WO2017110549A1 - 発光素子及び表示装置 - Google Patents
発光素子及び表示装置 Download PDFInfo
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- WO2017110549A1 WO2017110549A1 PCT/JP2016/086888 JP2016086888W WO2017110549A1 WO 2017110549 A1 WO2017110549 A1 WO 2017110549A1 JP 2016086888 W JP2016086888 W JP 2016086888W WO 2017110549 A1 WO2017110549 A1 WO 2017110549A1
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- Prior art keywords
- light emitting
- light
- layer
- group
- cathode
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- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
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- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 125000003373 pyrazinyl group Chemical group 0.000 description 1
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- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
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- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical class C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical class C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- 235000021286 stilbenes Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 125000005106 triarylsilyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
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Definitions
- the present disclosure relates to a light emitting element and a display device.
- an organic electroluminescence display device (hereinafter simply referred to as an “organic EL display device”) using an organic electroluminescence element (hereinafter sometimes simply referred to as “organic EL element”). ” May be abbreviated as“) ”.
- the organic EL display device is a self-luminous type, has characteristics of low power consumption, and is considered to have sufficient responsiveness to high-definition high-speed video signals, Development and commercialization for practical application are underway.
- one pixel has a red light emitting layer, a sub-pixel composed of a light emitting element that emits red light, and a light emitting element that has a green light emitting layer and emits green light.
- a red light emitting layer a sub-pixel composed of a light emitting element that emits red light
- a light emitting element that has a green light emitting layer and emits green light.
- a method of forming a white light emitting layer over all pixels and coloring white light using a color filter layer that is, a light emitting element having a white light emitting layer (referred to as “white light emitting element”) and a red color filter layer, A red subpixel (referred to as “red light emitting element”) by a combination of the above, a green subpixel (referred to as “green light emitting element”) by a combination of a white light emitting element and a green color filter layer, a white light emitting element and a blue color filter layer, Development of a technique for forming one pixel from three sub-pixels (light-emitting elements) of blue sub-pixels (referred to as “blue light-emitting elements”) by a combination of the above is underway.
- the white light emitting layer is formed as a continuous layer over the all white light emitting element. Since it is not necessary to form a red light emitting layer, a green light emitting layer, and a blue light emitting layer for each subpixel, the pixel pitch can be reduced.
- the white light-emitting layer is formed between the anode and the cathode, and is composed of two or more light-emitting regions that emit different colors from the anode side to the cathode side (for example, special features). (See Open 2013-258022).
- the chromaticity coordinate values (u ′, v ′) of white light emitted from the white light emitting element greatly change depending on the amount of current (current density) flowing between the anode and the cathode.
- Such a phenomenon is considered to be caused by a difference in carrier mobility in each of two or more light emitting regions that emit light of different colors formed from the anode side to the cathode side, and in a recombination region in the light emitting region.
- a color change occurs between an image in a region where the current density is high and an image in a region where the current density is low. There arises a problem of causing a decrease.
- an object of the present disclosure is to provide a light-emitting element having a configuration in which a color change depending on a current density hardly occurs, and a display device using the light-emitting element.
- the light-emitting element according to the first to third aspects of the present disclosure for achieving the above object has a structure in which an anode, an organic material, an organic layer including a light-emitting layer, and a cathode are stacked.
- the light emitting layer is composed of two or more light emitting regions that emit different colors from the anode side to the cathode side, and each light emitting region includes a host material and a dopant material (guest material).
- the absolute value of the ionization potential of the host material included in the light emitting region close to the cathode is greater than the absolute value of the ionization potential of the host material included in the light emitting region close to the anode. Is also big.
- the difference ⁇ u′v ′ from the chromaticity coordinate value of white light emitted from the light emitting layer when a current of 50 mA / cm 2 is passed between the anode and the cathode is 0.02 or less.
- the host material included in the light emitting region adjacent to the cathode suppresses the movement of holes from the light emitting region adjacent to the light emitting region adjacent to the cathode.
- a display device for achieving the above object includes a plurality of light emitting elements according to the first to third aspects of the present disclosure arranged in a two-dimensional matrix.
- the relationship between the ionization potential values of the light emitting regions is defined.
- the current density The amount of change ⁇ u′v ′ of the chromaticity coordinate value of white light based on the above is defined, and in the light emitting device according to the third aspect of the present disclosure, the host material included in the light emitting region adjacent to the cathode Therefore, depending on the amount of current (current density) flowing between the anode and the cathode, the chromaticity coordinate value of the white light emitted from the white light emitting element hardly changes.
- the effects described in the present specification are merely examples and are not limited, and may have additional effects.
- FIG. 1 is a schematic partial cross-sectional view of the light emitting device of Example 1.
- FIG. FIG. 2 is a schematic partial cross-sectional view of the display device according to the second embodiment.
- 3A is a schematic partial cross-sectional view of a light emitting layer and an energy level diagram of the light emitting layer in the light emitting device of Example 1, respectively.
- 3B is a schematic partial cross-sectional view of a light emitting layer and an energy level diagram of the light emitting layer in the light emitting device of Example 1, respectively.
- FIG. 4 is a graph showing changes in ⁇ u′v ′ depending on the current density when a current of 50 mA / cm 2 is passed between the anode and the cathode in the light emitting device of Example 1.
- Example 1 Light Emitting Element According to First to Third Aspects of Present Disclosure, and Display Device of Present Disclosure
- Example 2 Modification of Example 1 4).
- the light-emitting element according to the first aspect of the present disclosure or the light-emitting element according to the first aspect of the present disclosure constituting the display device of the present disclosure (hereinafter, these light-emitting elements are collectively referred to as “the first of the present disclosure.
- the absolute value of the ionization potential of the host material included in the light emitting region adjacent to the cathode can be set to 6.1 eV or more.
- the absolute value of the ionization potential of the host material included in the light emitting region adjacent to the cathode is
- the absolute value of the ionization potential of the host material included in the light emitting region adjacent to the light emitting region adjacent to the cathode is preferably satisfied ⁇ 0.1
- the band gap value of the host material contained in the light emitting region adjacent to the cathode is preferably 3.1 eV or more.
- the present disclosure that constitutes the light emitting element according to the second to third aspects of the present disclosure, such as the light emitting element according to the first aspect of the present disclosure including the preferred embodiments described above, or the display device of the present disclosure.
- the host material in the light-emitting region adjacent to the cathode is azine. It can be made into the form which consists of a system compound. The azine compound will be described later.
- the light-emitting layer can be configured to emit white light.
- the light emitting region is a region where holes injected from the anode side and electrons injected from the cathode side recombine when a voltage is applied to the anode and the cathode.
- the arrangement order of the light emitting regions that emit light of each color in the light emitting layer may be appropriately determined based on the carrier transportability of each light emitting region, the adjustment of the optical path length according to the emission wavelength of light extraction, and the like.
- the light emitting layer is the form comprised from the anode side to the cathode side, and is comprised from the 1st light emission area
- the first light emitting region emits red light (wavelength: 620 nm to 750 nm)
- the second light emitting region emits green light (wavelength: 495 nm to 570 nm)
- the third light emitting region emits blue light (wavelength: 450 nm to 450 nm). 495 nm) to emit white light as a whole.
- the first light-emitting region may emit red light
- the second light-emitting region may emit blue light
- the third light-emitting region may emit green light
- white light may be emitted as a whole.
- the light emitting layer can be formed from the first light emitting region and the second light emitting region from the anode side to the cathode side.
- the first light emitting region emits blue light
- the second light emitting region emits yellow light
- white light can be emitted as a whole.
- the first light-emitting region can emit yellow light
- the second light-emitting region can emit blue light
- white light can be emitted as a whole.
- the first light-emitting region emits blue light
- the second light-emitting region emits orange light
- white light can be emitted as a whole.
- the first light emitting region emits orange light
- the second light emitting region emits blue light
- white light can be emitted as a whole.
- the combination of the above emission colors is an example, and may be appropriately determined according to the color gamut set as the light emitting element or the display device. Actually, there are cases where light emitting areas emitting different colors are mixed and not clearly separated into the respective light emitting areas.
- an intermediate region is provided between the first light emitting region and the second light emitting region. (Buffer region) may be provided. The intermediate area (buffer area) will be described later.
- Such a white light emitting element includes a red color filter layer to form a red light emitting element, and the white light emitting element includes a green color filter layer to configure a green light emitting element.
- the blue light emitting element is configured by the white light emitting element including the blue color filter layer.
- One pixel is constituted by the red light emitting element, the green light emitting element, and the blue light emitting element. In some cases, one pixel may be constituted by a red light emitting element, a green light emitting element, a blue light emitting element, and a white light emitting element (or a light emitting element that emits complementary color light).
- one pixel is configured by one light-emitting element (display element), but is not limited thereto, but is an array of pixels (or sub-pixels).
- a stripe arrangement, a diagonal arrangement, a delta arrangement, or a rectangle arrangement can be given.
- the arrangement of pixels (or subpixels) is not limited, A stripe arrangement can be mentioned.
- the color filter layer is composed of a resin to which a colorant composed of a desired pigment or dye is added.
- a colorant composed of a desired pigment or dye
- the light transmittance in the target wavelength range such as red, green, and blue can be obtained. It is high and is adjusted so that the light transmittance in other wavelength regions is low.
- a transparent filter may be provided.
- a black matrix layer (light shielding layer) may be formed between the color filter layer and the color filter layer.
- the black matrix layer is, for example, a black resin film having an optical density of 1 or more mixed with a black colorant (specifically, made of, for example, a black polyimide resin), or a thin film filter using thin film interference.
- the thin film filter is formed, for example, by stacking two or more thin films made of metal, metal nitride, or metal oxide, and attenuates light by utilizing interference of the thin film.
- Specific examples of the thin film filter include one in which Cr and chromium oxide (III) (Cr 2 O 3 ) are alternately laminated.
- the light-emitting element may be formed of an organic electroluminescence element (organic EL element).
- the display apparatus of this indication including the various preferable forms demonstrated above can be set as the structure which consists of an organic electroluminescent display apparatus (organic EL display apparatus).
- the display device of the present disclosure includes a first substrate, a second substrate, and an image display unit sandwiched between the first substrate and the second substrate.
- a plurality of light-emitting elements according to the first to third aspects of the present disclosure including the preferred embodiments described above are arranged in a two-dimensional matrix.
- a light emitting element is formed on the first substrate side.
- a first electrode is formed on the first substrate side, and a second electrode is formed on the second substrate side.
- the anode may correspond to the first electrode and the cathode may correspond to the second electrode, and conversely, the anode may correspond to the second electrode and the cathode may correspond to the first electrode.
- the thickness of the entire organic layer can be exemplified as 1.2 ⁇ 10 ⁇ 7 m to 2 ⁇ 10 ⁇ 7 m. Further, as the thickness of the light emitting region, a thickness on the order of 10 ⁇ 8 m, for example, a thickness of 1 ⁇ 10 ⁇ 8 m can be exemplified. More specifically, the film thickness of the red light emitting region can be 5 nm to 15 nm, the film thickness of the green light emitting region can be 5 nm to 15 nm, and the film thickness of the blue light emitting region can be 5 nm. Although ⁇ 15 nm can be exemplified, it is not limited thereto.
- the organic layer and the second electrode are formed in a plurality of light emitting elements.
- a common form can be adopted.
- One or more hole supply layers (also referred to as a hole injection layer or a hole transport layer) or the like may be formed in a region (hole transport region) between the anode and the light emitting region adjacent to the anode.
- One or more electron transport layers (also referred to as an electron injection layer or an electron supply layer) or the like may be formed in a region (electron transport region) between the cathode and the light emitting region adjacent to the cathode.
- the organic layer may partially contain an inorganic compound. The hole transport region and the electron transport layer will be described later.
- a light emitting region adjacent to the anode means a light emitting region located closest to the anode, and does not mean that the light emitting region is in direct contact with the anode.
- a light emitting region adjacent to the cathode means a light emitting region located closest to the cathode, and does not mean that the light emitting region is in direct contact with the cathode.
- the light emitting region adjacent to the cathode is “light emitting region-A” and the light emitting region adjacent to the light emitting region is “light emitting region-B”, the light emitting region is directed from the cathode side toward the anode side. -A and light emitting region -B are provided in this order.
- An organic layer made of an organic material includes a light emitting layer. Specifically, for example, a stacked structure of a hole transport layer, a light emitting layer, and an electron transport layer, a hole injection layer, a hole transport layer, and a light emitting layer. It can be composed of a laminated structure of a layer, an electron transport layer, and an electron injection layer.
- a physical vapor deposition method such as a vacuum deposition method
- a printing method such as a screen printing method or an ink jet printing method
- a laser absorption layer formed on a transfer substrate Examples of the laser transfer method and various coating methods include separating the organic layer on the laser absorption layer by irradiating a laser on the laminated structure of the organic layer and transferring the organic layer.
- a vacuum evaporation method for example, using a so-called metal mask
- an organic layer can be obtained by depositing a material that has passed through an opening provided in the metal mask. It is preferable to form the entire surface without patterning.
- At least a part of the organic layer may be in a discontinuous state.
- PVD methods such as a vacuum evaporation method, can be illustrated.
- the thickness of the hole transport layer (hole supply layer) and the thickness of the electron transport layer (electron supply layer) are substantially equal.
- the electron transport layer (electron supply layer) may be thicker than the hole transport layer (hole supply layer), which is necessary for high efficiency with a low driving voltage and sufficient for the light emitting layer.
- Electronic supply is possible. That is, it is possible to increase the supply of holes by disposing a hole transport layer between the anode and the light emitting layer and forming it with a film thickness thinner than that of the electron transport layer. As a result, there is no excess or deficiency of holes and electrons, and a carrier balance with a sufficiently large amount of carrier supply can be obtained, so that high luminous efficiency can be obtained. In addition, since there is no excess or deficiency of holes and electrons, carrier balance is not easily lost, driving deterioration is suppressed, and the light emission life can be extended.
- the substrate includes a silicon semiconductor substrate on which a transistor (specifically, for example, a MOSFET) is formed and an interlayer insulating layer formed thereon, or the substrate is a transistor (specifically, for example, a thin film transistor). , TFT) and an interlayer insulating layer formed thereon, The first electrode and the first insulating layer are formed on the interlayer insulating layer, The first electrode and the transistor formed on the silicon semiconductor substrate (or substrate) can be connected to each other through a contact hole formed in the interlayer insulating layer.
- a transistor specifically, for example, a MOSFET
- TFT thin film transistor
- the display device of the present disclosure can be a top emission type (upper surface light emission type) display device (upper surface light emission type display device) that emits light from the second substrate, or alternatively, the light can be emitted from the first substrate.
- the bottom emission type (bottom emission type) display device (bottom emission type display device) can be used.
- a color filter layer and a black matrix layer may be formed on the surface side of the second substrate facing the first substrate.
- a color filter layer and a black matrix layer may be formed on the surface side of the first substrate facing the second substrate.
- the silicon semiconductor substrate (or substrate) corresponds to the first substrate.
- the first substrate or the second substrate is a high strain point glass substrate, a soda glass (Na 2 O ⁇ CaO ⁇ SiO 2 ) substrate, a borosilicate glass (Na 2 O ⁇ B 2 O 3 ⁇ SiO 2 ) substrate, a forsterite ( 2MgO ⁇ SiO 2 ) substrate, lead glass (Na 2 O ⁇ PbO ⁇ SiO 2 ) substrate, various glass substrates with an insulating film formed on the surface, quartz substrate, quartz substrate with an insulating film formed on the surface, silicon semiconductor substrate , Silicon semiconductor substrate with an insulating film formed on the surface, polymethyl methacrylate (polymethyl methacrylate, PMMA), polyvinyl alcohol (PVA), polyvinylphenol (PVP), polyethersulfone (PES), polyimide, polycarbonate (PC) , Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene naphth An organic polymer exemplified by a
- the materials constituting the first substrate and the second substrate may be the same or different.
- the second substrate is required to be transparent to the light from the light emitting element.
- the first substrate is from the light emitting element. It is required to be transparent to light.
- the substrate is composed of an organic polymer, it is preferable to have a laminated structure or to perform surface treatment in order to suppress water permeability and gas permeability.
- the first electrode functions as an anode (anode electrode) as the material constituting the first electrode
- an electrode material having a large work function from the vacuum level in order to inject holes efficiently.
- platinum (Pt), gold (Au), silver (Ag), silver (Ag) alloy, chromium (Cr), tungsten (W), nickel (Ni), copper (Cu), iron ( Fe or cobalt (Co), tantalum (Ta), molybdenum (Mo), titanium (Ti) high work function metal or alloy for example, silver as a main component, 0.3 mass% to 1 mass% palladium (Ag—Pd—Cu alloy, Al—Nd alloy, Al—Ni alloy) containing (Pd) and 0.3 mass% to 1 mass% of copper (Cu).
- Examples of the thickness of the first electrode include 0.1 ⁇ m to 1 ⁇ m.
- transparent conductive materials having excellent hole injection characteristics such as indium and tin oxide (ITO), indium and zinc oxide (IZO), tin and antimony oxide, and zinc and aluminum oxide. Holes such as oxides of indium and tin (ITO) and oxides of indium and zinc (IZO) on a highly light reflective reflective film such as a dielectric multilayer film or aluminum (Al)
- a structure in which transparent conductive materials having excellent injection characteristics are laminated may also be used.
- a laminated structure of a first layer having excellent light reflectivity and a second layer having light transmittance and a large work function can be used.
- the second layer is located on the organic layer side.
- the first layer is preferably made of an aluminum alloy mainly composed of aluminum (Al).
- Al aluminum
- the work function of the lanthanoid series elements is not large, but the inclusion of these elements improves the stability of the first electrode and also improves the hole injection property of the first electrode.
- elements such as silicon (Si), copper (Cu), nickel (Ni), titanium (Ti), etc. may be used as subcomponents.
- the content of subcomponents in the aluminum alloy constituting the first layer of the first electrode is, for example, about 10 in total in the case of neodymium (Nd), nickel (Ni), titanium (Ti), or the like that stabilizes aluminum. It is preferable that it is below mass%. Accordingly, the first layer can be stably maintained in the manufacturing process of the light emitting element while maintaining the reflectance of the first layer made of the aluminum alloy. Further, high processing accuracy and chemical stability can be obtained. Furthermore, the conductivity of the first electrode is also improved. Since metals such as neodymium (Nd) have a small work function, the use of amine-based materials generally used for the hole supply layer increases the hole injection barrier.
- an acceptor material such as 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (F4-TCNQ) is mixed with the amine-based material, or polyethylene
- F4-TCNQ 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane
- PEDOT-PSS oxythiophene-polystyrene sulfonic acid
- the hole injection barrier is reduced, and an increase in driving voltage can be suppressed.
- an azatriphenylene derivative the light emitting element can be stabilized while suppressing an increase in driving voltage.
- the second layer of the first electrode is composed of an oxide of an Al alloy, an oxide of molybdenum (Mo), an oxide of zirconium (Zr), an oxide of chromium (Cr), and an oxide of tantalum (Ta). can do.
- the second layer is composed of an oxide layer of an aluminum alloy containing a lanthanoid series element as an accessory component (including a natural oxide film)
- the oxide of the lanthanoid series element has a high light transmittance.
- the transmittance of light of the second layer containing the is improved. As a result, the reflectance on the surface of the first layer is maintained high.
- the electron injection characteristic of the first electrode can be improved by forming the second layer from a transparent conductive layer such as ITO or IZO.
- a transparent conductive layer such as ITO or IZO.
- ITO and IZO have a large work function, the carrier injection efficiency can be increased by using it for the first layer.
- the first electrode when the first electrode functions as a cathode (cathode electrode), it is desirable that the first electrode is made of a conductive material having a small work function value and high light reflectance. It can also be used as a cathode by improving electron injection properties by providing an appropriate electron injection layer in a highly conductive material.
- the second electrode functions as a cathode (cathode electrode) as a material constituting the second electrode (semi-light transmissive material or light transmissive material), the luminescent light is transmitted and electrons are efficiently transmitted to the organic layer.
- a cathode cathode electrode
- silver Ag
- magnesium Mg
- calcium Ca
- sodium Na
- strontium Sr
- the second electrode examples include 4 nm to 50 nm, preferably 4 nm to 20 nm, and more preferably 6 nm to 12 nm.
- the second electrode is laminated from the organic layer side with the material layer described above and a so-called transparent electrode made of, for example, ITO or IZO (for example, a thickness of 3 ⁇ 10 ⁇ 8 m to 1 ⁇ 10 ⁇ 6 m). It can also be a structure.
- the second electrode can be composed of a mixed layer containing an organic light emitting material such as an aluminum quinoline complex, a styrylamine derivative, or a phthalocyanine derivative. In this case, a light-transmitting layer such as Mg—Ag may be further provided.
- the average light transmittance of the second electrode is 50% to 90%, preferably 60% to 90%.
- the second electrode may have a two-layer structure.
- the first layer is formed of a material having a small work function and good light transmittance. It is preferable.
- the material constituting the first layer for example, Li 2 O, Cs 2 Co 3 , Cs 2 SO 4 , MgF, alkali metal oxides such as LiF and CaF 2 , alkali metal fluorides, alkaline earths, etc. Metal oxides and alkaline earth fluorides.
- the second electrode when the second electrode is made to function as an anode (anode electrode), it is desirable that the second electrode is made of a conductive material that transmits luminescent light and has a large work function value.
- a bus electrode (auxiliary electrode) made of a low-resistance material such as aluminum, aluminum alloy, silver, silver alloy, copper, copper alloy, gold, or gold alloy is provided for the second electrode, thereby reducing the resistance of the second electrode as a whole. You may plan.
- Examples of methods for forming the anode and cathode include, for example, electron beam evaporation, hot filament evaporation, evaporation including vacuum evaporation, sputtering, and chemical vapor deposition (CVD). , MOCVD, combination of ion plating and etching; various printing methods such as screen printing, ink jet printing, metal mask printing; plating (electroplating and electroless plating); lift-off method; laser ablation Sol-gel method and the like. According to various printing methods and plating methods, it is possible to directly form an anode or cathode (first electrode or second electrode) having a desired shape (pattern).
- CVD chemical vapor deposition
- the second electrode When the second electrode is formed after the organic layer is formed, the second electrode may be formed on the basis of a film forming method having a small energy of film forming particles such as a vacuum evaporation method or a film forming method such as an MOCVD method. From the viewpoint of preventing damage to the organic layer. When the organic layer is damaged, there is a possibility that a non-light emitting pixel (or non-light emitting sub-pixel) called a “dark spot” is generated due to generation of a leak current. Further, it is preferable to perform the formation from the formation of the organic layer to the formation of these electrodes without exposure to the atmosphere from the viewpoint of preventing the deterioration of the organic layer due to moisture in the atmosphere. As described above, the second electrode does not need to be patterned and can be a so-called common electrode.
- the first electrode is provided on the interlayer insulating layer.
- the interlayer insulating layer covers the light emitting element driving unit formed on the first substrate (or on the first substrate).
- the light emitting element driving unit is composed of one or a plurality of transistors (for example, MOSFET and TFT), and the transistor and the first electrode are electrically connected via a contact hole (contact plug) provided in the interlayer insulating layer. It is connected to the.
- the light emitting element driving unit can have a known circuit configuration.
- known processes such as a CVD method, a coating method, a sputtering method, and various printing methods can be used.
- the protective film is less affected by the formation of the protective film, particularly by a film forming method such as a vacuum vapor deposition method with a small energy of film forming particles or a film forming method such as a CVD method or a MOCVD method. This is preferable.
- the film forming temperature is set to room temperature, and further, in order to prevent the protective film from peeling off, the protective film is used under the condition that the stress of the protective film is minimized. It is desirable to form a film.
- the protective film is preferably formed without exposing the already formed electrode to the atmosphere, whereby the organic layer can be prevented from being deteriorated by moisture or oxygen in the atmosphere.
- the protective film is preferably made of a material that transmits, for example, 80% or more of the light generated in the light emitting layer.
- an inorganic amorphous insulating material for example, the following materials is exemplified. can do. Since such an inorganic amorphous insulating material does not generate grains, it has low water permeability and constitutes a good protective film.
- amorphous silicon ⁇ -Si
- amorphous silicon carbide ⁇ -SiC
- amorphous silicon nitride ⁇ -Si 1-x N x
- amorphous silicon oxide ⁇ -Si 1-y O y
- amorphous carbon ⁇ -C
- ⁇ -SiON amorphous oxide / silicon nitride
- Al 2 O 3 amorphous oxide / silicon nitride
- the protective film may be made of a transparent conductive material such as ITO or IZO.
- the protective film and the second substrate are bonded via, for example, a resin layer (sealing resin layer).
- Thermosetting adhesives such as acrylic adhesives, epoxy adhesives, urethane adhesives, silicone adhesives, cyanoacrylate adhesives, and ultraviolet curable adhesives are used as the material for the resin layer (sealing resin layer). Mention may be made of adhesives.
- An ultraviolet absorbing layer, a contamination prevention layer, a hard coat layer, and an antistatic layer may be formed on the outermost surface of the display device (the outer surface of the second substrate), or a protective member may be provided.
- the display device may include a resonator structure in order to further improve the light extraction efficiency.
- the first electrode is constituted by an interface between the first electrode and the organic layer (or an interface between the light reflection layer provided below the first electrode via an interlayer insulating layer and the interlayer insulating layer).
- the light emitted from the light emitting layer is resonated between the interface and the second interface constituted by the interface between the second electrode and the organic layer, and a part thereof is emitted from the second electrode.
- the distance from the maximum light emission position of the light emitting layer to the first interface is L 1
- the optical distance is OL 1
- the distance from the maximum light emission position of the light emitting layer to the second interface is L 2
- the optical distance is OL 2 , m
- ⁇ Maximum peak wavelength of the spectrum of light generated in the light emitting layer (or a desired wavelength in the light generated in the light emitting layer)
- ⁇ 1 Phase shift amount of light reflected from the first interface (unit: radians)
- -2 ⁇ ⁇ 1 ⁇ 0 ⁇ 2 Phase shift amount of light reflected by the second interface (unit: radians)
- the distance L 1 from the maximum light emitting position of the light emitting layer to the first interface refers to the actual distance (physical distance) from the maximum light emitting position of the light emitting layer to the first interface, and from the maximum light emitting position of the light emitting layer.
- the distance L 2 to the second interface refers to the actual distance (physical distance) from the maximum light emission position of the light emitting layer to the second interface.
- the optical distance is also called an optical path length, and generally indicates n ⁇ L when a light beam passes through a medium having a refractive index n by a distance L. The same applies to the following.
- the average refractive index n ave is the sum of the refractive index and thickness products of each layer constituting the organic layer (or organic layer and interlayer insulating layer), and the organic layer (or organic layer and interlayer insulating layer). ) Divided by the thickness.
- the first electrode, the second electrode, and the light reflecting layer absorb a part of the incident light and reflect the rest. Therefore, a phase shift occurs in the reflected light.
- the phase shift amounts ⁇ 1 and ⁇ 2 are obtained by measuring the values of the real part and the imaginary part of the complex refractive index of the material constituting the first electrode, the second electrode, and the light reflecting layer, for example, using an ellipsometer. It can be obtained by performing a calculation based on the value (see, for example, “Principles of Optic”, Max Born and Emil Wolf, 1974 (PERGAMON PRESS)).
- the refractive index of the organic layer and various interlayer insulating layers can also be determined by measuring using an ellipsometer.
- a red light emitting element configured by a white light emitting element including a red color filter layer actually emits red light emitted from the light emitting layer. Resonate and emit reddish light (light having a light spectrum peak in the red region) from the second electrode.
- the green light-emitting element configured by including the green color filter layer in the white light-emitting element resonates the green light emitted from the light-emitting layer and has greenish light (having a light spectrum peak in the green region). Light) is emitted from the second electrode.
- a blue light-emitting element configured by including a blue color filter layer in a white light-emitting element resonates blue light emitted from the light-emitting layer to produce bluish light (a peak of the light spectrum in the blue region).
- Light is emitted from the second electrode. That is, a desired wavelength ⁇ (specifically, a red wavelength, a green wavelength, and a blue wavelength) of the light generated in the light emitting layer is determined, and the equations (A-1) and (A-2) Based on the formulas (A-3) and (A-4), various parameters such as OL 1 and OL 2 in the red light emitting element, the green light emitting element, and the blue light emitting element are obtained, and each light emitting element is designed. That's fine.
- aluminum As a material constituting the light reflecting layer, aluminum, aluminum alloy (eg, Al—Nd), Ti / Al laminated structure, chromium (Cr), silver (Ag), silver alloy (eg, Ag—Pd—Cu, Ag—) Sm-Cu), for example, electron beam evaporation method, hot filament evaporation method, evaporation method including vacuum evaporation method, sputtering method, CVD method or ion plating method; plating method (electroplating method or electroless method) Plating method); lift-off method; laser ablation method; sol-gel method or the like.
- the intermediate region contains, for example, a compound represented by the following formula (1).
- Ar 1 to Ar 3 are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. It is a cyclic group. However, any one of Ar 1 and Ar 2 , Ar 1 and Ar 3 , and Ar 2 and Ar 3 are combined to form a substituted or unsubstituted nitrogen-containing complex containing a nitrogen atom in formula (1). A ring may be formed. Examples of nitrogen-containing heterocycles include carbazole rings.
- the “ring-forming carbon” means a carbon atom constituting a saturated ring, an unsaturated ring or an aromatic ring
- the “ring-forming atom” means a hetero ring (including a saturated ring, an unsaturated ring and an aromatic ring).
- At least one of Ar 1 , Ar 2 and Ar 3 in the formula (1) is a heterocyclic group represented by the following formula (2). That is, the compound of Formula (1) has one or more dibenzofuran rings or dibenzothiophene rings.
- X is an oxygen atom or a sulfur atom.
- Y 1 ⁇ Y 8 is a carbon atom, one of Y 1 ⁇ Y 8 is a carbon atom bonded with L 1.
- L 1 is a linking group bonded to the nitrogen atom in formula (1), and is a single bond or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms. Seven of Y 1 to Y 8 other than the carbon atom bonded to L 1 are each a carbon atom bonded to the following R, or form a substituted or unsubstituted ring containing adjacent carbon atoms. .
- R represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, or a substituted or unsubstituted trialkyl having 3 to 10 carbon atoms.
- Silyl group substituted or unsubstituted ring aryl carbon group having 18 to 30 carbon atoms, substituted or unsubstituted alkyl aryl silyl group having 8 to 15 carbon atoms (provided that the aryl moiety has 6 to 14 ring carbon atoms) ), A substituted or unsubstituted aryl group having 6 to 16 ring carbon atoms, a substituted amino group, a group having a substituted amino group, a halogen atom, or a cyano group.
- a benzene ring etc. can be mentioned as a ring containing an adjacent carbon atom.
- intermediate region In the intermediate region (intermediate layer), electrons are blocked at the interface between the light emitting region located on the cathode side with respect to the intermediate region (referred to as “cathode side light emitting region” for convenience) and the intermediate region.
- cathode side light emitting region In the anode side light emitting region, the electron emission efficiency is improved and the electrons are sufficiently moved to the light emitting region located on the anode side with respect to the intermediate region (referred to as “anode side light emitting region” for convenience). It is desirable to improve the luminous efficiency of the cathode side light emission and to prevent the cathode side light emission region from deteriorating at the interface between the cathode side light emission region and the intermediate region.
- the properties required for the material constituting such an intermediate region include a hole-transport property, a sufficient energy gap, and a sufficient LUMO standard to block electrons to the cathode-side light-emitting region. And has a sufficient energy gap to confine the emission energy of the light emitting region, and in addition, has a property of having an appropriate electron transport capability while having a hole transportability. it can.
- the compound of the formula (1) is an amine compound having a dibenzofuran structure or a dibenzothiophene structure. Since this compound has dibenzofuran or dibenzothiophene, it has a large energy gap and is suitable for confining exciton energy. That is, when an amine compound having dibenzofuran or dibenzothiophene as in formula (1) is used as an intermediate region, high luminous efficiency can be obtained by confining exciton energy, and the transport of holes and the transport of electrons are balanced. The light emission of two or more light emitting regions can be obtained with good balance. In addition, since the electron density is high, there is an effect of promoting electron transport.
- the compound of Formula (1) is an amine compound, it has hole transportability. That is, since the intermediate region made of the compound represented by the formula (1) has both functions of blocking and moving electrons in a well-balanced manner, it blocks electrons at the interface between the cathode side light emitting region and the intermediate region. Further, the electrons are sufficiently transferred to the anode side light emitting region. For this reason, electrons are not accumulated at the interface between the intermediate region and the cathode side light emitting region, and the light emitting region is hardly deteriorated and a long-life light emitting element can be realized.
- the film thickness of the intermediate region can be set thick, and furthermore, the change in the light emission balance of each color with respect to the film thickness variation of the intermediate region is small.
- a film thickness margin in the intermediate region can be increased, and a light-emitting element with high mass productivity can be realized.
- a combination of the optimal light emitting region and the carrier transport property can realize a light emitting element in which all the light emitting regions emit light in a well-balanced manner.
- the aromatic hydrocarbon group having 6 to 50 ring carbon atoms preferably has 6 to 20 ring carbon atoms, more preferably 6 to 16 ring carbon atoms, and particularly preferably 6 to 12 ring carbon atoms. It is.
- monovalent aromatic hydrocarbon groups aryl groups
- the aromatic hydrocarbon group having a substituent include
- Examples of the aromatic hydrocarbon group represented by L 1 include a divalent group in which one hydrogen atom of the monovalent aromatic hydrocarbon group is a single bond.
- the aromatic hydrocarbon group represented by R is an aromatic hydrocarbon group having 6 to 16 ring carbon atoms among the above aromatic hydrocarbon groups.
- the heterocyclic group having 5 to 30 ring atoms preferably has 5 to 20 ring atoms, and more preferably 5 to 14 ring atoms.
- monovalent aromatic heterocyclic groups include pyrrolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridyl, triazinyl, indolyl, isoindolyl, imidazolyl, and benzimidazolyl.
- indazolyl group imidazo [1,2-a] pyridinyl group, furyl group, benzofuranyl group, isobenzofuranyl group, dibenzofuranyl group, azadibenzofuranyl group, thiophenyl group, benzothiophenyl group, dibenzothiophenyl Group, azadibenzothiophenyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, quinazolinyl group, naphthyridinyl group, carbazolyl group, azacarbazolyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, phenazinyl group, phenothiadi Group, phenoxazinyl group, oxazolyl group, oxadiazolyl group, furazanyl group, benzoxazolyl group, thienyl group, thieny
- alkyl group having 1 to 10 carbon atoms examples include linear and branched alkyl groups.
- linear and branched alkyl groups methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group N-heptyl group, n-octyl group, etc., preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group. More preferred examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, and a t-butyl group.
- Examples of the cycloalkyl group having 3 to 10 ring carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, and a 2-norbornyl group.
- a cyclopentyl group and a cyclohexyl group can be mentioned.
- the trialkylsilyl group having 3 to 10 carbon atoms is represented as —Si (R a ) (R b ) (R c ), and is described above as an example of (R a ), (R b ) and (R c ).
- An alkyl group can be mentioned. Specific examples include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, and a propyldimethylsilyl group.
- a triarylsilyl group having 18 to 30 ring carbon atoms is represented as —Si (Ar a ) (Ar b ) (Ar c ), and examples of (Ar a ), (Ar b ) and (Ar c ) include The aryl group mentioned above can be mentioned. Specific examples include a triphenylsilyl group.
- Examples of the alkylarylsilyl group having 8 to 15 carbon atoms include a dialkylarylsilyl group and an alkyldiarylsilyl group.
- the dialkylarylsilyl group is represented by —Si (R a ) (R b ) (Ar c ), and examples of (R a ) and (R b ) include the alkyl groups described above, and (Ar c )
- the above-mentioned aromatic hydrocarbon group can be mentioned. Specific examples include a phenyldimethylsilyl group.
- the alkyldiarylsilyl group is represented by —Si (R a ) (Ar b ) (Ar c ), and examples of (R a ) include the alkyl groups described above. Examples of (Ar b ) and (Ar c ) As mentioned above, the aryl group mentioned above can be mentioned. Specific examples include a methyldiphenylsilyl group.
- the substituted amino group is represented by —N (Ar a ) (Ar b ), and examples of (Ar a ) and (Ar b ) include the aryl group and heteroaryl group described above. Specific examples include a diphenylamino group, a dibiphenylamino group, and a dibenzofuranylbiphenylamino group. Examples of the group having a substituted amino group include an aryl group substituted with the substituted amino group.
- halogen atoms include F, Cl, Br, and I.
- each group of the compound represented by the formula (1) As a substituent of each group of the compound represented by the formula (1), the above alkyl group, cycloalkyl group, substituted silyl group, aromatic hydrocarbon group, heterocyclic group, halogen atom, alkoxy group, aralkyl Group, silyl group, hydroxyl group, nitro group, cyano group, carboxy group, aryloxy group, substituted amino group and the like. “Unsubstituted” means that hydrogen atoms are bonded.
- one or more of Ar 1 , Ar 2 , Ar 3 are bonded to a group having a substituted amino group, or a substituted or unsubstituted carbazole group, so that a diamine compound or a triamine compound It may be a compound that forms Examples of the group having a substituted amino group include the above-described substituted or unsubstituted aromatic hydrocarbon group or a group having an amino group having a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. it can.
- a diphenylamino group, a dibiphenylamino group, a dibenzofuranylbiphenylamino group, or a substituted amino group thereof is an aromatic hydrocarbon group (benzene, naphthalene, anthracene, 9,9-dimethylfluorenyl group). Etc.).
- JP-A-2006-151844, JP-A-2008-021687, WO2007-125714, WO2010-061824, and JP-A-2005-112765 can be referred to.
- the thickness of the intermediate region is 0.1 nm to 20 nm, preferably 5 nm to 10 nm.
- the compound represented by the formula (1) as an intermediate region, the electrons at the interface between the cathode side light emitting region and the intermediate region can be blocked and the electron supply to the anode side light emitting region can be performed in a balanced manner.
- the thickness of the region can be made thicker than before.
- the content of the compound represented by the formula (1) in the intermediate region is not particularly limited, but is preferably 1% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and particularly preferably 100% by mass. Examples of other compounds that can be used in the intermediate region include a host material in the light emitting region and a compound used in the hole transport region or the electron transport region.
- Examples of the azine compounds described above include compounds represented by the following formula (3).
- X 1 is —CH or a nitrogen atom
- X 2 is —CH or a nitrogen atom
- X 3 is —CH or a nitrogen atom, provided that X 1 , X 2 and X 3 are simultaneously —CH
- l is 0 or 1
- m is 0, 1 or 2
- n is 0, 1 or 2
- A is a carbazolyl group, dibenzofuranyl group or dibenzothiophene group
- B is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted group
- C is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring atom number.
- D is substituted or unsubstituted Ring formation 30 following aromatic having 6 or more carbon atoms hydrocarbon group, or a substituted or unsubstituted ring atoms 5 to 30 heterocyclic group
- L A is a substituted or unsubstituted ring-forming carbon atoms
- L C is a substituted or unsubstituted ring group having 6 to 30 ring carbon atoms.
- X 1 is a nitrogen atom
- X 2 is a nitrogen atom
- X 3 is —CH.
- A is a 3-carbazolyl group, 9-carbazolyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 2-dibenzothiophenyl group, or 4-dibenzothiophenyl group. It is.
- the aromatic hydrocarbon of B is phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, pyrenyl, chrysenyl, fluorenyl, 9,9 diphenylfluorenyl, or spirofluorenyl.
- the heterocyclic group of B is any one of pyridine, pyrimidine, triazine, indole, imidazole, purine, isoquinoline, quinoline, quinazoline, carbazole, phenanthridine, acridine, or phenanthroline.
- the C, D, L A and L C aromatic hydrocarbons are each independently selected from the above-mentioned definition of B aromatic hydrocarbons.
- the heterocyclic groups for C, D, L A and L C are each independently selected from the definition of the heterocyclic group for B described above.
- the material constituting the light emitting region is a charge injection function (a function capable of injecting holes from an anode or a hole supply layer when an electric field is applied and a function of injecting electrons from a cathode or an electron supply layer), a transport function It preferably has (a function of moving injected holes and electrons by the force of an electric field) and a light emitting function (a function of providing a field for recombination of electrons and holes and connecting them to light emission).
- a charge injection function a function capable of injecting holes from an anode or a hole supply layer when an electric field is applied and a function of injecting electrons from a cathode or an electron supply layer
- a transport function It preferably has (a function of moving injected holes and electrons by the force of an electric field) and a light emitting function (a function of providing a field for recombination of electrons and holes and connecting them to light emission).
- the light emitting region may be a fluorescent light emitting region or a phosphorescent light emitting region.
- Examples of the host material that constitutes the fluorescence emission region other than the azine-based compound include styryl derivatives, naphthacene derivatives, and aromatic amines.
- Examples of styryl derivatives include distil derivatives, tristil derivatives, tetrastil derivatives, and styrylamine derivatives.
- Examples of the aromatic amine include compounds having 2 to 4 nitrogen atoms substituted with an aromatic ring group.
- At least one light emitting region other than the light emitting region containing the azine compound as the host material described above preferably includes a material having an ionization potential of less than 5.6 eV as the host material.
- the light emitting region is preferably the light emitting region closest to the anode among the plurality of light emitting regions. This stabilizes hole injection from the anode.
- Examples of the compound (hole transporting material) having an ionization potential of less than 5.6 eV include polycyclic aromatic hydrocarbon compounds having a parent skeleton of 4 to 7 ring members.
- the mother skeleton is preferably pyrene, benzopyrene, chrysene, naphthacene, benzonaphthacene, dibenzonaphthacene, perylene, or coronene.
- R 21 to R 28 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted cyclohexane having 3 to 10 carbon atoms.
- Alkyl group substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 8 to 30 ring carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted Or an unsubstituted aryloxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring atom having 5 to 30 ring atoms. It is a heterocyclic group. Specific examples of these groups include the same groups as shown as examples of the compounds of formulas (1) and (3) described above.
- dopant materials in the fluorescence emission region include styrylbenzene dyes, oxazole dyes, perylene dyes, coumarin dyes, laser dyes such as acridine dyes, anthracene derivatives, naphthacene derivatives, pentacene derivatives, chrysene derivatives, diketo Polycyclic aromatic hydrocarbon materials such as pyrrolopyrrole derivatives, pyran derivatives or styryl derivatives, pyromethene skeleton compounds, or metal complexes, quinacridone derivatives, cyanomethylenepyran derivatives (DCM, DCJTB), benzothiazole compounds, benzimidazoles
- Fluorescent materials such as a system compound and a metal chelated oxinoid compound, can be mentioned.
- the doping concentration of each of these fluorescent materials is preferably 0.5% or more and 15% or less in terms of film thickness ratio.
- the light-emitting region containing a hole transporting material preferably contains a perylene derivative, a diketopyrrolopyrrole derivative, a pyromethene complex, a pyran derivative, or a styryl derivative as a dopant material.
- a host suitable for the phosphorescent emission region is a compound having a function of causing the phosphorescent compound to emit light as a result of energy transfer from the excited state to the phosphorescent compound.
- the host compound is not particularly limited as long as it has a large triplet energy gap and can transfer exciton energy to the phosphorescent compound, and can be appropriately selected according to the purpose.
- host compounds include condensed ring compounds composed of combinations of benzene rings, naphthalene rings, and heterocyclic rings, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, Pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene series Compounds, porphyrin compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, full For metal complexes of
- a phosphorescent compound is a compound that can emit light from triplet excitons. As long as it emits light from triplet excitons, it is not particularly limited, but is preferably a metal complex containing at least one metal selected from the group consisting of Ir, Ru, Pd, Pt, Os and Re, and a porphyrin metal complex Or orthometalated metal complexes are more preferred.
- a porphyrin metal complex is a porphyrin platinum complex.
- the phosphorescent compound may be used alone or in combination of two or more.
- ligands that form orthometalated metal complexes.
- Preferred ligands include 2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2- (2-thienyl) pyridine derivatives, Examples include 2- (1-naphthyl) pyridine derivatives and 2-phenylquinoline derivatives. These derivatives may have a substituent as necessary.
- a fluorinated compound or a compound having a trifluoromethyl group introduced is preferred as a blue dopant.
- a known phosphorescent dopant having a desired emission color can also be used.
- Specific examples include amines having a stilbene structure, aromatic amines, perylene derivatives, coumarin derivatives, borane derivatives, and pyran derivatives.
- the content of the phosphorescent compound (phosphorescent dopant) in the light emitting region is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is 0.1% by mass to 70% by mass, 1% by mass to 30% by mass is preferable. When the content of the phosphorescent compound is 0.1% by mass or more, light emission can be prevented from being weakened, and the content effect can be sufficiently exhibited. On the other hand, when the content is 70% by mass or less, a phenomenon called concentration quenching can be suppressed and deterioration of the performance of the light emitting element can be prevented.
- the red light emitting region is preferably composed of the above hole transporting material.
- the green light emitting region can be composed of a fluorescent light emitting material or a phosphorescent light emitting material.
- blue light emission can be generated by using the above-mentioned azine compound as a host material and doping it with a blue fluorescent dopant material.
- a compound having an emission peak in the range of about 400 nm to 490 nm can be exemplified.
- examples of such compounds include organic substances such as naphthalene derivatives, anthracene derivatives, naphthacene derivatives, styrylamine derivatives, and bis (azinyl) methene boron complexes.
- organic substances such as naphthalene derivatives, anthracene derivatives, naphthacene derivatives, styrylamine derivatives, and bis (azinyl) methene boron complexes.
- aminonaphthalene derivatives, aminoanthracene derivatives, aminochrysene derivatives, aminopyrene derivatives, styrylamine derivatives, and bis (azinyl) methene boron complexes are preferably used.
- the organic layer has a structure in which a first light emitting region, an intermediate region, a second light emitting region, and a third light emitting region are laminated in this order from the anode side, and the first light emitting region has at least the above-described hole transport property as a host material. It is preferable that the second light-emitting region and the third light-emitting region contain the azine derivative described above as the host material.
- At least one light emitting region other than the light emitting region containing the above-mentioned azine derivative as the host material may contain at least a phosphorescent material as the host material.
- the phosphorescent material is preferably a carbazole derivative or a quinoline complex derivative.
- the organic layer has a first light emitting region, an intermediate region, and a second light emitting region stacked from the anode side, the first light emitting region includes at least a phosphorescent light emitting material as a host material, and the second light emitting region as a host material. It is preferable to contain an azine derivative.
- the layer forming the hole transport region functions as a buffer layer for increasing the efficiency of hole injection into the light emitting region and preventing leakage.
- the film thickness of the hole supply layer depends on the configuration of the entire light emitting element, particularly the relationship with the electron supply layer, but is preferably 5 nm to 300 nm, preferably 10 nm to 200 nm, for example.
- the material constituting the hole supply layer may be appropriately selected in relation to the electrode and the material constituting the adjacent layer.
- the hole supply layer has a two-layer structure
- ⁇ -naphthylphenylphenylenediamine, porphyrin, metal tetraphenylporphyrin, metal naphthalene are used as materials constituting the first layer (anode side) and the second layer (light emitting region side).
- Phthalocyanine hexacyanoazatriphenylene, 7,7,8,8-tetracyanoquinodimethane (TCNQ), F4-TCNQ, tetracyano 4,4,4-tris (3-methylphenylphenylamino) triphenylamine, N, N , N ′, N′-tetrakis (p-tolyl) p-phenylenediamine, N, N, N ′, N′-tetraphenyl-4,4′-diaminobiphenyl, N-phenylcarbazole, 4-di-p- Tolylaminostilbene, poly (paraphenylene vinylene), poly (thiophene vinylene), poly (2,2′-thio Nirupiroru), and the like.
- the electron supply layer supplies electrons to the light emitting region from the hole supply layer. Hole supply to the light emitting region can be optimized.
- R 1 to R 6 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an arylamino group, a carbonyl group having 20 or less carbon atoms, or a carbonyl ester group having 20 or less carbon atoms.
- substituents selected from silyl groups or derivatives thereof, and adjacent R 1 to R 6 may be bonded to each other to form a cyclic structure.
- X 1 to X 6 are each independently a carbon atom or a nitrogen atom.
- the azatriphenylene derivative represented by the above formula (21) is preferably used for the hole supply layer because X is replaced with a nitrogen atom, so that the nitrogen content in the compound increases.
- Specific examples of the azatriphenylene derivative represented by the formula (21) include compounds such as the following formula (21-1).
- a 0 to A 2 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an aldehyde group, a carbonyl group, a carbonyl ester group, an alkyl group, an alkenyl group, a cyclic alkyl group, an alkoxy group, An aromatic group having 6 to 30 carbon atoms substituted by an aryl group, amino group, heterocyclic group, cyano group, nitrile group, nitro group, or silyl group.
- Specific examples of the amine derivative represented by the formula (22) include compounds such as the following formulas (22-1) to (22-9).
- a 3 to A 6 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an aldehyde group, a carbonyl group, a carbonyl ester group, an alkyl group, an alkenyl group, a cyclic alkyl group, an alkoxy group, An aromatic group having 6 to 20 carbon atoms substituted by an aryl group, amino group, heterocyclic group, cyano group, nitrile group, nitro group or silyl group.
- a 3 and A 4 , and A 5 and A 6 may each be bonded via a linking group.
- Y is a ring carbon other than the bonding site with nitrogen (N), each independently a hydrogen atom, a halogen atom, a hydroxyl group, an aldehyde group, a carbonyl group, a carbonyl ester group, an alkyl group, an alkenyl group, or a cyclic alkyl group.
- N nitrogen
- m is an integer of 1 or more.
- Specific examples of the diamine derivative represented by the formula (23) include compounds such as the following formulas (23-1) to (23-84).
- a 7 to A 12 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an aldehyde group, a carbonyl group, a carbonyl ester group, an alkyl group, an alkenyl group, a cyclic alkyl group, an alkoxy group,
- Adjacent A 7 and A 9 , A 9 and A 10 , and A 11 and A 12 may each be bonded via a linking group.
- Z 1 to Z 3 are each independently a ring carbon other than the bonding site with nitrogen (N), a hydrogen atom, a halogen atom, a hydroxyl group, an aldehyde group, a carbonyl group, a carbonyl ester group, an alkyl group, or an alkenyl group.
- N nitrogen
- a hydrogen atom a hydrogen atom
- a halogen atom a hydroxyl group
- an aldehyde group a carbonyl group
- a carbonyl group a carbonyl ester group
- an alkyl group or an alkenyl group.
- the various compounds described above may be used for either the first layer or the second layer of the hole supply layer, but a compound having a high nitrogen content is preferably used for the first layer.
- the layer constituting the electron transport region examples include an electron injection layer and an electron transport layer (hereinafter sometimes referred to as an electron injection layer / transport layer).
- the electron injection layer / transport layer assists the injection of electrons into the light emitting region and transports electrons to the light emitting region, and has a high electron mobility.
- the thickness of the electron injecting layer / transporting layer can be several nm to several ⁇ m. In particular, when the film thickness is large, an electric field of 10 4 V / cm to 10 6 V / cm is used to avoid voltage increase.
- the electron mobility is preferably at least 10 ⁇ 5 cm 2 / V ⁇ s or more.
- 8-hydroxyquinoline or a metal complex of its derivative or a nitrogen-containing heterocyclic derivative is suitable.
- metal complexes of 8-hydroxyquinoline or its derivatives include metal chelate oxinoid compounds containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline), such as tris (8-quinolinol) aluminum.
- the nitrogen-containing heterocyclic derivative include oxazole, thiazole, oxadiazole, thiadiazole, triazole, pyridine, pyrimidine, triazine, phenanthroline, benzimidazole, imidazopyridine and the like. Among them, benzimidazole derivatives, phenanthroline derivatives And imidazopyridine derivatives are preferred.
- the electron supply layer is for transporting electrons injected from the cathode to the light emitting region.
- the film thickness of the electron supply layer depends on the entire structure of the light emitting element, but is, for example, 10 nm to 200 nm, preferably 20 nm to It is desirable that it is 180 nm.
- an organic material having an excellent electron transport ability is preferably used as a material for the electron transport layer. By increasing the efficiency of electron transport to the light emitting region, particularly the red light emitting region and the green light emitting region, changes in the light emission color in the red light emitting region and the green light emitting region due to the electric field intensity are suppressed.
- Specific examples of such an organic material include nitrogen-containing heterocyclic derivatives having an electron mobility of 10 ⁇ 6 cm 2 / V ⁇ s or more and 1.0 ⁇ 10 ⁇ 1 cm 2 / V ⁇ s or less. Can do.
- Specific materials include, but are not limited to, benzimidazole derivatives represented by the following formula (9).
- a 14 has a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms and a derivative thereof, or a polycyclic aromatic hydrocarbon group condensed with 3 to 40 aromatic rings.
- B is a single bond, a divalent aromatic ring group or a derivative thereof.
- R 31 and R 32 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms and derivatives thereof, an aromatic hydrocarbon group having 6 to 60 carbon atoms and derivatives thereof, or a nitrogen-containing heterocyclic group. And a derivative thereof, or an alkoxy group having 1 to 20 carbon atoms and a derivative thereof.
- Specific examples of the compound represented by the formula (9) include compounds such as the following formulas (9-1) to (9-49). “Ar ( ⁇ )” corresponds to the benzimidazole skeleton containing R 31 and R 32 in the formula (9), and “B” corresponds to B in the formula (9). “Ar (1)” and “Ar (2)” correspond to A 14 in Formula (9), and are bonded to B in the order of Ar (1) and Ar (2).
- the organic material used for the electron transport layer is preferably a compound having an anthracene skeleton such as the above compound, but is not limited thereto.
- a benzimidazole derivative having a pyrene skeleton or a chrysene skeleton may be used instead of the anthracene skeleton.
- the organic material used for the electron transport layer is not limited to one type, and a plurality of types may be mixed or laminated. Moreover, you may use the said compound for an electron injection layer.
- the display device of the present disclosure can be used as, for example, a monitor device constituting a personal computer, and is a monitor incorporated in a television receiver, a mobile phone, a PDA (personal digital terminal, personal digital assistant), or a game device. Can be used as a device. Alternatively, it can be applied to an electronic view finder (Electronic View Finder, EVF) or a head-mounted display (Head Mounted Display, HMD).
- EVF Electronic View Finder
- HMD Head Mounted Display
- Example 1 relates to a light emitting element according to the first to third aspects of the present disclosure and the display device of the present disclosure.
- the light emitting element is specifically composed of an organic electroluminescence element (organic EL element)
- the display apparatus of Example 1 is specifically composed of an organic electroluminescence display apparatus (organic EL display apparatus).
- the display device according to the first embodiment or the display device according to the second embodiment which will be described later is an active matrix color display device, and is a top emission display device. That is, light is emitted through the cathode (second electrode).
- the light-emitting element of Example 1 is composed of an anode 51 (corresponding to the first electrode in the example) 51, an organic material, and a light-emitting layer 80, as shown in FIG.
- the organic layer 70 and the cathode (corresponding to the second electrode in the embodiment) 52 are stacked.
- the light emitting layer 80 is composed of two or more light emitting regions that emit light of different colors from the anode 51 side to the cathode 52 side.
- Each of the light emitting regions 82 and 83 includes a host material and a dopant material (guest material).
- the display device according to the first embodiment includes a plurality of light emitting elements according to the first embodiment arranged in a two-dimensional matrix.
- the light emitting regions 81, 82, and 83 are regions where holes injected from the anode 51 side and electrons injected from the cathode 52 side recombine when a voltage is applied to the anode 51 and the cathode 52. . More specifically, the light emitting layer 80 extends from the anode 51 side to the cathode 52 side, and includes a first light emitting region 81, an intermediate region (buffer region) 84, a second light emitting region 82, and a third light emitting region. The region 83 is configured.
- the first light emitting region 81 emits red light (wavelength: 620 nm to 750 nm), and the second light emitting region 82 emits blue light (wavelength: 450 nm to 495 nm).
- the third light emitting region 83 emits green light (wavelength: 495 nm to 570 nm), and emits white light as a whole. That is, the light emitting layer 80 emits white light.
- the intermediate region (buffer region) 84 is provided in order to suppress excessive carrier movement between the first light emitting region 81, the second light emitting region 82, and the third light emitting region 83.
- Table 1 further shows the absolute value Ip 3 (unit: eV) of the ionization potential Ip of the host material constituting the third light emitting region 83, and the absolute value of the ionization potential of the host material constituting the third light emitting region 83.
- the value ⁇ Ip (unit: eV) obtained by subtracting the absolute value of the ionization potential of the host material constituting the two light emitting region 82, the value of the band gap Eg (unit: eV), the value of LUMO energy Ea (unit: eV), triplet
- the excited state energy T1 (unit: eV), ⁇ u′v ′, and (x, y) values (represented by CIE_x and CIE_y in Table 1) in the chromaticity diagram are listed.
- An energy level diagram of the light emitting layer 80 is shown in FIG. 3B.
- the value of ⁇ u′v ′ is based on the u′v ′ system UCS chromaticity diagram of CIE 1976. Specifically, the value of the chromaticity coordinates (u ′ 1 , v) of white light emitted from the light emitting layer 80 when a current of 0.1 mA / cm 2 is passed between the anode 51 and the cathode 52. ' 1 ) is obtained by measurement, and the value of chromaticity coordinates (u ′ 2 , v ′) of white light emitted from the light emitting layer 80 when a current of 50 mA / cm 2 is passed between the anode 51 and the cathode 52. 2 ) Obtain by measurement.
- FIG. 4 shows changes in ⁇ u′v ′ depending on the current density when a current of 50 milliamperes / cm 2 is passed between the anode 51 and the cathode 52.
- a broken line shows the data of Example 1A
- a continuous line shows the data of Comparative Example 1B. From FIG. 4, it can be seen that the change in ⁇ u′v ′ depending on the current density is large in Comparative Example 1A and small in Example 1A.
- FIG. 4 shows changes in ⁇ u′v ′ depending on the current density when a current of 50 milliamperes / cm 2 is passed between the anode 51 and the cathode 52.
- a broken line shows the data of Example 1A
- a continuous line shows the data of Comparative Example 1B.
- the value of the chromaticity coordinate of the white light emitted from the light emitting layer 80 when a current of 0.1 mA / cm 2 is passed between the anode 51 and the cathode 52 is 0.01 or less. It is.
- ⁇ u′v ′ ⁇ (u ′ 1 ⁇ u ′ 2 ) 2 + (v ′ 1 ⁇ v ′ 2 ) 2 ⁇ 1/2
- region A A region of the display device in which a current of 0.1 milliamperes / cm 2 is passed between the anode (first electrode) 51 and the cathode (second electrode) 52;
- region B a region of the display device in which a current of 50 milliamperes / cm 2 was passed between the cathode 52 and the cathode 52.
- the absolute value of the ionization potential of the host material contained in the light emitting region close to the cathode 52 is close to the light emitting region (in Example 1). Is larger than the absolute value of the ionization potential of the host material contained in the second light-emitting region 82), or is included in the light-emitting region adjacent to the cathode 52 (the third light-emitting region 83 in Example 1).
- the absolute value of the ionization potential of the host material is a light emitting region (the third light emitting region 83 in the first embodiment) adjacent to the cathode 52 (the second light emitting in the first embodiment). Due to the fact that it is larger than the absolute value of the ionization potential of the host material contained in the region 82), there is no significant difference in the colors displayed in the regions A and B.
- the host material contained in the light emitting region adjacent to the cathode 52 is the light emitting region adjacent to the cathode 52 (the third light emitting region in the first embodiment).
- the host material contained in the light emitting region adjacent to the cathode 52 is the light emitting region adjacent to the cathode 52 (the third light emitting region in the first embodiment).
- the function of suppressing the movement of holes from the light emitting region adjacent to the third light emitting region 83 (in the first embodiment, the second light emitting region 82) has the function of suppressing the movement of holes from the light emitting region adjacent to the cathode 52 ( In Example 1, no significant difference was observed in the colors displayed in these areas A and B by being applied to the third light emitting area 83).
- the absolute value of the ionization potential of the host material contained in the light emitting region adjacent to the cathode 52 is 6.1 eV or more, and the light emission adjacent to the cathode 52 is used.
- the absolute value of the ionization potential of the host material contained in the region (the third light emitting region 83 in Example 1) is
- the value of the band gap of the host material contained in the light emitting region adjacent to the cathode 52 is preferably 3.1 eV or more. And even if these were satisfied, there was no significant difference in the colors displayed in these areas A and B.
- the movement of the hole can be prevented from greatly fluctuating, and the position of the recombination region in the light emitting region is unlikely to change, and as a result, the value of the chromaticity coordinate of the white light emitted by the white light emitting element is greatly changed.
- a light-emitting element having a structure that does not easily occur can be obtained.
- the display device As shown in FIG. 1, the display device according to the first embodiment or the display device according to the second embodiment described later includes the first substrate 11, the second substrate 12, and the first substrate 11 and the second substrate 12. And a plurality of light emitting elements (display elements) 10 arranged in a two-dimensional matrix, light is emitted through the second substrate 12, and each light emitting element 10 is provided from the first substrate side.
- the anode (first electrode) 51, the organic layer 70 having the light emitting layer 80, the cathode (second electrode) 52, and the sealing layer 15 are laminated.
- Organic EL elements which are light emitting elements are arranged in a two-dimensional matrix in a first direction and a second direction extending in a direction perpendicular to the first direction.
- the display device of the first embodiment or the display device of the second embodiment to be described later can be expressed by the first substrate 11, the second substrate 12, and the first substrate 11 and the second substrate 12.
- the image display unit 13 is sandwiched, and the image display unit 13 includes a plurality of light emitting elements 10 arranged in a two-dimensional matrix.
- a color filter layer CF is formed between the sealing layer 15 and the second substrate 12, and the color filter layer CF (CF R , CF A light shielding layer (black matrix layer) BM is formed between G , CF B ) and the color filter layer CF.
- the color filter layer CF and the light shielding layer BM are formed in contact with the second substrate 12.
- One pixel includes three sub-pixels ( 3 , red display sub-pixel SP R (red light-emitting element 10R), green display sub-pixel SP G (green light-emitting element 10G), and blue display sub-pixel SP B (blue light-emitting element 10B).
- Each color light emitting subpixel is composed of a light emitting element (organic EL element) that emits white light including color filter layers CF R , CF G , and CF B. That is, the light emitting layer itself emits white light as a whole.
- the red light emitting element (red display element) 10R, the green light emitting element (green display element) 10G, and the blue light emitting element (blue display element) 10B have the same configuration and structure except for the color filter layer CF.
- the number of pixels is, for example, 1920 ⁇ 1080, one light emitting element 10 constitutes one subpixel, and the light emitting element (specifically, organic EL element) 10 is three times the number of pixels.
- the first substrate 11 is made of a glass substrate
- the anode (first electrode) 51 is a light reflecting material, specifically, an Al—Nd alloy or Made of Al-Ni alloy.
- the second substrate 12 is made of a glass substrate
- the cathode (second electrode) 52 is made of a transparent conductive material such as ITO.
- the anode 51 is formed based on a combination of a vacuum deposition method and an etching method.
- the cathode 52 is formed by a film forming method in which the energy of film forming particles is small, such as vacuum deposition, and is not patterned.
- the organic layer 70 is also not patterned.
- the anode (first electrode) 51 is provided on the interlayer insulating layer 40 made of SiON formed based on the CVD method.
- the interlayer insulating layer 40 covers the organic EL element driving unit formed on the first substrate 11.
- the organic EL element driving unit includes a plurality of TFTs (thin film transistors) 20, and the TFTs 20 and the anodes 51 are electrically connected through contact plugs 26 provided in the interlayer insulating layer 40.
- the portion of the organic layer 70 that actually emits light is surrounded by an insulating layer 60 made of SiO 2 .
- one TFT 20 is shown for one organic EL element driving unit.
- the light emitting element 10 may have a resonator structure in which the organic layer 70 is a resonance part.
- the thickness of the organic layer 70 is 8 ⁇ 10 ⁇ 8 m or more, It is preferably 5 ⁇ 10 ⁇ 7 m or less, more preferably 1.5 ⁇ 10 ⁇ 7 m or more and 3.5 ⁇ 10 ⁇ 7 m or less.
- Protective film 14 (specifically, for example, made of SiO 2 material or SiN material) is provided.
- the protective film 14 and the second substrate 12 are bonded via a sealing layer (sealing resin layer) 15 made of, for example, an acrylic adhesive or an epoxy adhesive.
- the TFT 20 includes a gate electrode 21 formed on the first substrate 11, a gate insulating layer 22 formed on the first substrate 11 and the gate electrode 21, a source / drain region 24 formed on the gate insulating layer 22, a gate.
- the channel forming region 23 is formed between the source / drain regions 24 so as to face the electrode 21.
- Example 1 An outline of a method for manufacturing the display device (organic EL display device) of Example 1 will be described.
- 2nd substrate 12 is prepared. Specifically, the color filter layer CF and the light shielding layer BM are formed on the second substrate 12 based on a known method.
- the interlayer insulating layer 40 is formed on the entire surface based on the CVD method. Then, a connection hole is formed in the portion of the interlayer insulating layer 40 located above the one source / drain region 24 of the TFT 20 based on the photolithography technique and the etching technique. Thereafter, a metal layer is formed on the interlayer insulating layer 40 including the connection holes based on, for example, a sputtering method, and then the metal layer is patterned on the interlayer insulating layer 40 based on a photolithography technique and an etching technique.
- the anode 51 can be formed. Further, the contact plug 26 can be formed in the interlayer insulating layer 40. The anode 51 is separated for each light emitting element.
- an insulating layer 60 made of SiO 2 is formed on the entire surface based on the CVD method, and then an opening 61 is formed in the portion of the insulating layer 60 located above the anode 51 based on the photolithography technique and the etching technique.
- the anode 51 is exposed at the bottom of the opening 61.
- Examples of the planar shape of the opening 61 include a square, a square with rounded corners, a rectangle, and a rectangle with rounded four corners, a circle, and an ellipse.
- the organic layer 70 is formed on the portion of the anode 51 exposed at the bottom of the opening 61 and the insulating layer 60 by, for example, a PVD method such as a vacuum deposition method or a sputtering method, a coating method such as a spin coating method or a die coating method, or the like. Form a film.
- the cathode 52 is formed on the entire surface of the organic layer 70 based on, for example, a vacuum deposition method or the like. In this way, the organic layer 70 and the cathode 52 can be continuously formed on the anode 51 in, for example, a vacuum atmosphere.
- the protective film 14 is formed on the entire surface by, eg, CVD or PVD.
- Step-130 Finally, the protective film 14 and the second substrate 12 are bonded together via the sealing layer (sealing resin layer) 15. In this way, the display device shown in FIG. 1 can be obtained.
- Example 2 is a modification of Example 1.
- a light reflection layer is formed below the anode (first electrode) via an interlayer insulating layer, and a resonator structure is configured between the light reflection layer and the cathode (second electrode).
- FIG. 2 shows a schematic partial cross-sectional view of a display device of Example 2 in which the display device of Example 1 is modified.
- the light emitting device 10 of Example 2 is Lower layer / interlayer insulating layer 31, A light reflecting layer 37 formed on the lower layer / interlayer insulating layer 31; An upper layer / interlayer insulating layer 32 covering the lower layer / interlayer insulating layer 31 and the light reflecting layer 37; An anode 51 formed on the upper layer / interlayer insulating layer 32; An insulating layer 60 formed on at least the region of the upper layer / interlayer insulating layer 32 where the anode 51 is not formed, An organic layer 70 formed on the insulating layer 60 from the anode 51 and having a light emitting layer made of an organic light emitting material, and The cathode 52 formed on the organic layer 70 is provided.
- the display device of Example 2 is A display device in which a plurality of pixels including a first light emitting element 10R, a second light emitting element 10G, and a third light emitting element 10B are arranged in a two-dimensional matrix,
- the pixel has a stacked structure in which a lowermost layer / interlayer insulating layer 33, a first interlayer insulating layer 34, a second interlayer insulating layer 35, and an uppermost layer / interlayer insulating layer 36 are sequentially stacked.
- each light emitting element 10R, 10G, 10B is: An anode 51 formed on the uppermost layer / interlayer insulating layer 36; An insulating layer 60 formed on at least the region of the uppermost layer / interlayer insulating layer 36 where the anode 51 is not formed, An organic layer 70 formed on the insulating layer 60 from the anode 51 and having a light emitting layer made of an organic light emitting material, and A cathode 52 formed on the organic layer 70,
- the first light emitting element 10R includes a first light reflecting layer 38R formed between the lowermost layer / interlayer insulating layer 33 and the first interlayer insulating layer 34
- the second light emitting element 10G includes a second light reflecting layer 38G formed between the first interlayer insulating layer 34 and the second interlayer insulating layer 35
- the third light emitting element 10 ⁇ / b> B includes a third light reflecting layer 38 ⁇ / b> B formed between the second interlayer insulating layer 35 and the uppermost layer /
- the first interlayer insulating layer 34, the second interlayer insulating layer 35, and the uppermost layer / interlayer insulating layer 36 are collectively referred to as an interlayer insulating layer / laminated structure 30.
- the display device includes the first substrate 11, the second substrate 12, and the image display unit 13 sandwiched between the first substrate 11 and the second substrate 12.
- the image display unit 13 a plurality of light emitting elements 10 (10R, 10G, 10B) of Example 2 are arranged in a two-dimensional matrix.
- a light emitting element is formed on the first substrate side.
- the anode 51 is made of ITO.
- the light reflecting layer 37 (the first light reflecting layer 38R, the second light reflecting layer 38G, and the third light reflecting layer 38B) has a laminated structure of titanium (Ti) / aluminum (Al).
- the first substrate 11 is made of a silicon semiconductor substrate
- the second substrate 12 is made of a glass substrate.
- MOSFET is formed in the silicon semiconductor substrate instead of TFT.
- the light emitted from the organic layer 70 is white.
- the light emitting layer has three regions: a red light emitting region that emits red light, a green light emitting region that emits green light, and a blue light emitting region that emits blue light.
- the red light emitting element 10R, the green light emitting element 10G, and the blue light emitting element 10B have the same configuration and structure except the configuration of the color filter layer and the position of the light reflection layer.
- the lowermost layer / interlayer insulating layer 33, the interlayer insulating layer / laminated structure 30, the organic layer 70, and the cathode 52 are shared by a plurality of light emitting elements. That is, the lowermost layer / interlayer insulating layer 33, the interlayer insulating layer / laminated structure 30, the organic layer 70, and the cathode 52 are not patterned and are in a so-called solid film state.
- the angle of view is several inches or less
- a small and high-resolution display device having a pixel pitch of several tens of micrometers or less can also be supported.
- the light emitting element 10 has a resonator structure in which the organic layer 70 is a resonance part.
- the thickness of the organic layer 70 is 8 ⁇ 10 ⁇ . It is preferably 8 m or more and 5 ⁇ 10 ⁇ 7 m or less, more preferably 1.5 ⁇ 10 ⁇ 7 m or more and 3.5 ⁇ 10 ⁇ 7 m or less.
- the red light emitting element 10R actually resonates the red light emitted from the light emitting layer to produce reddish light (the peak of the light spectrum in the red region).
- the green light emitting element 10G resonates the green light emitted from the light emitting layer and emits greenish light (light having a light spectrum peak in the green region) from the cathode 52.
- the blue light emitting element 10 ⁇ / b> B resonates the blue light emitted from the light emitting layer and emits bluish light (light having a light spectrum peak in a blue region) from the cathode 52.
- a transistor 120 formed on a silicon semiconductor substrate (first substrate 11) below the lower layer / interlayer insulating layer 31 (lowermost layer / interlayer insulating layer 33).
- the anode 51 and the transistor 120 formed on the silicon semiconductor substrate (first substrate 11) are contact holes (contact plugs) 26 formed in the lowermost layer / interlayer insulating layer 33 and the interlayer insulating layer / stacked structure 30. Connected through.
- the transistor 120 made of a MOSFET includes a gate electrode 121, a gate insulating layer 122, a channel formation region 123, and a source / drain region 124, and an element isolation region 125 is formed between the transistors 120. Thereby, the transistors 120 are isolated from each other.
- the configuration and structure of the display device according to the second embodiment can be the same as the configuration and structure of the display device according to the first embodiment.
- one pixel is composed of three subpixels exclusively from a combination of a white light emitting element and a color filter layer.
- one pixel is composed of four subpixels including a light emitting element that emits white light. It may be configured.
- the bottom emission type (bottom emission type) display device (bottom emission type display device) can be used.
- the color filter layer is provided on the second substrate, an OCCF (on-chip color filter) structure display device in which the color filter layer is provided on the first substrate can be used instead.
- Light-emitting element first embodiment >> A structure comprising an anode, an organic material, an organic layer having a light emitting layer, and a cathode, The light emitting layer is composed of two or more light emitting regions that emit different colors from the anode side to the cathode side, Each light emitting region includes a host material and a dopant material, A light-emitting element in which an absolute value of an ionization potential of a host material included in a light-emitting region near a cathode is larger than an absolute value of an ionization potential of a host material included in a light-emitting region near an anode.
- a structure comprising an anode, an organic material, an organic layer having a light emitting layer, and a cathode,
- the light emitting layer is composed of two or more light emitting regions that emit different colors from the anode side to the cathode side,
- Each light emitting region includes a host material and a dopant material,
- the host material contained in the light emitting region adjacent to the cathode is a light emitting element that suppresses movement of holes from the light emitting region adjacent to the light emitting region adjacent to the cathode.
- the light emitting layer extends from the anode side to the cathode side, and includes any one of [A01] to [A08] including a first light emitting region, an intermediate region, a second light emitting region, and a third light emitting region.
- [A10] The light-emitting element according to any one of [A01] to [A09], which includes an organic electroluminescence element.
- SYMBOLS 10 Light emitting element (display element), 10R ... Red light emitting element (first light emitting element), 10G ... Green light emitting element (second light emitting element), 10B ... Blue light emitting element (third light emitting element) Element), SP R ... red display subpixel, SP G ... green display subpixel, SP B ... blue display subpixel, 11 ... first substrate, 12 ... second substrate, 13 ... Image display part, 14 ... Protective film, 15 ... Sealing layer (sealing resin layer), 20 ... TFT (thin film transistor), 120 ... MOSFET, 21, 121 ... Gate Electrode, 22, 122 ... Gate insulating layer, 23, 123 ... Channel formation region, 24, 124 ...
- cathode (second electrode), 60 ..insulating layer, 61... Opening, 70. ... light emitting layer, 81 ... first light emitting area, 82 ... second light emitting area, 83 ... third light emitting area, 84 ... intermediate area (buffer area), CF, CF R , CF G , CF B: Color filter layer, BM: Light shielding layer (black matrix layer)
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Abstract
Description
1.本開示の第1の態様~第3の態様に係る発光素子、及び、本開示の表示装置、全般に関する説明
2.実施例1(本開示の第1の態様~第3の態様に係る発光素子、及び、本開示の表示装置)
3.実施例2(実施例1の変形)
4.その他
本開示の第1の態様に係る発光素子、あるいは、本開示の表示装置を構成する本開示の第1の態様に係る発光素子(以下、これらの発光素子を総称して、『本開示の第1の態様に係る発光素子等』と呼ぶ)において、陰極に隣接する発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値は6.1eV以上である形態とすることができ、これによって、一層確実に、陽極と陰極との間に流す電流量(電流密度)に依って、白色発光素子が発光する白色光の色度座標の値に大きな変化が生じ難くなる。そして、この場合、陰極に隣接する発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値を|Ip1|、陰極に隣接する発光領域に隣接する発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値を|Ip2|としたとき、|Ip1|-|Ip2|≧0.1を満足することが好ましい。更には、これらの場合、陰極に隣接する発光領域に含まれるホスト材料のバンドギャップの値は3.1eV以上であることが好ましい。
基体は、トランジスタ(具体的には、例えば、MOSFET)が形成されたシリコン半導体基板及びその上に形成された層間絶縁層から成り、あるいは又、基体は、トランジスタ(具体的には、例えば、薄膜トランジスタ、TFT)が形成された基板及びその上に形成された層間絶縁層から成り、
第1電極及び第1絶縁層は層間絶縁層上に形成されており、
第1電極とシリコン半導体基板(あるいは基板)に形成されたトランジスタとは、層間絶縁層に形成されたコンタクトホールを介して接続されている形態とすることができる。
(A-1)
0.7{-Φ2/(2π)+m2}≦2×OL2/λ≦1.2{-Φ2/(2π)+m2}
(A-2)
L1<L2 (A-3)
m1<m2 (A-4)
ここで、
λ :発光層で発生した光のスペクトルの最大ピーク波長(あるいは又、発光層で発生した光の内の所望の波長)
Φ1:第1界面で反射される光の位相シフト量(単位:ラジアン)
但し、-2π<Φ1≦0
Φ2:第2界面で反射される光の位相シフト量(単位:ラジアン)
但し、-2π<Φ2≦0である。
一方、第1基板11に発光素子駆動部を公知のTFT製造プロセスに基づき形成した後、全面に、層間絶縁層40をCVD法に基づき形成する。そして、TFT20の一方のソース/ドレイン領域24の上方に位置する層間絶縁層40の部分に、フォトリソグラフィ技術及びエッチング技術に基づき接続孔を形成する。その後、接続孔を含む層間絶縁層40の上に金属層を、例えば、スパッタリング法に基づき形成し、次いで、フォトリソグラフィ技術及びエッチング技術に基づき金属層をパターニングすることで、層間絶縁層40上に陽極51を形成することができる。また、層間絶縁層40にコンタクトプラグ26を形成することができる。陽極51は、各発光素子毎に分離されている。
その後、全面に、CVD法に基づき、SiO2から成る絶縁層60を形成した後、フォトリソグラフィ技術及びエッチング技術に基づき、陽極51の上方に位置する絶縁層60の部分に開口部61を形成し、開口部61の底部に陽極51を露出させる。開口部61の平面形状として、正方形、四隅が丸みを帯びた正方形、長方形、四隅が丸みを帯びた長方形、円形、楕円形を例示することができる。
その後、開口部61の底部に露出した陽極51の部分及び絶縁層60上に、有機層70を、例えば、真空蒸着法やスパッタリング法といったPVD法、スピンコート法やダイコート法等のコーティング法等によって成膜する。次いで、例えば真空蒸着法等に基づき、有機層70の全面に陰極52を形成する。このようにして、陽極51上に、有機層70及び陰極52を、例えば、真空雰囲気において連続して成膜することができる。その後、例えばCVD法又はPVD法によって、全面に保護膜14を形成する。
最後に、封止層(封止樹脂層)15を介して、保護膜14と第2基板12とを貼り合わせる。こうして、図1に示した表示装置を得ることができる。
下層・層間絶縁層31、
下層・層間絶縁層31上に形成された光反射層37、
下層・層間絶縁層31及び光反射層37を覆う上層・層間絶縁層32、
上層・層間絶縁層32上に形成された陽極51、
少なくとも陽極51が形成されていない上層・層間絶縁層32の領域の上に形成された絶縁層60、
陽極51上から絶縁層60上に亙り形成され、有機発光材料から成る発光層を有する有機層70、並びに、
有機層70上に形成された陰極52、を備えている。
第1発光素子10R、第2発光素子10G及び第3発光素子10Bから構成された画素が、複数、2次元マトリクス状に配列されて成る表示装置であって、
画素は、最下層・層間絶縁層33、第1層間絶縁層34、第2層間絶縁層35及び最上層・層間絶縁層36が、順次、積層された積層構造を有している。そして、各発光素子10R,10G,10Bは、
最上層・層間絶縁層36上に形成された陽極51、
少なくとも陽極51が形成されていない最上層・層間絶縁層36の領域の上に形成された絶縁層60、
陽極51上から絶縁層60上に亙り形成され、有機発光材料から成る発光層を有する有機層70、並びに、
有機層70上に形成された陰極52、を備えており、
第1発光素子10Rは、最下層・層間絶縁層33と第1層間絶縁層34との間に形成された第1光反射層38Rを備えており、
第2発光素子10Gは、第1層間絶縁層34と第2層間絶縁層35との間に形成された第2光反射層38Gを備えており、
第3発光素子10Bは、第2層間絶縁層35と最上層・層間絶縁層36との間に形成された第3光反射層38Bを備えている。
[A01]《発光素子:第1の態様》
陽極、有機材料から成り、発光層を備えた有機層、及び、陰極が積層された構造を有し、
発光層は、陽極側から陰極側に亙り、異なる色を発光する2以上の発光領域から構成されており、
各発光領域は、ホスト材料及びドーパント材料を含み、
陰極に近い発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値は、陽極に近い発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値よりも大きい発光素子。
[A02]陰極に隣接する発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値は6.1eV以上である[A01]に記載の発光素子。
[A03]陰極に隣接する発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値を|Ip1|、陰極に隣接する発光領域に隣接する発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値を|Ip2|としたとき、|Ip1|-|Ip2|≧0.1を満足する[A02]に記載の発光素子。
[A04]陰極に隣接する発光領域に含まれるホスト材料のバンドギャップの値は3.1eV以上である[A02]又は[A03]に記載の発光素子。
[A05]《発光素子:第2の態様》
陽極、有機材料から成り、発光層を備えた有機層、及び、陰極が積層された構造を有し、
発光層は、陽極側から陰極側に亙り、異なる色を発光する2以上の発光領域から構成されており、
各発光領域は、ホスト材料及びドーパント材料を含み、
陽極と陰極との間に0.1ミリアンペア/cm2の電流を流したときに発光層が発光する白色光の色度座標の値(u’1,v’1)と、陽極と陰極との間に50ミリアンペア/cm2の電流を流したときに発光層が発光する白色光の色度座標の値(u’2,v’2)との差Δu’v’の値が、0.02以下である発光素子。
[A06]《発光素子:第3の態様》
陽極、有機材料から成り、発光層を備えた有機層、及び、陰極が積層された構造を有し、
発光層は、陽極側から陰極側に亙り、異なる色を発光する2以上の発光領域から構成されており、
各発光領域は、ホスト材料及びドーパント材料を含み、
陰極に隣接する発光領域に含まれるホスト材料は、陰極に隣接する発光領域に隣接する発光領域からの正孔の移動を抑制する発光素子。
[A07]陰極に隣接する発光領域におけるホスト材料はアジン系化合物から成る[A01]乃至[A06]のいずれか1項に記載の発光素子。
[A08]発光層は白色光を発光する[A01]乃至[A07]のいずれか1項に記載の発光素子。
[A09]発光層は、陽極側から陰極側に亙り、第1発光領域、中間領域、第2発光領域、及び、第3発光領域から構成されている[A01]乃至[A08]のいずれか1項に記載の発光素子。
[A10]有機エレクトロルミネッセンス素子から成る[A01]乃至[A09]のいずれか1項に記載の発光素子。
[B01]《表示装置》
[A01]乃至[A10]のいずれか1項に記載の発光素子が、複数、2次元マトリクス状に配列されて成る表示装置。
Claims (11)
- 陽極、有機材料から成り、発光層を備えた有機層、及び、陰極が積層された構造を有し、
発光層は、陽極側から陰極側に亙り、異なる色を発光する2以上の発光領域から構成されており、
各発光領域は、ホスト材料及びドーパント材料を含み、
陰極に近い発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値は、陽極に近い発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値よりも大きい発光素子。 - 陰極に隣接する発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値は6.1eV以上である請求項1に記載の発光素子。
- 陰極に隣接する発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値を|Ip1|、陰極に隣接する発光領域に隣接する発光領域に含まれるホスト材料のイオン化ポテンシャルの絶対値を|Ip2|としたとき、|Ip1|-|Ip2|≧0.1を満足する請求項2に記載の発光素子。
- 陰極に隣接する発光領域に含まれるホスト材料のバンドギャップの値は3.1eV以上である請求項2に記載の発光素子。
- 陽極、有機材料から成り、発光層を備えた有機層、及び、陰極が積層された構造を有し、
発光層は、陽極側から陰極側に亙り、異なる色を発光する2以上の発光領域から構成されており、
各発光領域は、ホスト材料及びドーパント材料を含み、
陽極と陰極との間に0.1ミリアンペア/cm2の電流を流したときに発光層が発光する白色光の色度座標の値と、陽極と陰極との間に50ミリアンペア/cm2の電流を流したときに発光層が発光する白色光の色度座標の値との差Δu’v’の値が、0.02以下である発光素子。 - 陽極、有機材料から成り、発光層を備えた有機層、及び、陰極が積層された構造を有し、
発光層は、陽極側から陰極側に亙り、異なる色を発光する2以上の発光領域から構成されており、
各発光領域は、ホスト材料及びドーパント材料を含み、
陰極に隣接する発光領域に含まれるホスト材料は、陰極に隣接する発光領域に隣接する発光領域からの正孔の移動を抑制する発光素子。 - 陰極に隣接する発光領域におけるホスト材料はアジン系化合物から成る請求項1、請求項5又は請求項6に記載の発光素子。
- 発光層は白色光を発光する請求項1、請求項5又は請求項6に記載の発光素子。
- 発光層は、陽極側から陰極側に亙り、第1発光領域、中間領域、第2発光領域、及び、第3発光領域から構成されている請求項1、請求項5又は請求項6に記載の発光素子。
- 有機エレクトロルミネッセンス素子から成る請求項1、請求項5又は請求項6に記載の発光素子。
- 請求項1乃至請求項10のいずれか1項に記載の発光素子が、複数、2次元マトリクス状に配列されて成る表示装置。
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US15/781,538 US11276834B2 (en) | 2015-12-25 | 2016-12-12 | Light emitting element and display device |
KR1020187016627A KR20180098543A (ko) | 2015-12-25 | 2016-12-12 | 발광 소자 및 표시 장치 |
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KR20180083020A (ko) * | 2017-01-11 | 2018-07-20 | 삼성디스플레이 주식회사 | 표시 장치 |
JP6964421B2 (ja) | 2017-03-23 | 2021-11-10 | ローム株式会社 | 半導体発光装置 |
WO2018227059A1 (en) * | 2017-06-09 | 2018-12-13 | Revolution Display, Llc | Visual-display structure having a metal contrast enhancer, and visual displays made therewith |
TWI679627B (zh) * | 2018-06-28 | 2019-12-11 | 友達光電股份有限公司 | 顯示裝置 |
WO2023288030A1 (en) * | 2021-07-14 | 2023-01-19 | The Trustees Of Dartmouth College | Liquid metal printed 2d ultrahigh mobility conducting oxide transistors |
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