102 than the region where the concentration is high.
- the light emitting device of one aspect of the present invention having the above configuration has a very long life.
- the time until the brightness reaches 95% also referred to as LT95
- LT95 95%
- FIG. 7 shows a perspective view of the display device 100A
- FIG. 8A shows a cross-sectional view of the display device 100A.
- the display device 100A has a configuration in which the substrate 152 and the substrate 151 are bonded together.
- the substrate 152 is clearly indicated by a broken line.
- the display device 100A includes a display unit 162, a circuit 164, wiring 165, and the like.
- FIG. 7 shows an example in which an IC (integrated circuit) 173 and an FPC 172 are mounted on the display device 100A. Therefore, the configuration shown in FIG. 7 can be said to be a display module having a display device 100A, an IC, and an FPC.
- a scanning line drive circuit can be used.
- the wiring 165 has a function of supplying signals and electric power to the display unit 162 and the circuit 164.
- the signal and power are input to the wiring 165 from the outside via the FPC 172 or from the IC 173.
- FIG. 7 shows an example in which the IC173 is provided on the substrate 151 by the COG (Chip On Glass) method, the COF (Chip on Film) method, or the like.
- the IC 173 an IC having, for example, a scanning line drive circuit or a signal line drive circuit can be applied.
- the display device 100A and the display module may be configured without an IC. Further, the IC may be mounted on the FPC by the COF method or the like.
- FIG. 8A shows an example of a cross section of the display device 100A when a part of the region including the FPC 172, a part of the circuit 164, a part of the display unit 162, and a part of the region including the end are cut. Shown.
- the display device 100A shown in FIG. 8A has a transistor 201, a transistor 205, a light emitting device 190R, a light emitting device 190G, a light emitting device 190B, and the like between the substrate 151 and the substrate 152.
- the protective layer 195 and the substrate 152 are adhered to each other via the adhesive layer 142.
- a solid sealing structure, a hollow sealing structure, or the like can be applied to the sealing of the light emitting device 190.
- the space 143 surrounded by the substrate 152, the adhesive layer 142, and the substrate 151 is filled with an inert gas (nitrogen, argon, etc.), and a hollow sealing structure is applied.
- the adhesive layer 142 may be provided so as to overlap with the light emitting device 190.
- the space 143 surrounded by the substrate 152, the adhesive layer 142, and the substrate 151 may be filled with a resin different from that of the adhesive layer 142.
- the light emitting device 190R has a laminated structure in which the pixel electrode 191 and the optical adjustment layer 199R, the common layer 112, the light emitting layer 193R, the common layer 114, and the common electrode 115 are laminated in this order from the insulating layer 214 side.
- the light emitting device 190G has a laminated structure in which the pixel electrode 191 and the optical adjustment layer 199G, the common layer 112, the light emitting layer 193G, the common layer 114, and the common electrode 115 are laminated in this order from the insulating layer 214 side.
- the light emitting device 190B has a laminated structure in which the pixel electrode 191 and the optical adjustment layer 199B, the common layer 112, the light emitting layer 193B, the common layer 114, and the common electrode 115 are laminated in this order from the insulating layer 214 side.
- the pixel electrode 191 is connected to the conductive layer 222b of the transistor 205 via an opening provided in the insulating layer 214.
- the end of the pixel electrode 191 is covered with a partition wall 216.
- the pixel electrode 191 contains a material that reflects visible light
- the common electrode 115 contains a material that transmits visible light.
- the light emitted by the light emitting device 190 is emitted to the substrate 152 side. It is preferable to use a material having high transparency to visible light for the substrate 152.
- Both the transistor 201 and the transistor 205 are formed on the substrate 151. These transistors can be manufactured by the same material and the same process.
- An insulating layer 211, an insulating layer 213, an insulating layer 215, and an insulating layer 214 are provided on the substrate 151 in this order.
- a part of the insulating layer 211 functions as a gate insulating layer of each transistor.
- a part of the insulating layer 213 functions as a gate insulating layer of each transistor.
- the insulating layer 215 is provided so as to cover the transistor.
- the insulating layer 214 is provided so as to cover the transistor and has a function as a flattening layer.
- the number of gate insulating layers and the number of insulating layers covering the transistors are not limited, and may be a single layer or two or more layers, respectively.
- the insulating layer can function as a barrier layer. With such a configuration, it is possible to effectively suppress the diffusion of impurities from the outside into the transistor, and it is possible to improve the reliability of the display device.
- an inorganic insulating film as the insulating layer 211, the insulating layer 213, and the insulating layer 215, respectively.
- an inorganic insulating film for example, a silicon nitride film, a silicon nitride film, a silicon oxide film, a silicon nitride film, an aluminum oxide film, an aluminum nitride film, or the like can be used.
- a hafnium oxide film, an yttrium oxide film, a zirconium oxide film, a gallium oxide film, a tantalum oxide film, a magnesium oxide film, a lanthanum oxide film, a cerium oxide film, a neodymium oxide film and the like may be used. Further, two or more of the above-mentioned insulating films may be laminated and used.
- the organic insulating film often has a lower barrier property than the inorganic insulating film. Therefore, the organic insulating film preferably has an opening near the end of the display device 100A. As a result, it is possible to prevent impurities from entering from the end of the display device 100A via the organic insulating film.
- the organic insulating film may be formed so that the end portion of the organic insulating film is inside the end portion of the display device 100A so that the organic insulating film is not exposed at the end portion of the display device 100A.
- An organic insulating film is suitable for the insulating layer 214 that functions as a flattening layer.
- the material that can be used for the organic insulating film include acrylic resin, polyimide resin, epoxy resin, polyamide resin, polyimideamide resin, siloxane resin, benzocyclobutene resin, phenol resin, and precursors of these resins. ..
- an opening is formed in the insulating layer 214.
- an organic insulating film is used for the insulating layer 214, it is possible to prevent impurities from entering the display unit 162 from the outside through the insulating layer 214. Therefore, the reliability of the display device 100A can be improved.
- the transistors 201 and 205 are a conductive layer 221 that functions as a gate, an insulating layer 211 that functions as a gate insulating layer, a conductive layer 222a and a conductive layer 222b that function as sources and drains, a semiconductor layer 231 and an insulation that functions as a gate insulating layer. It has a layer 213 and a conductive layer 223 that functions as a gate. Here, the same hatching pattern is attached to a plurality of layers obtained by processing the same conductive film.
- the insulating layer 211 is located between the conductive layer 221 and the semiconductor layer 231.
- the insulating layer 213 is located between the conductive layer 223 and the semiconductor layer 231.
- the structure of the transistor included in the light emitting device of the present embodiment is not particularly limited.
- a planar type transistor, a stagger type transistor, an inverted stagger type transistor and the like can be used.
- either a top gate type or a bottom gate type transistor structure may be used.
- gates may be provided above and below the semiconductor layer on which the channel is formed.
- a configuration in which a semiconductor layer on which a channel is formed is sandwiched between two gates is applied to the transistor 201 and the transistor 205.
- the transistor may be driven by connecting two gates and supplying the same signal to them.
- the threshold voltage of the transistor may be controlled by giving one of the two gates a potential for controlling the threshold voltage and giving the other a potential for driving.
- the crystallinity of the semiconductor material used for the transistor is also not particularly limited, and either an amorphous semiconductor or a semiconductor having crystallinity (microcrystalline semiconductor, polycrystalline semiconductor, single crystal semiconductor, or 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.
- the semiconductor layer of the transistor preferably has a metal oxide (also referred to as an oxide semiconductor). That is, it is preferable that the display device of the present embodiment uses a transistor (hereinafter, OS transistor) in which a metal oxide is used in the channel forming region.
- OS transistor a transistor
- the semiconductor layer of the transistor may have silicon. Examples of silicon include amorphous silicon and crystalline silicon (low temperature polysilicon, single crystal silicon, etc.).
- the semiconductor layers include, for example, indium and M (M is gallium, aluminum, silicon, boron, ittrium, tin, copper, vanadium, beryllium, titanium, iron, nickel, germanium, zirconium, molybdenum, lantern, cerium, neodymium, etc. It is preferable to have one or more selected from hafnium, tantalum, tungsten, and gallium) and zinc.
- M is preferably one or more selected from aluminum, gallium, yttrium, and tin.
- an oxide containing indium (In), gallium (Ga), and zinc (Zn) also referred to as IGZO
- IGZO oxide containing indium (In), gallium (Ga), and zinc (Zn)
- the atomic number ratio of In in the In-M-Zn oxide is preferably equal to or higher than the atomic number ratio of M.
- the atomic number ratio of In is 4
- the atomic number ratio of Ga is 1 or more and 3 or less.
- the case where the atomic number ratio of Zn is 2 or more and 4 or less is included.
- the atomic number ratio of Ga is larger than 0.1 when the atomic number ratio of In is 5. This includes cases where the number of atoms is 2 or less and the atomic number ratio of Zn is 5 or more and 7 or less.
- the atomic number ratio of Ga is larger than 0.1 when the atomic number ratio of In is 1. This includes the case where it is 2 or less and the atomic number ratio of Zn is larger than 0.1 and 2 or less.
- the transistor included in the circuit 164 and the transistor included in the display unit 162 may have the same structure or different structures.
- the structures of the plurality of transistors included in the circuit 164 may all be the same, or may have two or more types.
- the structures of the plurality of transistors included in the display unit 162 may all be the same, or may be two or more types.
- a connecting portion 204 is provided in a region of the substrate 151 where the substrates 152 do not overlap.
- the wiring 165 is electrically connected to the FPC 172 via the conductive layer 166 and the connection layer 242.
- the conductive layer 166 is a laminated structure of a conductive film obtained by processing the same conductive film as the pixel electrode 191 and a conductive film obtained by processing the same conductive film as the optical adjustment layer. Shown.
- the conductive layer 166 is exposed on the upper surface of the connecting portion 204.
- the connection portion 204 and the FPC 172 can be electrically connected via the connection layer 242.
- a light-shielding layer BM on the surface of the substrate 152 on the substrate 151 side.
- various optical members can be arranged on the outside of the substrate 152.
- the optical member include a polarizing plate, a retardation plate, a light diffusing layer (diffusing film, etc.), an antireflection layer, a light collecting film, and the like.
- an antistatic film for suppressing the adhesion of dust, a water-repellent film for preventing the adhesion of dirt, a hard coat film for suppressing the occurrence of scratches due to use, a shock absorbing layer, etc. are arranged on the outside of the substrate 152. You may.
- the protective layer 195 that covers the light emitting device 190 By providing the protective layer 195 that covers the light emitting device 190, it is possible to suppress the entry of impurities such as water into the light emitting device 190 and improve the reliability of the light emitting device 190.
- the insulating layer 215 and the protective layer 195 are in contact with each other through the opening of the insulating layer 214.
- the inorganic insulating film of the insulating layer 215 and the inorganic insulating film of the protective layer 195 are in contact with each other.
- FIG. 8B shows an example in which the protective layer 195 has a three-layer structure.
- the protective layer 195 has an inorganic insulating layer 195a on the common electrode 115, an organic insulating layer 195b on the inorganic insulating layer 195a, and an inorganic insulating layer 195c on the organic insulating layer 195b.
- the end of the inorganic insulating layer 195a and the end of the inorganic insulating layer 195c extend outward from the end of the organic insulating layer 195b and are in contact with each other. Then, the inorganic insulating layer 195a comes into contact with the insulating layer 215 (inorganic insulating layer) through the opening of the insulating layer 214 (organic insulating layer). As a result, the light emitting device 190 can be surrounded by the insulating layer 215 and the protective layer 195, so that the reliability of the light emitting device 190 can be improved.
- the protective layer 195 may have a laminated structure of an organic insulating film and an inorganic insulating film. At this time, it is preferable that the end portion of the inorganic insulating film extends outward from the end portion of the organic insulating film.
- Glass, quartz, ceramic, sapphire, resin and the like can be used for the substrate 151 and the substrate 152, respectively.
- the flexibility of the display device can be increased.
- various curable adhesives such as a photocurable adhesive such as an ultraviolet curable type, a reaction curable type adhesive, a thermosetting type adhesive, and an anaerobic type adhesive can be used.
- these adhesives include epoxy resin, acrylic resin, silicone resin, phenol resin, polyimide resin, imide resin, PVC (polyvinyl chloride) resin, PVB (polyvinyl butyral) resin, EVA (ethylene vinyl acetate) resin and the like.
- a material having low moisture permeability such as epoxy resin is preferable.
- a two-component mixed type resin may be used.
- connection layer 242 an anisotropic conductive film (ACF: Anisotropic Conductive Film), an anisotropic conductive paste (ACP: Anisotropic Connective Paste), or the like can be used.
- ACF Anisotropic Conductive Film
- ACP Anisotropic Connective Paste
- the light emitting device 190 includes a top emission type, a bottom emission type, and a dual emission type.
- a conductive film that transmits visible light is used for the electrode on the side that extracts light. Further, it is preferable to use a conductive film that reflects visible light for the electrode on the side that does not take out light.
- the light emitting device 190 has at least a light emitting layer 193.
- the light emitting device 190 includes a substance having high hole injecting property, a substance having high hole transporting property, a hole blocking material, a substance having high electron transporting property, a substance having high electron injecting property, or a bipolar. It may further have a layer containing a sex substance (a substance having high electron transport property and hole transport property) and the like.
- the common layer 112 preferably has one or both of a hole injection layer and a hole transport layer.
- the common layer 114 preferably has one or both of an electron transport layer and an electron injection layer.
- the preferred configuration of the light emitting device 190 is as described above (FIGS. 4 to 6).
- Either a low molecular weight compound or a high molecular weight compound can be used for the common layer 112, the light emitting layer 193, and the common layer 114, and an inorganic compound may be contained.
- the layers constituting the common layer 112, the light emitting layer 193, and the common layer 114 can be formed by a method such as a vapor deposition method (including a vacuum vapor deposition method), a transfer method, a printing method, an inkjet method, or a coating method, respectively. ..
- the light emitting layer 193 is a layer containing a light emitting substance.
- the light emitting layer 193 can have one or more kinds of light emitting substances.
- the luminescent substance a substance exhibiting a luminescent color such as blue, purple, bluish purple, green, yellowish green, yellow, orange, and red is appropriately used.
- Materials that can be used for conductive layers such as transistor gates, sources and drains, as well as various wirings and electrodes that make up display devices include aluminum, titanium, chromium, nickel, copper, yttrium, zirconium, molybdenum, and silver. Examples thereof include metals such as tantalum and tungsten, and alloys containing the metal as a main component. A film containing these materials can be used as a single layer or as a laminated structure.
- a conductive oxide such as indium oxide, indium tin oxide, indium zinc oxide, zinc oxide, zinc oxide containing gallium, or graphene can be used.
- metal materials such as gold, silver, platinum, magnesium, nickel, tungsten, chromium, molybdenum, iron, cobalt, copper, palladium, and titanium, and alloy materials containing the metal materials can be used.
- a nitride of the metal material for example, titanium nitride
- the laminated film of the above material can be used as the conductive layer.
- a laminated film of an alloy of silver and magnesium and an indium tin oxide because the conductivity can be enhanced.
- These can also be used for conductive layers such as various wirings and electrodes constituting the display device, and conductive layers (conductive layers that function as pixel electrodes and common electrodes) of the light emitting device.
- Examples of the insulating material that can be used for each insulating layer include resins such as acrylic resin and epoxy resin, and inorganic insulating materials such as silicon oxide, silicon oxide, silicon nitride, silicon nitride, and aluminum oxide.
- FIG. 9A shows a cross-sectional view of the display device 100B.
- the perspective view of the display device 100B is the same as that of the display device 100A (FIG. 7).
- FIG. 9A shows an example of a cross section of the display device 100B when a part of the region including the FPC 172, a part of the circuit 164, and a part of the display unit 162 are cut.
- FIG. 9A shows an example of a cross section of the display unit 162 when a region including a light emitting device 190G that emits green light and a light emitting device 190B that emits blue light is cut.
- the display device 100B shown in FIG. 9A has a transistor 202, a transistor 210, a light emitting device 190G, a light emitting device 190B, and the like between the substrate 153 and the substrate 154.
- the substrate 154 and the protective layer 195 are adhered to each other via the adhesive layer 142.
- the adhesive layer 142 is provided so as to overlap the light emitting device 190G and the light emitting device 190B, respectively, and a solid sealing structure is applied to the display device 100B.
- the substrate 153 and the insulating layer 212 are bonded to each other by an adhesive layer 155.
- a manufacturing substrate provided with an insulating layer 212, each transistor, each light emitting device, and the like and a substrate 154 provided with a light-shielding layer BM are bonded together by an adhesive layer 142. Then, by peeling off the production substrate and attaching the substrate 153 to the exposed surface, each component formed on the production substrate is transposed to the substrate 153. It is preferable that the substrate 153 and the substrate 154 each have flexibility. Thereby, the flexibility of the display device 100B can be increased.
- an inorganic insulating film that can be used for the insulating layer 211, the insulating layer 213, and the insulating layer 215 can be used, respectively.
- the light emitting device 190G has a laminated structure in which the pixel electrode 191 and the common layer 112, the light emitting layer 193G, the common layer 114, and the common electrode 115 are laminated in this order from the insulating layer 214 side.
- the light emitting device 190B has a laminated structure in which the pixel electrode 191 and the common layer 112, the light emitting layer 193B, the common layer 114, and the common electrode 115 are laminated in this order from the insulating layer 214 side.
- the pixel electrode 191 is connected to the conductive layer 222b of the transistor 210 via an opening provided in the insulating layer 214.
- the conductive layer 222b is connected to the low resistance region 231n via the openings provided in the insulating layer 215 and the insulating layer 225.
- the transistor 210 has a function of controlling the drive of the light emitting device 190.
- the end of the pixel electrode 191 is covered with a partition wall 216.
- the pixel electrode 191 contains a material that reflects visible light
- the common electrode 115 contains a material that transmits visible light.
- the light emitted by the light emitting device 190G and the light emitting device 190B is emitted to the substrate 154 side. It is preferable to use a material having high transparency to visible light for the substrate 154.
- the pixel electrode 191 included in each light emitting device can be manufactured by the same material and the same process.
- the common layer 112, the common layer 114, and the common electrode 115 are commonly used in the light emitting device 190G and the light emitting device 190B.
- the light emitting devices of each color can all have a common configuration except that the configuration of the light emitting layer 193 is different.
- a connecting portion 204 is provided in a region of the substrate 153 where the substrates 154 do not overlap.
- the wiring 165 is electrically connected to the FPC 172 via the conductive layer 166 and the connection layer 242.
- the conductive layer 166 can be obtained by processing the same conductive film as the pixel electrode 191. As a result, the connection portion 204 and the FPC 172 can be electrically connected via the connection layer 242.
- the transistor 202 and the transistor 210 include a conductive layer 221 that functions as a gate, an insulating layer 211 that functions as a gate insulating layer, a semiconductor layer having a channel forming region 231i and a pair of low resistance regions 231n, and one of a pair of low resistance regions 231n.
- the insulating layer 211 is located between the conductive layer 221 and the channel forming region 231i.
- the insulating layer 225 is located between the conductive layer 223 and the channel forming region 231i.
- the conductive layer 222a and the conductive layer 222b are each connected to the low resistance region 231n via an opening provided in the insulating layer 215.
- the conductive layer 222a and the conductive layer 222b one functions as a source and the other functions as a drain.
- FIG. 9A shows an example in which the insulating layer 225 covers the upper surface and the side surface of the semiconductor layer.
- the conductive layer 222a and the conductive layer 222b are connected to the low resistance region 231n via openings provided in the insulating layer 225 and the insulating layer 215, respectively.
- the insulating layer 225 overlaps with the channel forming region 231i of the semiconductor layer 231 and does not overlap with the low resistance region 231n.
- the structure shown in FIG. 9B can be produced by processing the insulating layer 225 using the conductive layer 223 as a mask.
- the insulating layer 215 is provided so as to cover the insulating layer 225 and the conductive layer 223, and the conductive layer 222a and the conductive layer 222b are connected to the low resistance region 231n, respectively, through the openings of the insulating layer 215.
- an insulating layer 218 may be provided to cover the transistor.
- the reliability of the light emitting device can be improved by using the light emitting device in which the initial deterioration is suppressed and the drive life is very long.
- FIG. 10A shows a block diagram of pixels.
- the pixel shown in FIG. 10A has a memory (Memory) in addition to a switching transistor (Switching Tr), a driving transistor (Driving Tr), and a light emitting device (OLED).
- Memory Memory
- switching Tr switching transistor
- driving Tr driving transistor
- OLED light emitting device
- Data Data_W is supplied to the memory.
- the data Data_W is supplied to the pixels in addition to the display data Data.
- the light emitting device By driving the light emitting device included in the display device of one aspect of the present invention based on the display data Data and the data Data_W, the light emitting device can be made to emit light with high brightness.
- FIG. 10B shows a specific circuit diagram of the pixel circuit.
- the pixel shown in FIG. 10B has a transistor M1, a transistor M2, a transistor M3, a transistor M4, a capacitance Cs, a capacitance Cw, and a light emitting device EL.
- One of the source and drain of the transistor M1 is electrically connected to one electrode of the capacitance Cw.
- the other electrode of capacitance Cw is electrically connected to one of the source or drain of the transistor M4.
- One of the source and drain of the transistor M4 is electrically connected to the gate of the transistor M2.
- the gate of the transistor M2 is electrically connected to one electrode of the capacitance Cs.
- the other electrode of capacitance Cs is electrically connected to one of the source or drain of the transistor M2.
- One of the source or drain of the transistor M2 is electrically connected to one of the source or drain of the transistor M3.
- One of the source or drain of the transistor M3 is electrically connected to one electrode of the light emitting device EL.
- Each transistor shown in FIG. 10B has a back gate that is electrically connected to the gate, but the connection of the back gate is not limited to this. Further, the transistor does not have to be provided with a back gate.
- a node to which the other electrode of the capacitance Cw, one of the source or drain of the transistor M4, the gate of the transistor M2, and one electrode of the capacitance Cs is connected is referred to as a node NM.
- a node to which the other electrode of the capacitance Cs, one of the source or drain of the transistor M2, one of the source or drain of the transistor M3, and one electrode of the light emitting device EL are connected is referred to as a node NA.
- the gate of the transistor M1 is electrically connected to the wiring G1.
- the gate of the transistor M3 is electrically connected to the wiring G1.
- the gate of the transistor M4 is electrically connected to the wiring G2.
- the other of the source or drain of the transistor M1 is electrically connected to the wiring DATA.
- the other of the source or drain of the transistor M3 is electrically connected to the wiring V0.
- the other of the source or drain of the transistor M4 is electrically connected to the wiring DATA_W.
- the other of the source or drain of the transistor M2 is electrically connected to the wiring anode (high potential side).
- the other electrode of the light emitting device EL is electrically connected to the wiring Cathode (low potential side).
- the wiring G1 and the wiring G2 can have a function as a signal line for controlling the operation of the transistor.
- the wiring DATA can have a function as a signal line for supplying an image signal to the pixels.
- the wiring DATA_W can have a function as a signal line for writing data to the storage circuit MEM.
- the wiring DATA_W can have a function as a signal line for supplying a correction signal to the pixels.
- the wiring V0 has a function as a monitor line for acquiring the electrical characteristics of the transistor M4. Further, the writing of the image signal can be stabilized by supplying a specific potential from the wiring V0 to the other electrode of the capacitance Cs via the transistor M3.
- the transistor M2, the transistor M4, and the capacitance Cw form a storage circuit MEM.
- the node NM is a storage node, and by conducting the transistor M4, the signal supplied to the wiring DATA_W can be written to the node NM.
- the potential of the node NM can be maintained for a long time.
- the transistor M4 for example, a transistor (OS transistor) in which a metal oxide is used in the channel forming region can be used.
- OS transistor a transistor in which a metal oxide is used in the channel forming region
- the off-current of the transistor M4 can be made extremely low, and the potential of the node NM can be maintained for a long time.
- OS transistors as other transistors constituting the pixels.
- a specific example of the metal oxide can be referred to in Embodiment 1.
- the OS transistor Since the OS transistor has a large energy gap, it exhibits extremely low off-current characteristics. Further, the OS transistor has features different from those of a transistor having Si in the channel formation region (hereinafter referred to as Si transistor), such as no impact ionization, avalanche breakdown, and short channel effect, and forms a highly reliable circuit. can do.
- Si transistor a transistor having Si in the channel formation region
- a Si transistor may be applied to the transistor M4. At this time, it is preferable to use Si transistors as other transistors constituting the pixels.
- Examples of the Si transistor include a transistor having amorphous silicon, a transistor having crystalline silicon (typically, low-temperature polysilicon), and a transistor having single crystal silicon.
- one pixel may have both an OS transistor and a Si transistor.
- the signal written in the node NM is capacitively coupled with the image signal supplied from the wiring DATA, and can be output to the node NA.
- the transistor M1 can have a function of selecting pixels.
- the correction signal can be added to the supplied image signal. Since the correction signal may be attenuated by an element on the transmission path, it is preferable to generate the correction signal in consideration of the attenuation.
- the light emitting device By causing the light emitting device to emit light using the image signal and the correction signal, the current flowing through the light emitting device can be increased, and high brightness can be expressed. Since a voltage higher than the output voltage of the source driver can be applied as the gate voltage of the drive transistor, the power consumption of the source driver can be reduced.
- the metal oxide preferably contains at least indium or zinc. In particular, it preferably contains indium and zinc. In addition to them, it is preferable that aluminum, gallium, yttrium, tin and the like are contained. It may also contain one or more selected from boron, silicon, titanium, iron, nickel, germanium, zirconium, molybdenum, lanthanum, cerium, neodymium, hafnium, tantalum, tungsten, magnesium, cobalt and the like. ..
- FIG. 11A is a diagram illustrating classification of crystal structures of oxide semiconductors, typically IGZO (metal oxides containing In, Ga, and Zn).
- IGZO metal oxides containing In, Ga, and Zn
- oxide semiconductors are roughly classified into “Amorphous (amorphous)", “Crystalline”, and “Crystal”.
- Amorphous includes “completable amorphous”.
- Crystalline includes CAAC (c-axis-aligned crystalline), nc (nanocrystalline), and CAC (cloud-aligned composite).
- single crystal, poly crystal, and single crystal amorphous are excluded from the classification of "Crystalline”.
- “Crystal” includes single crystal and poly crystal.
- the structure in the thick frame shown in FIG. 11A is an intermediate state between "Amorphous” and “Crystal", and belongs to a new boundary region (New crystal line phase). .. That is, the structure can be rephrased as a structure completely different from the energetically unstable "Amorphous” and "Crystal".
- the crystal structure of the film or substrate can be evaluated using an X-ray diffraction (XRD: X-Ray Evaluation) spectrum.
- XRD X-ray diffraction
- GIXD Gazing-Incidence XRD
- IGZO also referred to as crystalline IGZO
- FIGS. 11B and 11C show the XRD spectra obtained by GIXD measurement of a quartz glass substrate and an IGZO (also referred to as crystalline IGZO) film having a crystal structure classified as "Crystalline"
- the GIXD method is also referred to as a thin film method or a Seemann-Bohlin method.
- the XRD spectrum obtained by the GIXD measurement shown in FIGS. 11B and 11C will be simply referred to as an XRD spectrum.
- FIG. 11B is a quartz glass substrate
- FIG. 11C is an XRD spectrum of a crystalline IGZO film.
- the thickness of the crystalline IGZO film shown in FIG. 11C is 500 nm.
- the shape of the peak of the XRD spectrum is substantially symmetrical on the quartz glass substrate.
- the shape of the peak of the XRD spectrum is asymmetrical in the crystalline IGZO film.
- the asymmetrical shape of the peaks in the XRD spectrum clearly indicates the presence of crystals in the film or substrate. In other words, the film or substrate cannot be said to be in an amorphous state unless the shape of the peak of the XRD spectrum is symmetrical.
- the crystal structure of the film or substrate can be evaluated by a diffraction pattern (also referred to as a microelectron diffraction pattern) observed by a micro electron diffraction method (NBED: Nano Beam Electron Diffraction).
- a diffraction pattern also referred to as a microelectron diffraction pattern
- FIG. 11D is a quartz glass substrate
- FIG. 11E is a diffraction pattern of an IGZO film.
- oxide semiconductors may be classified differently from FIG. 11A.
- oxide semiconductors are divided into single crystal oxide semiconductors and other non-single crystal oxide semiconductors.
- the non-single crystal oxide semiconductor include the above-mentioned CAAC-OS and nc-OS.
- the non-single crystal oxide semiconductor includes a polycrystalline oxide semiconductor, a pseudo-amorphous oxide semiconductor (a-like OS: amorphous-like oxide semiconductor), an amorphous oxide semiconductor, and the like.
- CAAC-OS CAAC-OS
- nc-OS nc-OS
- a-like OS the details of the above-mentioned CAAC-OS, nc-OS, and a-like OS will be described.
- CAAC-OS is an oxide semiconductor having a plurality of crystal regions, the plurality of crystal regions having the c-axis oriented in a specific direction.
- the specific direction is the thickness direction of the CAAC-OS film, the normal direction of the surface to be formed of the CAAC-OS film, or the normal direction of the surface of the CAAC-OS film.
- the crystal region is a region having periodicity in the atomic arrangement. When the atomic arrangement is regarded as a lattice arrangement, the crystal region is also a region in which the lattice arrangement is aligned. Further, the CAAC-OS has a region in which a plurality of crystal regions are connected in the ab plane direction, and the region may have distortion.
- the strain refers to a region in which a plurality of crystal regions are connected in which the orientation of the lattice arrangement changes between a region in which the lattice arrangement is aligned and a region in which another grid arrangement is aligned.
- CAAC-OS is an oxide semiconductor that is c-axis oriented and not clearly oriented in the ab plane direction.
- Each of the plurality of crystal regions is composed of one or a plurality of minute crystals (crystals having a maximum diameter of less than 10 nm).
- the maximum diameter of the crystal region is less than 10 nm.
- the size of the crystal region may be about several tens of nm.
- CAAC-OS has indium (In) and oxygen. It tends to have a layered crystal structure (also referred to as a layered structure) in which a layer (hereinafter, In layer) and a layer having elements M, zinc (Zn), and oxygen (hereinafter, (M, Zn) layer) are laminated. There is. Indium and element M can be replaced with each other. Therefore, the (M, Zn) layer may contain indium. In addition, the In layer may contain the element M. In addition, Zn may be contained in the In layer.
- the layered structure is observed as a lattice image in, for example, a high-resolution TEM (Transmission Electron Microscope) image.
- the position of the peak indicating the c-axis orientation may vary depending on the type and composition of the metal elements constituting CAAC-OS.
- a plurality of bright spots are observed in the electron diffraction pattern of the CAAC-OS film.
- a certain spot and another spot are observed at point-symmetrical positions with the spot of the incident electron beam passing through the sample (also referred to as a direct spot) as the center of symmetry.
- the lattice arrangement in the crystal region is based on a hexagonal lattice, but the unit lattice is not limited to a regular hexagon and may be a non-regular hexagon. Further, in the above strain, it may have a lattice arrangement such as a pentagon or a heptagon.
- a clear grain boundary cannot be confirmed even in the vicinity of strain. That is, it can be seen that the formation of grain boundaries is suppressed by the distortion of the lattice arrangement. This is because CAAC-OS can tolerate distortion because the arrangement of oxygen atoms is not dense in the ab plane direction and the bond distance between atoms changes due to the replacement of metal atoms. It is thought that this is the reason.
- CAAC-OS for which no clear crystal grain boundary is confirmed, is one of the crystalline oxides having a crystal structure suitable for the semiconductor layer of the transistor.
- a configuration having Zn is preferable.
- In-Zn oxide and In-Ga-Zn oxide are more suitable than In oxide because they can suppress the generation of grain boundaries.
- CAAC-OS is an oxide semiconductor having high crystallinity and no clear grain boundary is confirmed. Therefore, it can be said that CAAC-OS is unlikely to cause a decrease in electron mobility due to grain boundaries. Further, since the crystallinity of the oxide semiconductor may be lowered due to the mixing of impurities or the generation of defects, CAAC-OS can be said to be an oxide semiconductor having few impurities and defects (oxygen deficiency, etc.). Therefore, the oxide semiconductor having CAAC-OS has stable physical properties. Therefore, the oxide semiconductor having CAAC-OS is resistant to heat and has high reliability. CAAC-OS is also stable against high temperatures in the manufacturing process (so-called thermal budget). Therefore, when CAAC-OS is used for the OS transistor, the degree of freedom in the manufacturing process can be expanded.
- nc-OS has periodicity in the atomic arrangement in a minute region (for example, a region of 1 nm or more and 10 nm or less, particularly a region of 1 nm or more and 3 nm or less).
- nc-OS has tiny crystals. Since the size of the minute crystal is, for example, 1 nm or more and 10 nm or less, particularly 1 nm or more and 3 nm or less, the minute crystal is also referred to as a nanocrystal.
- nc-OS does not show regularity in crystal orientation between different nanocrystals. Therefore, no orientation is observed in the entire film.
- the nc-OS may be indistinguishable from the a-like OS and the amorphous oxide semiconductor depending on the analysis method.
- a peak indicating crystallinity is not detected in the Out-of-plane XRD measurement using a ⁇ / 2 ⁇ scan.
- electron beam diffraction also referred to as limited field electron diffraction
- a diffraction pattern such as a halo pattern is performed. Is observed.
- electron diffraction also referred to as nanobeam electron diffraction
- an electron beam having a probe diameter for example, 1 nm or more and 30 nm or less
- An electron diffraction pattern in which a plurality of spots are observed in a ring-shaped region centered on a direct spot may be acquired.
- the a-like OS is an oxide semiconductor having a structure between nc-OS and an amorphous oxide semiconductor.
- the a-like OS has a void or low density region. That is, the a-like OS has lower crystallinity than the nc-OS and CAAC-OS.
- a-like OS has a higher hydrogen concentration in the membrane than nc-OS and CAAC-OS.
- CAC-OS relates to the material composition.
- CAC-OS is, for example, a composition of a material in which the elements constituting the metal oxide are unevenly distributed in a size of 0.5 nm or more and 10 nm or less, preferably 1 nm or more and 3 nm or less, or a size close thereto.
- the metal oxide one or more metal elements are unevenly distributed, and the region having the metal element has a size of 0.5 nm or more and 10 nm or less, preferably 1 nm or more and 3 nm or less, or a size close thereto.
- the mixed state is also called a mosaic shape or a patch shape.
- CAC-OS has a structure in which a material is separated into a first region and a second region to form a mosaic shape, and the first region is distributed in a film (hereinafter, also referred to as a cloud shape). It says.). That is, CAC-OS is a composite metal oxide having a structure in which the first region and the second region are mixed.
- the atomic number ratios of In, Ga, and Zn with respect to the metal elements constituting CAC-OS in the In-Ga-Zn oxide are expressed as [In], [Ga], and [Zn], respectively.
- the first region is a region in which [In] is larger than [In] in the composition of the CAC-OS film.
- the second region is a region in which [Ga] is larger than [Ga] in the composition of the CAC-OS film.
- the first region is a region in which [In] is larger than [In] in the second region and [Ga] is smaller than [Ga] in the second region.
- the second region is a region in which [Ga] is larger than [Ga] in the first region and [In] is smaller than [In] in the first region.
- the first region is a region in which indium oxide, indium zinc oxide, or the like is the main component.
- the second region is a region in which gallium oxide, gallium zinc oxide, or the like is the main component. That is, the first region can be rephrased as a region containing In as a main component. Further, the second region can be rephrased as a region containing Ga as a main component.
- CAC-OS in In-Ga-Zn oxide is a region containing Ga as a main component and a part of In as a main component in a material composition containing In, Ga, Zn, and O. Each of the regions is mosaic, and these regions are randomly present. Therefore, it is presumed that CAC-OS has a structure in which metal elements are non-uniformly distributed.
- the CAC-OS can be formed by a sputtering method, for example, under the condition that the substrate is not intentionally heated.
- a sputtering method one or more selected from an inert gas (typically argon), an oxygen gas, and a nitrogen gas may be used as the film forming gas. Good.
- the flow rate ratio of the oxygen gas to the total flow rate of the film-forming gas at the time of film formation is low. Is preferably 0% or more and 10% or less.
- EDX Energy Dispersive X-ray spectroscopy
- the first region is a region having higher conductivity as compared with the second region. That is, when the carrier flows through the first region, the conductivity as a metal oxide is exhibited. Therefore, a high field effect mobility ( ⁇ ) can be realized by distributing the first region in the metal oxide in a cloud shape.
- the second region is a region having a higher insulating property than the first region. That is, the leakage current can be suppressed by distributing the second region in the metal oxide.
- CAC-OS when used for a transistor, the conductivity caused by the first region and the insulating property caused by the second region act in a complementary manner to switch the function (On / Off). Function) can be added to CAC-OS. That is, the CAC-OS has a conductive function in a part of the material and an insulating function in a part of the material, and has a function as a semiconductor in the whole material. By separating the conductive function and the insulating function, both functions can be maximized. Therefore, by using CAC-OS for the transistor, high on-current ( Ion ), high field effect mobility ( ⁇ ), and good switching operation can be realized.
- Ion on-current
- ⁇ high field effect mobility
- CAC-OS is most suitable for various semiconductor devices including display devices.
- Oxide semiconductors have various structures, and each has different characteristics.
- the oxide semiconductor according to one aspect of the present invention has two or more of amorphous oxide semiconductor, polycrystalline oxide semiconductor, a-like OS, CAC-OS, nc-OS, and CAAC-OS. You may.
- the oxide semiconductor as a transistor, a transistor having high field effect mobility can be realized. Moreover, a highly reliable transistor can be realized.
- the carrier concentration of the oxide semiconductor is 1 ⁇ 10 17 cm -3 or less, preferably 1 ⁇ 10 15 cm -3 or less, more preferably 1 ⁇ 10 13 cm -3 or less, and more preferably 1 ⁇ 10 11 cm ⁇ . It is 3 or less, more preferably less than 1 ⁇ 10 10 cm -3 , and more than 1 ⁇ 10 -9 cm -3 .
- the impurity concentration in the oxide semiconductor film may be lowered to lower the defect level density.
- a low impurity concentration and a low defect level density is referred to as high-purity intrinsic or substantially high-purity intrinsic.
- An oxide semiconductor having a low carrier concentration may be referred to as a high-purity intrinsic or substantially high-purity intrinsic oxide semiconductor.
- the trap level density may also be low.
- the charge captured at the trap level of the oxide semiconductor takes a long time to disappear, and may behave as if it were a fixed charge. Therefore, a transistor in which a channel forming region is formed in an oxide semiconductor having a high trap level density may have unstable electrical characteristics.
- Impurities include hydrogen, nitrogen, alkali metals, alkaline earth metals, iron, nickel, silicon and the like.
- the concentration of silicon and carbon in the oxide semiconductor and the concentration of silicon and carbon near the interface with the oxide semiconductor are set to 2. ⁇ 10 18 atoms / cm 3 or less, preferably 2 ⁇ 10 17 atoms / cm 3 or less.
- the oxide semiconductor contains an alkali metal or an alkaline earth metal
- a defect level may be formed and carriers may be generated. Therefore, a transistor using an oxide semiconductor containing an alkali metal or an alkaline earth metal tends to have a normally-on characteristic. Therefore, the concentration of the alkali metal or alkaline earth metal in the oxide semiconductor obtained by SIMS is set to 1 ⁇ 10 18 atoms / cm 3 or less, preferably 2 ⁇ 10 16 atoms / cm 3 or less.
- the nitrogen concentration in the oxide semiconductor obtained by SIMS is less than 5 ⁇ 10 19 atoms / cm 3 , preferably 5 ⁇ 10 18 atoms / cm 3 or less, more preferably 1 ⁇ 10 18 atoms / cm 3 or less. , More preferably 5 ⁇ 10 17 atoms / cm 3 or less.
- hydrogen contained in an oxide semiconductor reacts with oxygen bonded to a metal atom to become water, which may form an oxygen deficiency.
- oxygen deficiency When hydrogen enters the oxygen deficiency, electrons that are carriers may be generated.
- a part of hydrogen may be combined with oxygen that is bonded to a metal atom to generate an electron as a carrier. Therefore, a transistor using an oxide semiconductor containing hydrogen tends to have a normally-on characteristic. Therefore, it is preferable that hydrogen in the oxide semiconductor is reduced as much as possible.
- the hydrogen concentration obtained by SIMS is less than 1 ⁇ 10 20 atoms / cm 3 , preferably less than 1 ⁇ 10 19 atoms / cm 3 , more preferably 5 ⁇ 10 18 atoms / cm. Less than 3 , more preferably less than 1 ⁇ 10 18 atoms / cm 3 .
- the electronic device of the present embodiment has the display device of one aspect of the present invention in the display unit, it has a long life and high reliability. Further, by using the display device of one aspect of the present invention for the display unit, the electronic device can have a long life and a large screen.
- the display unit of the electronic device of the present embodiment can display, for example, a full high-definition image having a resolution of 4K2K, 8K4K, 16K8K, or higher.
- the screen size of the display unit can be 20 inches or more diagonally, 30 inches or more diagonally, 50 inches or more diagonally, 60 inches or more diagonally, or 70 inches or more diagonally.
- electronic devices for example, relatively large screens such as television devices, desktop or notebook personal computers, monitors for computers, digital signage (electronic signs), and large game machines such as pachinko machines.
- digital cameras, digital video cameras, digital photo frames, mobile phones, portable game machines, personal digital assistants, sound reproduction devices, and the like can be mentioned.
- the electronic device of the present embodiment can be incorporated along the inner or outer wall of a house or building, or along the curved surface of the interior or exterior of an automobile.
- the electronic device of the present embodiment may have an antenna.
- the display unit can display images, information, and the like.
- the antenna may be used for non-contact power transmission.
- the electronic device of the present embodiment has sensors (force, displacement, position, velocity, acceleration, angular velocity, rotation speed, distance, light, liquid, magnetism, temperature, chemical substance, voice, time, hardness, electric field, current, voltage. , Including the ability to measure power, radiation, flow rate, humidity, gradient, vibration, odor or infrared rays).
- the electronic device of the present embodiment can have various functions. For example, a function to display various information (still images, moving images, text images, etc.) on the display unit, a touch panel function, a function to display a calendar, date or time, a function to execute various software (programs), wireless communication. It can have a function, a function of reading a program or data recorded on a recording medium, and the like.
- the electronic device 6500 shown in FIG. 12A is a portable information terminal that can be used as a smartphone.
- the electronic device 6500 includes a housing 6501, a display unit 6502, a power button 6503, a button 6504, a speaker 6505, a microphone 6506, a camera 6507, a light source 6508, and the like.
- the display unit 6502 has a touch panel function.
- a display device can be applied to the display unit 6502.
- FIG. 12B is a schematic cross-sectional view including an end portion of the housing 6501 on the microphone 6506 side.
- a translucent protective member 6510 is provided on the display surface side of the housing 6501, and the display panel 6511, the optical member 6512, the touch sensor panel 6513, and the printed circuit board are provided in the space surrounded by the housing 6501 and the protective member 6510.
- a substrate 6517, a battery 6518, and the like are arranged.
- a display panel 6511, an optical member 6512, and a touch sensor panel 6513 are fixed to the protective member 6510 by an adhesive layer (not shown).
- a part of the display panel 6511 is folded back, and the FPC 6515 is connected to the folded back portion.
- IC6516 is mounted on FPC6515.
- the FPC6515 is connected to a terminal provided on the printed circuit board 6517.
- a flexible display device can be applied to the display panel 6511. Therefore, an extremely lightweight electronic device can be realized. Further, since the display panel 6511 is extremely thin, it is possible to mount a large-capacity battery 6518 while suppressing the thickness of the electronic device. Further, by folding back a part of the display panel 6511 and arranging the connection portion with the FPC 6515 on the back side of the pixel portion, an electronic device having a narrow frame can be realized.
- 13 to 15 show an example of an electronic device having a flexible display device and capable of being folded into a small size.
- the electronic devices shown in FIGS. 13 and 14 have a two-fold mechanism and can be folded so that the display surfaces face each other.
- the electronic device shown in FIG. 15 has a tri-folding mechanism, and has a region that can be folded so that the display surfaces face each other and a region that can be folded so that the surfaces opposite to the display surface face each other.
- the electronic device shown in FIGS. 13 to 15 has a display device having a relatively large aspect ratio such as 16: 9, 18: 9, 21: 9, the creases are provided in the minor axis direction. It can be folded into a small size to improve the portability of electronic devices. Further, when the electronic device is folded into a small size, the invisible display area is hidden, so that the power consumption can be greatly reduced.
- FIG. 13A is a diagram showing a state in which the electronic device 800A is folded to the minimum size (folded in half).
- FIG. 13B is a diagram showing a state in which the electronic device 800B is folded to the minimum size (folded in half).
- FIG. 13C is a diagram showing a state in which the electronic device 800A or the electronic device 800B is deployed.
- the electronic device 800A and the electronic device 800B each have a flexible display panel 801a, a housing 802a, a housing 802b, and a hinge 803.
- a seamless and flexible display panel can be used.
- a display device according to one aspect of the present invention can be used for the display panel 801a.
- the display panel 801a In the deployed state of the electronic device 800A or the electronic device 800B, the display panel 801a has a first region 811a overlapping the housing 802a, a second region 811b overlapping the hinge 803, and a third region 811c overlapping the housing 802b. Have. These three areas are preferably included in the display area of the display panel 801a. In the state shown in FIGS. 13A and 13B, the first region 811a and the third region 811c overlap each other. When the electronic device 800A and the electronic device 800B are folded as shown in FIGS. 13A and 13B, the second region 811b is bent so that the display surfaces of the first region 811a and the third region 811c are respectively displayed. Face each other.
- the housing 802a is connected to the housing 802b via a hinge 803.
- At least a part of the display panel 801a may be fixed to the housing 802a. At least a part of the display panel 801a may be fixed to the housing 802b.
- the electronic device 800B further includes a display panel 801b.
- the display panel 801a and the display panel 801b overlap each other via the housing 802a.
- the display surface of the display panel 801a and the display surface of the display panel 801b face in opposite directions.
- the display panel 801a may be fixed to the first surface
- the display panel 801b may be fixed to the second surface facing the first surface.
- the display device of one aspect of the present invention can be used for one or both of the display panel 801a and the display panel 801b included in the electronic device 800B.
- the electronic device 800B When the electronic device 800B is folded, the user can visually recognize the display on the display panel 801b. When the electronic device 800B is deployed, the user can visually recognize the display on the display panel 801a.
- FIG. 14A is a diagram showing a state in which the electronic device 800C is folded to the minimum size (folded in half).
- FIG. 14B is a diagram showing a state in which the electronic device 800C is deployed.
- the electronic device 800C has a flexible display panel 801 and a housing 802a, a housing 802b, and a hinge 803.
- a seamless single flexible display panel can be used.
- a display device according to one aspect of the present invention can be used for the display panel 801.
- the display panel 801 is located between the first region 811a and the second region 811b, the first region 811a and the second region 811b that overlap each other via the housing 802a. It also has a third region 811c having a curved surface, a fourth region 811d overlapping the hinge 803, and a fifth region 811e overlapping the housing 802b. These five areas are preferably included in the display area of the display panel 801.
- the first region 811a, the second region 811b, and the fifth region 811e overlap each other.
- the user can visually recognize the display of the first region 811a and the third region 811c.
- the user can visually recognize the display of the second region 811b, the fourth region 811d, and the fifth region 811e (further, the third region 811c).
- the display surface faces the same direction, and in the second region 811b, the display surface faces the direction facing the direction. There is.
- the display surfaces of the second region 811b and the fifth region 811e face each other.
- the housing 802a is connected to the housing 802b via a hinge 803.
- At least a part of the display panel 801 may be fixed to the housing 802a.
- the display panel 801 has three continuous surfaces of the housing 802a (a first surface, a second surface facing the first surface, and a third surface (side surface) between the first surface and the second surface. )) Is provided.
- the first region 811a of the display panel 801 may be fixed to the first surface.
- the second region 811b of the display panel may be fixed to the second surface.
- the third region 811c of the display panel 801 may be fixed to the third surface.
- At least a part of the display panel 801a may be fixed to the housing 802b.
- the fifth region 811e of the display panel 801 may be fixed to the housing 802b.
- FIG. 15A is a diagram showing a state in which the electronic device 800D is folded to the minimum size (folded in three).
- FIG. 15B is a diagram showing a state in which the electronic device 800D is deployed.
- FIG. 15C is a diagram showing a state in which the electronic device 800E is folded to the minimum size (folded in three).
- FIG. 15D is a diagram showing a state in which the electronic device 800E is deployed.
- the electronic device 800D and the electronic device 800E each have a flexible display panel 801 and a housing 802a, a housing 802b, a housing 802c, a hinge 803a, and a hinge 803b.
- a seamless single flexible display panel can be used.
- a display device according to one aspect of the present invention can be used for the display panel 801.
- the display panel 801 In the deployed state of the electronic device 800D or the electronic device 800E, the display panel 801 has a first region 811a overlapping the housing 802a, a second region 811b overlapping the hinge 803a, and a third region 811c overlapping the housing 802b. It has a fourth region 811d that overlaps the hinge 803b and a fifth region 811e that overlaps the housing 802c. These five areas are preferably included in the display area of the display panel 801. In the state shown in FIGS. 15A and 15C, the first region 811a, the third region 811c, and the fifth region 811e overlap each other. In the state shown in FIGS. 15A and 15C, the user can visually recognize the display of the first region 811a and the second region 811b. In the state shown in FIGS. 15B and 15D, the user can visually recognize the display of all five areas.
- the second region 811b bends so as to display the display surfaces of the first region 811a and the third region 811c, respectively. Opposing surfaces face each other.
- the display surfaces of the third region 811c and the fifth region 811e are formed by bending the fourth region 811d. Face each other.
- the housing 802a is connected to the housing 802b via a hinge 803a.
- the housing 802b is connected to the housing 802c via a hinge 803b.
- At least a part of the display panel 801 may be fixed to the housing 802a. At least a part of the display panel 801 may be fixed to the housing 802b. At least a part of the display panel 801 may be fixed to the housing 802c.
- one of the plurality of housings is thicker than the other housings.
- the housing 802b is thicker than the housing 802a.
- the housing 802c is thicker than the housing 802a and the housing 802b.
- a relatively large battery 827 can be housed inside the thick housing, and the electronic device can be operated for a long time. Further, by incorporating the relatively heavy battery 827 in the thick housing, the position of the center of gravity of the electronic device can be set inside the thick housing even in the deployed state. By having a housing thicker than other housings and having a center of gravity inside the thick housing, it is possible to improve the ease of holding the electronic device when it is deployed flat.
- the battery 827 it is preferable to use a lithium ion battery capable of increasing the capacity.
- the battery 827 is preferably provided with a protection circuit 828.
- the battery 827 is built in the housing 802a.
- the electronic device 800E has a grip portion 806 that is easy to grip at the end of the housing 802a, and the battery 827 can be embedded in the grip portion 806. Since the center of gravity of the electronic device 800E is located at the grip portion 806 containing the heavy battery 827, the ease of holding can be improved. Further, as shown in FIG. 15D, when deployed flat, the grip portion 806 serves as a leg and can be used in a stable form even on a desk. In addition, since the display surface is slanted, visibility can be improved.
- the deformation of the electronic device of the present embodiment may be performed manually, or may be performed by using electric power or mechanical power such as a spring.
- the electronic devices 800A to 800E are easy to operate regardless of the dominant hand. It is preferable that each of the electronic devices 800A to 800E can display an image in a direction that is easy for the user to see.
- This operation is performed, for example, by detecting the inclination of the electronic device with a sensor (acceleration sensor, gyro sensor, etc.) of the electronic device and determining the orientation of the image display from the inclination.
- the sensor can detect the shaking of the electronic device from the change in inclination. Since there are individual differences in shaking, it is possible to make the user judge by learning the shaking information with artificial intelligence (AI). Personal authentication can also be performed using this function.
- AI artificial intelligence
- the electronic devices 800A to 800E preferably have an antenna inside the housing.
- an example in which the antenna 825 and the antenna 826 are provided in the housing 802a is shown, but the number of antennas and the position where the antennas are provided are not limited to this.
- the antenna 825 is a 4th generation mobile communication system (4G) communication antenna
- the antenna 826 is a 5th generation mobile communication system (5G) communication antenna.
- the housing 802a By providing both the antenna 825 and the antenna 826 in the housing 802a, good communication can be easily performed.
- the electronic devices 800B to 800E are often used (placement, holding, etc.) so that the display is easy to see even when folded. Therefore, there are many opportunities for the housing 802a to face a direction in which radio waves can be easily received, which makes it easier to receive radio waves.
- FIG. 16A shows an example of a television device.
- the display unit 7000 is incorporated in the housing 7101.
- a configuration in which the housing 7101 is supported by the stand 7103 is shown.
- a display device can be applied to the display unit 7000.
- the operation of the television device 7100 shown in FIG. 16A can be performed by an operation switch included in the housing 7101 or a separate remote control operation machine 7111.
- the display unit 7000 may be provided with a touch sensor, and the television device 7100 may be operated by touching the display unit 7000 with a finger or the like.
- the remote controller 7111 may have a display unit that displays information output from the remote controller 7111.
- the channel and volume can be operated by the operation keys or the touch panel included in the remote controller 7111, and the image displayed on the display unit 7000 can be operated.
- the television device 7100 is configured to include a receiver, a modem, and the like.
- the receiver can receive general television broadcasts.
- information communication is performed in one direction (sender to receiver) or two-way (sender and receiver, or between recipients, etc.). It is also possible.
- FIG. 16B shows an example of a notebook personal computer.
- the notebook personal computer 7200 has a housing 7211, a keyboard 7212, a pointing device 7213, an external connection port 7214, and the like.
- a display unit 7000 is incorporated in the housing 7211.
- a display device can be applied to the display unit 7000.
- 16C and 16D show an example of digital signage.
- the digital signage 7300 shown in FIG. 16C includes a housing 7301, a display unit 7000, a speaker 7303, and the like. Further, it may have an LED lamp, an operation key (including a power switch or an operation switch), a connection terminal, various sensors, a microphone, and the like.
- FIG. 16D is a digital signage 7400 attached to a columnar pillar 7401.
- the digital signage 7400 has a display unit 7000 provided along the curved surface of the pillar 7401.
- the display device of one aspect of the present invention can be applied to the display unit 7000.
- the wider the display unit 7000 the more information can be provided at one time. Further, the wider the display unit 7000 is, the easier it is for people to see, and for example, the advertising effect of the advertisement can be enhanced.
- the touch panel By applying the touch panel to the display unit 7000, not only the image or moving image can be displayed on the display unit 7000, but also the user can intuitively operate the display unit 7000, which is preferable. In addition, when used for the purpose of providing information such as route information or traffic information, usability can be improved by intuitive operation.
- the digital signage 7300 or the digital signage 7400 can be linked with the information terminal 7311 or the information terminal 7411 such as a smartphone owned by the user by wireless communication.
- the information of the advertisement displayed on the display unit 7000 can be displayed on the screen of the information terminal 7311 or the information terminal 7411.
- the display of the display unit 7000 can be switched by operating the information terminal 7311 or the information terminal 7411.
- the digital signage 7300 or the digital signage 7400 can be made to execute a game using the screen of the information terminal 7311 or the information terminal 7411 as an operation means (controller). As a result, an unspecified number of users can participate in and enjoy the game at the same time.
- the electronic devices shown in FIGS. 17A to 17F include a housing 9000, a display unit 9001, a speaker 9003, an operation key 9005 (including a power switch or an operation switch), a connection terminal 9006, and a sensor 9007 (force, displacement, position, speed). Measures acceleration, angular velocity, rotation speed, distance, light, liquid, magnetism, temperature, chemicals, voice, time, hardness, electric field, current, voltage, power, radiation, flow rate, humidity, gradient, vibration, odor or infrared rays (Including the function of), microphone 9008, and the like.
- the electronic devices shown in FIGS. 17A to 17F have various functions. For example, a function to display various information (still images, moving images, text images, etc.) on the display unit, a touch panel function, a function to display a calendar, date or time, etc., a function to control processing by various software (programs), It can have a wireless communication function, a function of reading and processing a program or data recorded on a recording medium, and the like.
- the functions of the electronic device are not limited to these, and can have various functions.
- the electronic device may have a plurality of display units.
- the electronic device even if the electronic device is provided with a camera or the like, it has a function of shooting a still image or a moving image and saving it on a recording medium (external or built in the camera), a function of displaying the shot image on a display unit, and the like. Good.
- FIGS. 17A to 17F Details of the electronic devices shown in FIGS. 17A to 17F will be described below.
- FIG. 17A is a perspective view showing a mobile information terminal 9101.
- the mobile information terminal 9101 can be used as, for example, a smartphone.
- the mobile information terminal 9101 may be provided with a speaker 9003, a connection terminal 9006, a sensor 9007, and the like. Further, the mobile information terminal 9101 can display character and image information on a plurality of surfaces thereof.
- FIG. 17A shows an example in which three icons 9050 are displayed. Further, the information 9051 indicated by the broken line rectangle can be displayed on another surface of the display unit 9001. Examples of information 9051 include notification of incoming calls such as e-mail, SNS, and telephone, titles such as e-mail and SNS, sender name, date and time, time, remaining battery level, and antenna reception strength. Alternatively, an icon 9050 or the like may be displayed at the position where the information 9051 is displayed.
- FIG. 17B is a perspective view showing a mobile information terminal 9102.
- the mobile information terminal 9102 has a function of displaying information on three or more surfaces of the display unit 9001.
- information 9052, information 9053, and information 9054 are displayed on different surfaces.
- the user can check the information 9053 displayed at a position that can be observed from above the mobile information terminal 9102 with the mobile information terminal 9102 stored in the chest pocket of the clothes.
- the user can check the display without taking out the mobile information terminal 9102 from the pocket, and can determine, for example, whether or not to receive a call.
- FIG. 17C is a perspective view showing a wristwatch-type portable information terminal 9200.
- the mobile information terminal 9200 can be used as, for example, a smart watch.
- the display unit 9001 is provided with a curved display surface, and can display along the curved display surface.
- the mobile information terminal 9200 can also make a hands-free call by communicating with a headset capable of wireless communication, for example.
- the mobile information terminal 9200 can also perform data transmission and charge with other information terminals by means of the connection terminal 9006.
- the charging operation may be performed by wireless power supply.
- 17D to 17F are perspective views showing a foldable mobile information terminal 9201.
- 17D is a perspective view of the mobile information terminal 9201 in an unfolded state
- FIG. 17F is a folded state
- FIG. 17E is a perspective view of a state in which one of FIGS. 17D and 17F is in the process of changing to the other.
- the mobile information terminal 9201 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 unit 9001 included in the mobile information terminal 9201 is supported by three housings 9000 connected by a hinge 9055.
- the display unit 9001 can be bent with a radius of curvature of 0.1 mm or more and 150 mm or less.
- the HOMO level and LUMO level can be calculated based on cyclic voltammetry (CV) measurements.
- an electrochemical analyzer manufactured by BAS Co., Ltd., model number: ALS model 600A or 600C was used as the measuring device.
- dehydrated dimethylformamide (DMF) manufactured by Aldrich Co., Ltd., 99.8%, catalog number; 22705-6) was used as a solvent, and tetra-n-butylammonium perchlorate (supporting electrolyte) was used.
- n-Bu 4 NCLO 4 manufactured by Tokyo Kasei Co., Ltd., catalog number; T0836
- a platinum electrode manufactured by BAS Co., Ltd., PTE platinum electrode
- a platinum electrode manufactured by BAS Co., Ltd., Pt counter electrode for VC-3 (5 cm)
- auxiliary electrode is used as an auxiliary electrode.
- the potential energy of the reference electrode used in this reference example with respect to the vacuum level is known to be -4.94 eV
- the HOMO level [eV] -4.94-Ea
- the electron mobility can be measured by Impedance Spectroscopy (IS method).
- the carrier mobility of the EL material is measured from the IV characteristics of the transient photocurrent method (Time-of-flight: TOF method) and the space charge limiting current (Space-charge-limited current: SCLC) (SCLC method). ) Etc. have been known for a long time.
- the TOF method requires a sample having a considerably thicker film thickness than an actual organic EL device.
- the SCLC method has drawbacks such that the electric field strength dependence of carrier mobility cannot be obtained.
- the film thickness of the organic film required for measurement is as thin as several hundred nm, so it is possible to form a film even with a relatively small amount of EL material, and the film thickness moves close to that of an actual organic EL device.
- the feature is that the degree can be measured, and the electric field strength dependence of the carrier mobility can also be obtained.
- Equation (2) and (3) can be calculated by the single injection model, respectively.
- g (formula (4)) is a differential conductance.
- C is the capacitance
- ⁇ is ⁇ T and represents the traveling angle
- ⁇ represents the angular frequency
- T is the running time.
- the current equation, Poisson equation, and continuity current equation are used in the analysis, ignoring the existence of diffusion currents and trap levels.
- the method of calculating the mobility from the frequency characteristics of the capacitance is the ⁇ B method. Further, the method of calculating the mobility from the frequency characteristics of conductance is the ⁇ G method.
- An electron-only device of a material whose electron mobility is desired is manufactured.
- An electron-only device is a device designed so that only electrons flow as a carrier.
- ⁇ B method a method for calculating mobility from the frequency characteristics of capacitance
- the structure of the electron-only device manufactured for measurement is shown in FIG. 18A, and the specific configuration is shown in Table 1.
- the first layer 910, the second layer 911, and the third layer are formed between the first electrode 901 (anode) and the second electrode 902 (cathode). It has 912.
- the material for which the electron mobility is to be obtained may be used as the material for the second layer 911.
- FIG. 19 shows the current density-voltage characteristics of the electron-only device prepared by using the co-deposited film of ZADN and Liq as the second layer 911.
- the impedance measurement was performed under the conditions of an AC voltage of 70 mV and a frequency of 1 Hz to 3 MHz while applying a DC voltage in the range of 5.0 V to 9.0 V.
- the capacitance is calculated from the admittance (formula (1) described above), which is the reciprocal of the impedance obtained here.
- the frequency characteristics of the calculated capacitance C at the applied voltage of 7.0 V are shown in FIG.
- the frequency characteristic of the capacitance C is obtained because the space charge due to the carrier injected by the minute voltage signal cannot completely follow the minute AC voltage and a phase difference occurs in the current.
- the traveling time of the carriers in the membrane is defined by the time T at which the injected carriers reach the counter electrode, and is represented by the following equation (5).
- the traveling time T can be obtained from f'max obtained from the above measurement and analysis (Equation (6))
- the electron mobility at a voltage of 7.0 V can be obtained from the above equation (5). ..
- the electron mobility at each voltage (electric field strength) can be calculated, so that the electric field strength dependence of the mobility can also be measured.
- FIG. 22 shows the electric field strength dependence of the electron mobility of each organic compound finally obtained by the above calculation method, and the square root of the electric field strength [V / cm] read from the figure is 600 [V]. / Cm] Table 2 shows the electron mobility values at 1/2 .
- the square shows the result of cgDBCzPA
- the triangle shows the result of 2mDBTBPDBq-II
- the diamond shows the result of the co-deposited film of ZADN and Liq.
- a device R1 exhibiting red light, a device G1 exhibiting green light, and a device B1 exhibiting blue light will be described and evaluated.
- the structure of the device used in this embodiment is shown in FIG. 18B, and the specific configuration is shown in Table 3.
- the chemical formulas of the materials used in this example are shown below.
- a first electrode 130 is formed on a substrate (not shown), and holes are injected onto the first electrode 130.
- the layer 131, the hole transport layer 132a, the hole transport layer 132b, the light emitting layer 133, the electron transport layer 134, and the electron injection layer 135 were sequentially laminated, and a second electrode 140 was formed on the electron injection layer 135.
- Each device further has a buffer layer 136 on the second electrode 140.
- the buffer layer 136 has a function of reducing the loss of light energy due to the surface plasmon in the second electrode 140 (semi-transmissive / semi-reflective electrode).
- As the buffer layer 136 various organic films that can be used for the light emitting device can be adopted.
- the first electrode 130 was formed on the substrate.
- the electrode area was 4 mm 2 (2 mm ⁇ 2 mm).
- a glass substrate was used as the substrate.
- the first electrode 130 is formed by forming an alloy (Ag-Pd-Cu (APC)) of silver (Ag), palladium (Pd) and copper (Cu) by a sputtering method, and indium tin oxide containing silicon oxide (Ag-Pd-Cu (APC)).
- ITSO was formed by forming a film by a sputtering method.
- APC was formed to have a film thickness of 100 nm
- ITSO was formed to have a film thickness of 110 nm.
- device G1 and device B1 APC was formed to have a film thickness of 100 nm
- ITSO was formed to have a film thickness of 85 nm.
- the first electrode 130 functions as an anode.
- 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 vapor deposition apparatus whose internal pressure was reduced to about 10 -4 Pa, vacuum fired at 170 ° C. for 30 minutes in a heating chamber inside the vacuum vapor deposition apparatus, and then the substrate was released for about 30 minutes. It was chilled.
- the hole injection layer 131 was formed on the first electrode 130.
- the hole injection layer 131 is formed by reducing the pressure in the vacuum deposition apparatus to 10 -4 Pa, and then N, N-bis (4-biphenyl) -6-phenylbenzo [b] naphtho [1,2-d] furan-8.
- -Amine abbreviation: BBABnf
- ALD-MP001Q Analytical Studio Co., Ltd., material serial number: 1S20180314
- the hole transport layer 132a was formed on the hole injection layer 131.
- the hole transport layer 132a was formed by depositing BBABnf.
- the hole transport layer 132a was formed so as to have a film thickness of 30 nm in the device R1, a film thickness of 10 nm in the device G1, and a film thickness of 25 nm in the device B1.
- the hole transport layer 132b was formed on the hole transport layer 132a.
- the hole transport layer 132b of device R1 is N- (1,1'-biphenyl-4-yl) -N- [4- (9-phenyl-9H-carbazole-3-yl) phenyl] -9,9-. It was formed by vapor deposition using dimethyl-9H-fluorene-2-amine (abbreviation: PCBBiF) so as to have a film thickness of 50 nm.
- PCBBiF dimethyl-9H-fluorene-2-amine
- the hole transport layer 132b of the device G1 uses 4,4'-diphenyl-4''-(9-phenyl-9H-carbazole-3-yl) triphenylamine (abbreviation: PCBBi1BP) to a film thickness of 50 nm. It was formed by vapor deposition so as to become.
- PCBBi1BP 4,4'-diphenyl-4''-(9-phenyl-9H-carbazole-3-yl) triphenylamine
- the hole transport layer 132b of the device B1 uses 3,3'-(naphthalene-1,4-diyl) bis (9-phenyl-9H-carbazole) (abbreviation: PCzN2) so that the film thickness is 10 nm. It was formed by vapor deposition.
- the light emitting layer 133 was formed on the hole transport layer 132b.
- the light emitting layer 133 of the device G1 is composed of 8- (1,1'-biphenyl-4-yl) -4- [3- (dibenzothiophen-4-yl) phenyl]-[1] benzoflo [3,2-d].
- the light emitting layer 133 of the device B1 includes 9- (1-naphthyl) -10- [4- (2-naphthyl) phenyl] anthracene (abbreviation: ⁇ N- ⁇ NPAnth) and 3,10-bis [N- (9-).
- Phenyl-9H-carbazole-2-yl) -N-phenylamino] naphtho [2,3-b; 6,7-b'] bisbenzofuran (abbreviation: 3,10PCA2Nbf (IV) -02), weight ratio was formed by co-evaporation so that the thickness was 1: 0.015 ( ⁇ N- ⁇ NPAnth: 3,10PCA2Nbf (IV) -02) and the film thickness was 25 nm.
- 3,10PCA2Nbf (IV) -02 is a blue luminescent substance.
- the electron transport layer 134 was formed on the light emitting layer 133.
- the electron transport layer 134 in the light emitting device of this example is 2- ⁇ 4- [9,10-di (naphthalene-2-yl) -2-anthryl] phenyl ⁇ -1-phenyl-1H-benzimidazole (abbreviation: abbreviation:). It is a two-layer laminated structure in which the mixing ratios of ZADN) and 8-quinolinolato-lithium (abbreviation: Liq) are different from each other.
- the electron transport layer 134 has a lower Liq content on the cathode (second electrode 140) side than on the anode (first electrode 130) side.
- the electron injection layer 135 was formed on the electron transport layer 134.
- the electron injection layer 135 was formed by vapor deposition using Liq so that the film thickness was 1 nm.
- a second electrode 140 was formed on the electron injection layer 135.
- the second electrode 140 functions as a cathode.
- a buffer layer 136 was formed on the second electrode 140.
- the buffer layer 136 is deposited using 4,4', 4''- (benzene-1,3,5-triyl) tri (dibenzothiophene) (abbreviation: DBT3P-II) so that the film thickness is 80 nm. Formed.
- a light emitting device formed by sandwiching an EL layer between a pair of electrodes is formed on the substrate.
- the vapor deposition method by the resistance heating method was used.
- the light emitting device manufactured as shown above is sealed by another substrate (not shown).
- another substrate (not shown) coated with an adhesive that is solidified by ultraviolet light is fixed on the substrate in a glove box having a nitrogen atmosphere. Then, the substrates were adhered to each other so that the adhesive adhered to the periphery of the light emitting device formed on the substrate.
- the adhesive was stabilized by irradiating it with ultraviolet light of 365 nm 2 at 6 J / cm 2 to solidify the adhesive and heat-treating it at 80 ° C. for 1 hour.
- ⁇ Operating characteristics of light emitting device ⁇ The operating characteristics of device R1, device G1, and device B1 were measured. The measurement was performed at room temperature (atmosphere maintained at 25 ° C.).
- FIG. 23 to 27 show the characteristics of the device R1.
- FIG. 23 is a diagram showing the brightness-current density characteristics of the device R1.
- FIG. 24 is a diagram showing the luminance-voltage characteristics of the device R1.
- FIG. 25 is a diagram showing the current efficiency-luminance characteristic of the device R1.
- FIG. 26 is a diagram showing the current density-voltage characteristics of the device R1.
- FIG. 27 is a diagram showing an emission spectrum when a current is passed through the device R1 at a current density of 5 mA / cm 2 .
- FIG. 28 is a diagram showing the brightness-current density characteristics of the device G1.
- FIG. 29 is a diagram showing the luminance-voltage characteristics of the device G1.
- FIG. 30 is a diagram showing the current efficiency-luminance characteristic of the device G1.
- FIG. 31 is a diagram showing the current density-voltage characteristics of the device G1.
- FIG. 32 is a diagram showing an emission spectrum when a current is passed through the device G1 at a current density of 5 mA / cm 2 .
- FIG. 33 to 37 show the characteristics of the device B1.
- FIG. 33 is a diagram showing the luminance-current density characteristics of the device B1.
- FIG. 34 is a diagram showing the luminance-voltage characteristics of the device B1.
- FIG. 35 is a diagram showing the current efficiency-luminance characteristic of the device B1.
- FIG. 36 is a diagram showing the current density-voltage characteristics of the device B1.
- FIG. 37 is a diagram showing an emission spectrum when a current is passed through the device B1 at a current density of 14.7 mA / cm 2 .
- Table 4 shows the main initial characteristic values of each light emitting device at around 1000 cd / m 2 .
- the devices R1, G1 and B1 each exhibited high light emission with high color purity and were found to be highly efficient.
- device R1 showed an emission spectrum having a maximum peak near 610 nm. Further, as shown in FIG. 32, the device G1 showed an emission spectrum having a maximum peak near 521 nm. Further, as shown in FIG. 37, the device B1 showed an emission spectrum having a maximum peak near 459 nm.
- FIGS. 38 to 40 The results of the reliability test are shown in FIGS. 38 to 40.
- the vertical axis represents the normalized luminance (%) when the initial luminance is 100%
- the horizontal axis represents the driving time (h).
- the current density of the device R1 was set to 75 mA / cm 2
- the current density of the devices G1 and B1 was set to 50 mA / cm 2 , and each light emitting device was driven.
- the RESTI structure As described above, in this embodiment, by applying the RESTI structure, it was possible to manufacture a light emitting device having a long drive life in any light emitting device exhibiting red, green, or blue light. Further, in this embodiment, by applying the RESTI structure, it was possible to manufacture a light emitting device having a long drive life in both fluorescence emission and phosphorescence emission.
- the three light emitting devices produced in this example have light emitting layers containing materials different from each other.
- the three light emitting devices include a layer using the same material and a layer using the same material and having the same film thickness. Therefore, in the production of the display device of one aspect of the present invention, it was suggested that a common layer is provided for the light emitting devices of three colors, and the light emitting device having a long drive life can be produced with a small number of production steps.
- Example 1 For the method of manufacturing the light emitting device of this example, refer to Example 1.
- the chemical formulas of the materials used in this example are shown below.
- the chemical formulas of the materials already shown are omitted.
- the electron transport layer 134 in the light emitting device of this embodiment has a two-layer laminated structure in which the mixing ratios of ZADN and Liq are different from each other. Specifically, the electron transport layer 134 in the light emitting device of this embodiment has a lower Liq content on the cathode (second electrode 140) side than on the anode (first electrode 130) side.
- the light emitting layer 133 of the device G3 has 8BP-4mDBtPBfpm, ⁇ NCCP, and [2-methyl- (2-pyridinyl- ⁇ N) benzoflo [2,3-b] pyridine- ⁇ C] bis [2- (2-pyridinyl).
- ⁇ N) Phenyl ⁇ C] Iridium (III) (abbreviation: [Ir (ppy) 2 (mbfpypy)]) with a weight ratio of 0.6: 0.4: 0.1 ( 8BP-4mDBtPBfpm: ⁇ NCCP: [Ir (ppy) 2 (mbfpypy)] was formed by co-depositing so that the film thickness was 50 nm.
- the emission colors of the device R2 exhibiting red light, the device G2 exhibiting green light, and the device B2 exhibiting blue light in this embodiment are subordinate to a commercially available display device (smartphone) using an organic EL device, respectively. It was manufactured so as to have the same chromaticity as the pixel.
- the device R2 exhibiting red light, the device G2 exhibiting green light, and the device B2 exhibiting blue light are used as a light emitting device (organic) in the sub-pixel of the commercially available display device (smartphone).
- a reliability test was conducted by emitting light with the same brightness and chromaticity as the EL device).
- the brightness when each color is a single color and the brightness is set to a gradation of 255/255 (brightness 100%) is 108 cd / m 2 for red (R) and green (G).
- ) was 354 cd / m 2
- blue (B) was 32.9 cd / m 2 .
- the aperture ratio of the sub-pixel of the commercially available display device was 4.5% for red, 4.3% for green, and 6.8% for blue. From the value of the aperture ratio and each luminance of RGB in the display device, each luminance in the sub-pixel (RGB) can be obtained. Finally, by assuming that the transmittance including the circular polarizing plate is 40% (each brightness in the sub-pixel (RGB) is divided by 0.4), the brightness when driving the devices R2, G2, and B2. Can be determined.
- a color filter and a circular polarizing plate are provided for each sub-pixel, and the chromaticity and brightness of each organic EL device are measured through these. Also in the light emitting device of this embodiment, a color filter that transmits each color was placed on each light emitting device, and the chromaticity and brightness of each light emitting device were measured through the color filter.
- Table 6 shows the driving conditions in the reliability test of each light emitting device. That is, the devices R2, G2, and B2 were driven with a constant current under the conditions that the initial brightness was 6580 cd / m 2 , 200,000 cd / m 2 , and 1450 cd / m 2 , respectively.
- the LT95 of the device R2 (the time when the brightness decreases to 95% of the initial brightness) is 3000 hours or more, the LT95 of the device G2 is 480 hours, and the LT95 of the device B2 is 1640 hours. Met.
- the blue light emitting device tends to have the shortest drive life.
- the blue light emitting device is driven next to the red light emitting device. It had a long life.
- a light emitting layer that emits fluorescence and a RESTI structure are applied to a light emitting device that exhibits blue light. As a result, it is considered that the initial deterioration of the light emitting device exhibiting blue light can be suppressed and the drive life can be made very long.
- the required brightness can be changed by changing the aperture ratio of the sub-pixels of each color, so that the emission lifetime can be adjusted. Even in that case, the effect of suppressing the initial deterioration can be expected, so it can be said that a long-life light emitting device can be manufactured for each color. Since the life of the blue fluorescent device adopting the RESTI structure is very long, in the case of the OLED display, the aperture ratio of the blue sub-pixel can be made smaller than before. Further, since the red phosphorescence device using the RESTI structure and ExTET also has a very long life, the aperture ratio of the red sub-pixel of RGB can be minimized.
- the overall life can be extended while maintaining the balance of the white display.
- the fact that the aperture ratio of the blue and red sub-pixels can be reduced is also advantageous for increasing the definition of the pentile type display device.
- the RESTI structure As described above, in this embodiment, by applying the RESTI structure, it was possible to manufacture a light emitting device having a long drive life in any light emitting device exhibiting red, green, or blue light. Further, in this embodiment, by applying the RESTI structure, it was possible to manufacture a light emitting device having a long drive life in both fluorescence emission and phosphorescence emission.
- the three light emitting devices produced in this example have light emitting layers containing materials different from each other.
- the three light emitting devices include a layer using the same material and a layer using the same material and having the same film thickness. Therefore, in the production of the display device of one aspect of the present invention, it was suggested that a common layer is provided for the light emitting devices of three colors, and the light emitting device having a long drive life can be produced with a small number of production steps.
- the mixture was heated to 60 ° C., 23.3 mg of palladium (II) acetate and 66.4 mg of di (1-adamantyl) -n-butylphosphine were added, and the mixture was stirred at 120 ° C. for 27 hours.
- Water was added to the reaction solution, suction filtration was performed, and the obtained filtrate was washed with water, ethanol, and toluene.
- the filter was dissolved in heated toluene and passed through a filtration aid filled in the order of Celite, Alumina, and Celite.
- the obtained solution was concentrated, dried and recrystallized from toluene to obtain the desired white solid in a yield of 1.28 g and a yield of 74%.
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Abstract
Description
図2A及び図2Bは、表示装置の一例を示す断面図である。
図3は、表示装置の一例を示す断面図である。
図4A~図4Cは、発光デバイスの一例を示す断面図である。
図5A~図5Cは、発光デバイスの発光モデルを説明する概念図である。図5Dは、発光デバイスの時間経過に伴う規格化輝度を説明する図である。
図6A~図6Dは、電子輸送層における第1の物質の濃度を説明する図である。
図7は、表示装置の一例を示す斜視図である。
図8A及び図8Bは、表示装置の一例を示す断面図である。
図9Aは、表示装置の一例を示す断面図である。図9Bは、トランジスタの一例を示す断面図である。
図10Aは、画素の一例を示すブロック図である。図10Bは、画素回路の一例を示す回路図である。
図11AはIGZOの結晶構造の分類を説明する図である。図11Bは石英ガラス基板のXRDスペクトルを説明する図である。図11Cは結晶性IGZO膜のXRDスペクトルを説明する図である。図11Dは石英ガラス基板の極微電子線回折パターンを説明する図である。図11Eは結晶性IGZO膜の極微電子線回折パターンを説明する図である。
図12A、図12Bは、電子機器の一例を示す図である。
図13A~図13Cは、電子機器の一例を示す図である。
図14A、図14Bは、電子機器の一例を示す図である。
図15A~図15Dは、電子機器の一例を示す図である。
図16A~図16Dは、電子機器の一例を示す図である。
図17A~図17Fは、電子機器の一例を示す図である。
図18Aは、電子オンリーデバイスの構造を示す図である。図18Bは、実施例の発光デバイスの構造を示す図である。
図19は、電子オンリーデバイスの電流密度−電圧特性を示す図である。
図20は、直流電源7.0VにおけるZADN:Liq(1:1)の算出されたキャパシタンスCの周波数特性を示す図である。
図21は、直流電圧7.0VにおけるZADN:Liq(1:1)の−ΔBの周波数特性を示す図である。
図22は、各有機化合物における電子移動度の電界強度依存特性を示す図である。
図23は、輝度−電流密度特性を示す図である。
図24は、輝度−電圧特性を示す図である。
図25は、電流効率−輝度特性を示す図である。
図26は、電流密度−電圧特性を示す図である。
図27は、発光スペクトルを示す図である。
図28は、輝度−電流密度特性を示す図である。
図29は、輝度−電圧特性を示す図である。
図30は、電流効率−輝度特性を示す図である。
図31は、電流密度−電圧特性を示す図である。
図32は、発光スペクトルを示す図である。
図33は、輝度−電流密度特性を示す図である。
図34は、輝度−電圧特性を示す図である。
図35は、電流効率−輝度特性を示す図である。
図36は、電流密度−電圧特性を示す図である。
図37は、発光スペクトルを示す図である。
図38は、信頼性試験の結果を示す図である。
図39は、信頼性試験の結果を示す図である。
図40は、信頼性試験の結果を示す図である。
図41は、信頼性試験の結果を示す図である。
本実施の形態では、本発明の一態様の表示装置について図1~図9を用いて説明する。
図1Aに表示装置10Aの断面図を示す。
図1Bに表示装置10Bの断面図を示す。なお、以降の表示装置の説明において、先に説明した表示装置と同様の構成については、説明を省略することがある。
図2Aに表示装置10Cの断面図を示す。
図2Bに表示装置10Dの断面図を示す。
図3に表示装置10Eの断面図を示す。
図4A~図4Cに、本実施の形態の表示装置に用いることができる発光デバイスの一例を示す。
発光デバイスの一対の電極を形成する材料としては、金属、合金、電気伝導性化合物、及びこれらの混合物などを適宜用いることができる。具体的には、In−Sn酸化物(ITOともいう)、In−Si−Sn酸化物(ITSOともいう)、In−Zn酸化物、In−W−Zn酸化物が挙げられる。その他、アルミニウム(Al)、チタン(Ti)、クロム(Cr)、マンガン(Mn)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、ガリウム(Ga)、亜鉛(Zn)、インジウム(In)、スズ(Sn)、モリブデン(Mo)、タンタル(Ta)、タングステン(W)、パラジウム(Pd)、金(Au)、白金(Pt)、銀(Ag)、イットリウム(Y)、ネオジム(Nd)などの金属、及びこれらを適宜組み合わせて含む合金を用いることもできる。その他、上記例示のない元素周期表の第1族または第2族に属する元素(例えば、リチウム(Li)、セシウム(Cs)、カルシウム(Ca)、ストロンチウム(Sr))、ユウロピウム(Eu)、イッテルビウム(Yb)などの希土類金属及びこれらを適宜組み合わせて含む合金、グラフェン等を用いることができる。
正孔注入層121は、第1の化合物及び第2の化合物を有することが好ましい。
正孔輸送層122は、正孔注入層121によって注入された正孔を発光層123に輸送する層である。
発光層は、発光物質を含む層である。発光層は、1種または複数種の発光物質を有することができる。発光物質としては、青色、紫色、青紫色、緑色、黄緑色、黄色、橙色、赤色などの発光色を呈する物質を適宜用いる。また、発光物質として、近赤外光を発する物質を用いることもできる。
電子輸送層124は、陰極102から注入された電子を発光層123に輸送する層である。
電子注入層125は、陰極102からの電子の注入効率を高める層である。陰極102の材料の仕事関数の値と、電子注入層125に用いる材料のLUMO準位の値と、の差は、小さい(0.5eV以内)ことが好ましい。
本実施の形態の表示装置に用いることができる発光デバイスにおける発光モデルについて説明する。
図7に、表示装置100Aの斜視図を示し、図8Aに、表示装置100Aの断面図を示す。
図9Aに、表示装置100Bの断面図を示す。表示装置100Bの斜視図は表示装置100A(図7)と同様である。図9Aには、表示装置100Bの、FPC172を含む領域の一部、回路164の一部、及び、表示部162の一部をそれぞれ切断したときの断面の一例を示す。図9Aでは、表示部162のうち、特に、緑色の光を発する発光デバイス190Gと青色の光を発する発光デバイス190Bを含む領域を切断したときの断面の一例を示す。
本実施の形態では、本発明の一態様の表示装置について図10を用いて説明する。
本実施の形態では、上記の実施の形態で説明したOSトランジスタに用いることができる金属酸化物(酸化物半導体ともいう)について説明する。
まず、酸化物半導体における、結晶構造の分類について、図11Aを用いて説明を行う。図11Aは、酸化物半導体、代表的にはIGZO(Inと、Gaと、Znと、を含む金属酸化物)の結晶構造の分類を説明する図である。
なお、酸化物半導体は、結晶構造に着目した場合、図11Aとは異なる分類となる場合がある。例えば、酸化物半導体は、単結晶酸化物半導体と、それ以外の非単結晶酸化物半導体と、に分けられる。非単結晶酸化物半導体としては、例えば、上述のCAAC−OS、及びnc−OSがある。また、非単結晶酸化物半導体には、多結晶酸化物半導体、擬似非晶質酸化物半導体(a−like OS:amorphous−like oxide semiconductor)、非晶質酸化物半導体、などが含まれる。
CAAC−OSは、複数の結晶領域を有し、当該複数の結晶領域はc軸が特定の方向に配向している酸化物半導体である。なお、特定の方向とは、CAAC−OS膜の厚さ方向、CAAC−OS膜の被形成面の法線方向、またはCAAC−OS膜の表面の法線方向である。また、結晶領域とは、原子配列に周期性を有する領域である。なお、原子配列を格子配列とみなすと、結晶領域とは、格子配列の揃った領域でもある。さらに、CAAC−OSは、a−b面方向において複数の結晶領域が連結する領域を有し、当該領域は歪みを有する場合がある。なお、歪みとは、複数の結晶領域が連結する領域において、格子配列の揃った領域と、別の格子配列の揃った領域と、の間で格子配列の向きが変化している箇所を指す。つまり、CAAC−OSは、c軸配向し、a−b面方向には明らかな配向をしていない酸化物半導体である。
nc−OSは、微小な領域(例えば、1nm以上10nm以下の領域、特に1nm以上3nm以下の領域)において原子配列に周期性を有する。別言すると、nc−OSは、微小な結晶を有する。なお、当該微小な結晶の大きさは、例えば、1nm以上10nm以下、特に1nm以上3nm以下であることから、当該微小な結晶をナノ結晶ともいう。また、nc−OSは、異なるナノ結晶間で結晶方位に規則性が見られない。そのため、膜全体で配向性が見られない。従って、nc−OSは、分析方法によっては、a−like OSや非晶質酸化物半導体と区別が付かない場合がある。例えば、nc−OS膜に対し、XRD装置を用いて構造解析を行うと、θ/2θスキャンを用いたOut−of−plane XRD測定では、結晶性を示すピークが検出されない。また、nc−OS膜に対し、ナノ結晶よりも大きいプローブ径(例えば50nm以上)の電子線を用いる電子線回折(制限視野電子線回折ともいう。)を行うと、ハローパターンのような回折パターンが観測される。一方、nc−OS膜に対し、ナノ結晶の大きさと近いかナノ結晶より小さいプローブ径(例えば1nm以上30nm以下)の電子線を用いる電子線回折(ナノビーム電子線回折ともいう。)を行うと、ダイレクトスポットを中心とするリング状の領域内に複数のスポットが観測される電子線回折パターンが取得される場合がある。
a−like OSは、nc−OSと非晶質酸化物半導体との間の構造を有する酸化物半導体である。a−like OSは、鬆又は低密度領域を有する。即ち、a−like OSは、nc−OS及びCAAC−OSと比べて、結晶性が低い。また、a−like OSは、nc−OS及びCAAC−OSと比べて、膜中の水素濃度が高い。
次に、上述のCAC−OSの詳細について、説明を行う。なお、CAC−OSは材料構成に関する。
CAC−OSとは、例えば、金属酸化物を構成する元素が、0.5nm以上10nm以下、好ましくは、1nm以上3nm以下、またはその近傍のサイズで偏在した材料の一構成である。なお、以下では、金属酸化物において、一つまたは複数の金属元素が偏在し、該金属元素を有する領域が、0.5nm以上10nm以下、好ましくは、1nm以上3nm以下、またはその近傍のサイズで混合した状態をモザイク状、またはパッチ状ともいう。
続いて、上記酸化物半導体をトランジスタに用いる場合について説明する。
ここで、酸化物半導体中における各不純物の影響について説明する。
本実施の形態では、本発明の一態様の電子機器について、図12~図17を用いて説明する。
本参考例では、本発明の一態様の表示装置における、有機化合物のHOMO準位、LUMO準位、及び電子移動度の算出方法について説明する。
本実施例で作製したデバイスR1、デバイスG1、及びデバイスB1は、図18Bに示すように、基板(図示しない)上に第1の電極130が形成され、第1の電極130上に正孔注入層131、正孔輸送層132a、正孔輸送層132b、発光層133、電子輸送層134、及び、電子注入層135が順次積層され、電子注入層135上に第2の電極140が形成された構造を有する。各デバイスは、さらに、第2の電極140上に、バッファ層136を有する。バッファ層136は、第2の電極140(半透過・半反射電極)における表面プラズモンによる光エネルギーの損失を低減する機能を有する。バッファ層136としては、発光デバイスに用いることができる各種有機膜を採用することができる。
デバイスR1、デバイスG1、及びデバイスB1の動作特性について測定した。なお、測定は室温(25℃に保たれた雰囲気)で行った。
次に、各発光デバイスに対する信頼性試験を行った。信頼性試験の結果を図38~図40に示す。図38~図40において、縦軸は初期輝度を100%とした時の規格化輝度(%)を示し、横軸は駆動時間(h)を示す。なお、信頼性試験は、デバイスR1においては電流密度を75mA/cm2に設定し、デバイスG1、B1においては電流密度を50mA/cm2に設定し、各発光デバイスを駆動させた。
各発光デバイスに対する信頼性試験を行った。信頼性試験の結果を図41に示す。図41において、縦軸は初期輝度を100%とした時の規格化輝度(%)を示し、横軸は駆動時間(h)を示す。
本参考例では、実施例1及び実施例2で用いた8−(1,1’−ビフェニル−4−イル)−4−[3−(ジベンゾチオフェン−4−イル)フェニル]−[1]ベンゾフロ[3,2−d]ピリミジン(略称:8BP−4mDBtPBfpm)の合成方法について説明する。
Claims (17)
- 第1の発光デバイス及び第2の発光デバイスを有し、
前記第1の発光デバイスは、第1の電極及び共通電極を有し、
前記第2の発光デバイスは、第2の電極及び前記共通電極を有し、
前記第1の発光デバイスは、前記第1の電極及び前記共通電極のうち陽極として機能する電極側から順に、第1の発光層と、電子輸送層と、を有し、
前記第2の発光デバイスは、前記第2の電極と前記共通電極との間に、第2の発光層を有し、
前記第1の発光層は、第1の色の光を発する第1の有機化合物を有し、
前記第2の発光層は、第2の色の光を発する第2の有機化合物を有し、
前記電子輸送層は、第3の有機化合物と、第1の物質と、を有し、
前記第3の有機化合物は、電子輸送性材料であり、
前記第1の物質は、金属、金属塩、金属酸化物、または有機金属塩であり、
前記電子輸送層は、第1の領域と、第2の領域と、を有し、
前記第1の領域と前記第2の領域とは、前記第1の物質の濃度が互いに異なる、表示装置。 - 請求項1において、
前記第1の領域は、前記第2の領域よりも前記第1の発光層側に位置し、
前記第1の領域は、前記第2の領域に比べて、前記第1の物質の濃度が高い、表示装置。 - 請求項1または2において、
前記第2の発光デバイスは、前記第2の電極と前記共通電極との間に、前記第1の発光デバイスと共通の層を有する、表示装置。 - 請求項1乃至3のいずれか一において、
前記第3の有機化合物は、HOMO準位が−6.0eV以上であり、かつ電界強度[V/cm]の平方根が600における電子移動度が1×10−7cm2/Vs以上5×10−5cm2/Vs以下である、表示装置。 - 請求項1乃至4のいずれか一において、
前記第2の発光層は、さらに、第4の有機化合物及び第5の有機化合物を有し、
前記第4の有機化合物と前記第5の有機化合物は、励起錯体を形成する組み合わせである、表示装置。 - 請求項1乃至5のいずれか一において、
前記第1の発光デバイスは、さらに、正孔注入層を有し、
前記正孔注入層は、前記第1の電極及び前記共通電極のうち陽極として機能する電極に接し、
前記正孔注入層は、第1の化合物及び第2の化合物を有し、
前記第1の化合物は、前記第2の化合物に対する電子受容性を有し、
前記第2の化合物のHOMO準位は、−5.7eV以上−5.4eV以下である、表示装置。 - 請求項6において、
前記第1の発光デバイスは、さらに、第1の正孔輸送層を有し、
前記第1の正孔輸送層は、前記正孔注入層と前記第1の発光層との間に位置し、
前記第1の正孔輸送層は、第3の化合物を有し、
前記第3の化合物のHOMO準位は、前記第2の化合物のHOMO準位以下の値であり、
前記第3の化合物のHOMO準位と前記第2の化合物のHOMO準位との差は、0.2eV以内である、表示装置。 - 請求項7において、
前記第2の化合物及び前記第3の化合物は、それぞれ、カルバゾール骨格、ジベンゾフラン骨格、ジベンゾチオフェン骨格、及びアントラセン骨格のうち少なくとも一つを有する、表示装置。 - 請求項7において、
前記第1の発光デバイスは、さらに、第2の正孔輸送層を有し、
前記第2の正孔輸送層は、前記第1の正孔輸送層と前記第1の発光層との間に位置し、
前記第2の正孔輸送層は、第4の化合物を有し、
前記第4の化合物のHOMO準位は、前記第3の化合物のHOMO準位よりも低い、表示装置。 - 請求項9において、
前記第2の化合物、前記第3の化合物、及び前記第4の化合物は、それぞれ、カルバゾール骨格、ジベンゾフラン骨格、ジベンゾチオフェン骨格、及びアントラセン骨格のうち少なくとも一つを有する、表示装置。 - 請求項1乃至10のいずれか一において、
前記第1の有機化合物は、蛍光発光物質である、表示装置。 - 請求項1乃至11のいずれか一において、
前記第1の色は、青色であり、
前記第2の色は、赤色または緑色である、表示装置。 - 請求項1乃至12のいずれか一において、
前記第1の物質は、アルカリ金属またはアルカリ土類金属を有する、有機金属錯体である、表示装置。 - 請求項1乃至13のいずれか一において、
前記第1の物質は、窒素及び酸素を有する配位子と、アルカリ金属またはアルカリ土類金属と、を有する有機金属錯体である、表示装置。 - 請求項1乃至14のいずれか一において、
前記第1の物質は、キノリノール配位子と、アルカリ金属またはアルカリ土類金属と、を有する有機金属錯体である、表示装置。 - 請求項1乃至15のいずれか一に記載の表示装置と、コネクタまたは集積回路と、を有する、表示モジュール。
- 請求項16に記載の表示モジュールと、
アンテナ、バッテリ、筐体、カメラ、スピーカ、マイク、及び操作ボタンのうち、少なくとも一つと、を有する、電子機器。
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