WO2014185529A1 - 有機el素子、及び、有機el素子の製造方法 - Google Patents
有機el素子、及び、有機el素子の製造方法 Download PDFInfo
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- WO2014185529A1 WO2014185529A1 PCT/JP2014/063086 JP2014063086W WO2014185529A1 WO 2014185529 A1 WO2014185529 A1 WO 2014185529A1 JP 2014063086 W JP2014063086 W JP 2014063086W WO 2014185529 A1 WO2014185529 A1 WO 2014185529A1
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- light emitting
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-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
- H10K59/221—Static displays, e.g. displaying permanent logos
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/351—Thickness
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
Definitions
- the present invention relates to an organic EL element and a method for manufacturing the organic EL element.
- Patent Document 1 discloses an organic EL (Electro Luminescence) element that emits light with a predetermined light emission pattern.
- the organic EL element includes an anode 20, a cathode 40, and an organic light emitting film 30 disposed between the anode 20 and the cathode 40.
- the anode 20 includes a wide rough pattern including a light emission pattern.
- the cathode 40 is formed in a pattern corresponding to the light emission pattern, and the organic light emitting film 30 is formed in a non-patterned continuous surface including both the light emission pattern and each pattern of both electrodes.
- the light emission pattern corresponding to the pattern of an electrode (specifically cathode 40) is obtained.
- a photolithography method, an etching method, a vapor deposition method, and the like are conceivable as a method for forming an electrode having a pattern corresponding to a light emission pattern.
- a mask corresponding to the electrode pattern that is, the light emission pattern
- an object of the present invention is to provide an organic EL element capable of simplifying the manufacturing method and reducing the price, and a method for manufacturing the organic EL element.
- An organic EL device of the present invention includes an organic first electrode, an organic second electrode, and a light emitting layer disposed between the first electrode and the second electrode.
- the light emitting layer has a plurality of light emitting regions, and at least one of the light emission color and the light emission luminance is different in at least two light emitting regions of the plurality of light emitting regions.
- the method for producing an organic EL element of the present invention includes a step of forming a single first electrode and a light emitting layer having a plurality of light emitting regions, wherein at least two of the light emitting regions emit light.
- the region includes a step of forming a light emitting layer in which at least one of the emission color and the light emission luminance is different, and a step of forming a single second electrode.
- one electrode means a single plate-like electrode that is integrally formed, and physical cutting (that is, electrical disconnection) within the integrally formed electrode. It means not occurring.
- a predetermined light emission pattern such as a character or a picture is obtained by changing at least one of the light emission color and the light emission luminance for each of the plurality of light emitting regions in the light emitting layer. Therefore, both electrodes need only be formed in one piece, and it is not necessary to form the electrodes in a light emitting pattern. As a result, it is not necessary to prepare a mask for electrode formation in accordance with the light emission pattern. Therefore, when forming a plurality of types of light emitting patterns, it is not necessary to prepare a mask for forming an electrode for each light emitting pattern, and the manufacturing method can be simplified and the cost can be reduced.
- the light emitting material contained in the light emitting layer in each of the light emitting regions may be different in at least two of the light emitting regions described above.
- a coating liquid containing different light emitting materials is applied to each light emitting region by pattern coating to form a coating film.
- the light emitting layer of each light emitting region may be formed by solidifying the coating film.
- a predetermined light emission pattern such as a character or a picture can be formed by making the light emission color different for each of the plurality of light emitting regions in the light emitting layer.
- the light emitting layer in the boundary region between adjacent light emitting regions among the plurality of light emitting regions described above is adjacent to the light emitting material included in the light emitting layer in one light emitting region of the adjacent light emitting regions.
- the light emitting material contained in the light emitting layer in the other light emitting region may be included.
- the boundary region between adjacent light emitting regions among the plurality of light emitting regions is coated with the light emitting material of the light emitting layer in one of the adjacent light emitting regions. While applying a liquid, you may apply
- the boundary between adjacent light emitting regions may be blurred due to wet spreading of a coating liquid (for example, ink containing a light emitting material).
- a coating liquid for example, ink containing a light emitting material
- the inventors of the present application apply the coating liquid in the respective light emitting areas so as to overlap each other at the boundary between the light emitting areas. It has been found that the blur at the boundary of can be suppressed and the visibility can be improved. This is because the light emitting layer at the boundary between adjacent light emitting regions is thickened to form a contour with reduced light emission luminance, or the light emitting color is dark due to the light emitting color composition at the boundary between adjacent light emitting regions. This is considered to be due to the fact that these boundaries appear sharp when the contour is formed.
- the boundary region between the adjacent light emitting regions includes both light emitting materials of the adjacent light emitting regions by using the above-described coating method, it is possible to suppress blur at the boundary of these light emitting regions, Visibility can be improved.
- the light emitting layer in the boundary region between the adjacent light emitting regions among the plurality of light emitting regions described above includes the light emitting layer in one of the adjacent light emitting regions and the other of the adjacent light emitting regions.
- the thickness of the light emitting layer in the light emitting region may be thinner than that of the light emitting layer having a small thickness.
- the above-described step of forming the light emitting layer it is not necessary to apply a coating liquid containing a light emitting material in a boundary region between adjacent light emitting regions among the plurality of light emitting regions.
- the light emitting layer at the boundary between the adjacent light emitting regions is thinned to form a contour with high light emission luminance, or the light emitting color is combined at the boundary between the adjacent light emitting regions so that the light emitting color has a bright contour. It is formed.
- a three-dimensional visual effect can be obtained by intentionally shifting the light emission pattern at a predetermined position. For example, when there is a first light emitting region and a second light emitting region surrounding the first light emitting region, if the first light emitting region is shifted in a predetermined shift direction, the first light emitting region and the second light emitting region are located on one side of the shift direction. While the light emitting region can overlap, a gap is generated between the first light emitting region and the second light emitting region on the other side in the shift direction.
- the light emitting layer at the boundary between adjacent light emitting regions is thickened, thereby forming a contour with reduced light emission luminance, or the boundary between adjacent light emitting regions.
- the light emission color synthesis in to form a dark outline of the light emission color; and
- the light emitting layer at the boundary between adjacent light emitting regions is thinned to form a contour with high light emission luminance, or the light emission color at the boundary between adjacent light emitting regions.
- a contour having a reduced light emission luminance or a contour having a dark light emission color is formed in the boundary region between the light emitting regions adjacent to one side in the shift direction.
- a contour with high light emission luminance or a light color contour is formed, and a three-dimensional visual effect is obtained. Is obtained.
- the thickness of the light emitting layer in each light emitting region may be different.
- the coating amount of the coating liquid containing the light emitting material is set so that the thickness of the light emitting layer in each light emitting region is different with respect to at least two of the light emitting regions.
- the coating solution may be applied while differently.
- the thickness of the light emitting layer is increased, the electric resistance is increased, so that it is difficult for current to flow and the light emission luminance is lowered. Therefore, according to this, it is possible to form a predetermined light emission pattern such as a character or a picture by varying the light emission luminance for each of the plurality of light emission regions in the light emitting layer.
- the organic EL element described above further includes a functional layer that is disposed between the first electrode and the second electrode and is different from the light emitting layer, and in at least two light emitting regions of the plurality of light emitting regions, The thickness of the functional layer corresponding to each light emitting region may be different.
- the method further includes a step of forming a functional layer different from the light emitting layer between the first electrode and the second electrode, and in the step of forming the functional layer, With respect to at least two light-emitting regions among the plurality of light-emitting regions, the application is performed by varying the application amount of the coating liquid containing the material constituting the functional layer so that the thickness of the functional layer corresponding to each light-emitting region is different.
- a liquid film may be applied to form a coating film, and the coating film may be solidified to form a functional layer.
- a predetermined light emission pattern such as a character or a picture can be formed by making the light emission luminance different for each of the plurality of light emitting regions in the light emitting layer.
- the light emitting layer described above further includes a non-light emitting region, and the non-light emitting region is formed by applying two types of coating liquids, and one of the two types of coating liquids includes a plurality of light emitting regions.
- the same coating liquid for the light emitting layer in the light emitting area adjacent to itself, and the other of the two coating liquids is the same as the light emitting material of the coating liquid for the light emitting layer in the light emitting area adjacent to itself. It may contain a light emitting material or a non-light emitting material and may have a viscosity higher than that of the coating liquid for the light emitting layer in the light emitting region adjacent to itself.
- the step of forming the light emitting layer includes a sub-step of forming a non-light-emitting region in the light-emitting layer, and the sub-step of forming the non-light-emitting region includes a light-emitting region adjacent to itself among the plurality of light-emitting regions.
- a light emitting material having a viscosity equivalent to that of the light emitting layer coating liquid in the light emitting area adjacent to itself and different from the light emitting material of the light emitting layer coating liquid in the light emitting area adjacent to itself is used.
- the thickness of the coating liquid of the light emitting layer in the light emitting area adjacent to the other edge portion of the two kinds of coating liquid is reduced, and as a result, the periphery of the non-light emitting area is the two types of coating liquid. In some cases, light was emitted in the color of the light emitting material included in the other of the above.
- the other of the two types of coating liquid in the non-light emitting area is the same color as the coating liquid in the light emitting area adjacent to the non-light emitting area or a non-light emitting material. Since it has a viscosity larger than that of the coating solution for the light emitting layer in the light emitting region adjacent to itself, it is possible to eliminate blur due to the flow of ink and to provide a sharp non-light emitting region.
- the light emitting layer in one light emitting region of the adjacent light emitting regions and the light emitting layer in the other light emitting region of the adjacent light emitting regions May be in contact with each other.
- the light emitting layer in one of the adjacent light emitting regions and the light emitting region adjacent to each other may be applied so that the light emitting layer in the other light emitting region is in contact.
- a light emitting layer is formed without forming a barrier (bank) or the like at the boundary between adjacent light emitting regions, that is, without using a method using a mask (photolithographic method, etching method, vapor deposition method, etc.). Therefore, the manufacturing method can be further simplified and the price can be reduced.
- a coating liquid containing a light emitting material is applied to form a coating film having a film thickness of 1 ⁇ m or more and 6 ⁇ m or less before solidification, and the light emitting layer is formed by solidifying the coating film. May be.
- a coating liquid containing a material constituting the functional layer is applied to form a coating film having a film thickness of 1 ⁇ m or more and 6 ⁇ m or less before solidification, and the coating film is solidified.
- a functional layer may be formed.
- the film thickness of the peripheral portion (end portion) of the thin film after solidification may vary in thickness (thickening / thinning) with respect to the film thickness of the central portion. Yes (coffee stain phenomenon). More specifically, it is considered that the coating liquid at the peripheral portion of the coating film wetted and spread returns to the central portion during drying, so that the peripheral portion is thinned and the inner portion is thickened. Since the thinned portion becomes a bright line and the thickened portion becomes a dark line, the boundary between the two light emitting regions is visually recognized as a blurred border due to the bright line / dark line.
- the coating liquid shrinks from the peripheral part to the center part during drying. Can be suppressed, and retreat from the end of the application position can be suppressed. Therefore, it can suppress that the film thickness of the peripheral part (edge part) of the thin film after solidification changes in film thickness (thickening / thinning) with respect to the film thickness of the central part. As a result, the occurrence of bordering at the boundary between the two light emitting regions can be suppressed, and visibility can be improved.
- the light emitting layer may be formed by applying a coating liquid containing a light emitting material and having a viscosity of 7 cp to 20 cp to form a coating film and solidifying the coating film.
- a functional film is formed by applying a coating liquid having a viscosity of 7 cp or more and 20 cp or less containing the material constituting the functional layer to form a coated film, and solidifying the coated film. May be.
- the above-described method of applying the coating solution may be an inkjet printing method.
- the ink can be applied to the desired position with high accuracy, so that the light emitting layer and the like can be patterned with high accuracy.
- FIG. 1 is a view of an organic EL element according to the first embodiment of the present invention as seen from the light emitting surface side.
- FIG. 2 is an enlarged cross-sectional view taken along line II-II of the organic EL element shown in FIG.
- FIG. 3 is a view of an organic EL device according to the second embodiment of the present invention as seen from the light emitting surface side.
- FIG. 4 is an enlarged cross-sectional view taken along line IV-IV of the organic EL element shown in FIG.
- FIG. 5 is a view of an organic EL element according to the third embodiment of the present invention as seen from the light emitting surface side.
- FIG. 6 is an enlarged cross-sectional view taken along the line VI-VI of the organic EL element shown in FIG. FIG.
- FIG. 7 is a view of an organic EL device according to the fourth embodiment of the present invention as seen from the light emitting surface side.
- FIG. 8 is an enlarged cross-sectional view taken along line VIII-VIII of the organic EL element shown in FIG.
- FIG. 9 is a view of an organic EL element according to the fifth embodiment of the present invention viewed from the light emitting surface side.
- FIG. 10 is an enlarged cross-sectional view along the line XX of the organic EL element shown in FIG.
- FIG. 11 is the figure which looked at the organic EL element which concerns on the 6th Embodiment of this invention from the light emission surface side.
- 12 is a partially enlarged cross-sectional view of the non-light emitting region shown in FIG. FIGS.
- FIG. 13 (a) to 13 (b) show the imaging results of the light emitting surface when (a) Example 1, (b) Example 2, and (c) Example 3 emit light, respectively.
- 14 (a) to 14 (d) respectively show (a) the peripheral portion of the coating film that has spread after application of the coating solution, and (b) the peripheral edge of the thin film with film thickness variation during drying and after solidification of the coating film.
- (C) is a diagram showing a boundary between two light emitting regions accompanied by a film thickness variation, and (d) a boundary between two light emitting regions where the film thickness variation is suppressed.
- FIG. 15 shows the imaging results of the light emitting surface when Example 11 and Reference Examples 11 and 12 were caused to emit light.
- FIG. 16 shows the imaging results of the light emitting surface when Examples 21, 22 and Reference Example 21 were caused to emit light.
- FIG. 17 shows a photographing result of the light emitting surface when Examples 31 and 32 were caused to emit light.
- FIG. 1 is a view of the organic EL device according to the first embodiment of the present invention viewed from the light emitting surface side
- FIG. 2 is an enlarged cross-sectional view taken along line II-II of the organic EL device shown in FIG. .
- a predetermined functional layer other than the light emitting layer 50 may be provided between the electrodes 20 and 70.
- the functional layer include a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer. Below, the form provided with the positive hole injection layer 30, the positive hole transport layer 40, and the electron injection layer 60 as a functional layer is illustrated.
- the organic EL element 1 of the present embodiment includes a substrate 10, an anode 20 formed on the substrate 10, a hole injection layer 30 formed on the anode 20, and a hole injection layer 30.
- the substrate 10 side is a light emitting surface.
- the anode 20 and the cathode 70 are each formed as a single unit. In other words, the anode 20 and the cathode 70 are integrally formed, and form a single plate-like electrode.
- the light emitting layer 50 has two light emitting regions 51 and 52, and the light emitting material of the light emitting layer in each light emitting region is different in the two light emitting regions 51 and 52. As a result, the light emission colors of the two light emitting areas 51 and 52 are different.
- the light emitting region 51 includes a red light emitting material
- the light emitting region 52 includes a blue light emitting material.
- the light emitting region 51 may include a red light emitting material and a green light emitting material
- the light emitting region 52 may include a green light emitting material and a blue light emitting material. Details of each color light emitting material will be described later.
- the light emitting layer in the light emitting region 51 and the light emitting region 52 are in contact with each other at the boundary between the adjacent light emitting regions 51 and 52.
- the substrate 10 is a flexible substrate or a rigid substrate, such as a glass substrate or a plastic substrate.
- the anode 20 can be a thin film made of metal oxide, metal sulfide, metal, and the like. Specifically, indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (IndiumZincZOxide: abbreviation IZO). A thin film made of gold, platinum, silver, copper or the like is used. In the case of an organic EL device having a configuration in which light emitted from the light emitting layer is emitted outside the device through the anode, an electrode exhibiting optical transparency is used for the anode 20.
- a known hole injection material can be used for the hole injection layer 30.
- the hole injection material include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamine-based, starburst-type amine-based, phthalocyanine-based, amorphous carbon, polyaniline, and polythiophene derivatives. be able to.
- a known hole transport material can be used for the hole transport layer 40.
- a hole transport material polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, a polyaniline or Derivatives thereof, polythiophene or derivatives thereof, polyarylamine or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof it can.
- the light emitting layer 50 is generally formed of an organic substance that mainly emits fluorescence and / or phosphorescence, or an organic substance and a dopant that assists the organic substance.
- the dopant is added, for example, in order to improve the luminous efficiency and change the emission wavelength.
- the organic substance contained in the light emitting layer may be a low molecular compound or a high molecular compound.
- Examples of the light emitting material constituting the light emitting layer include known dye materials, metal complex materials, polymer materials, and dopant materials.
- dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds. Pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, oxadiazole dimers, pyrazoline dimers, quinacridone derivatives, coumarin derivatives, and the like.
- the metal complex material examples include rare earth metals such as Tb, Eu, and Dy, or Al, Zn, Be, Ir, Pt, etc. as a central metal, and oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline.
- the metal complex which has a structure etc. in a ligand can be mentioned.
- polystyrene resins polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, the above dye materials and metal complex light emitting materials are polymerized. The thing etc. can be mentioned.
- materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, and the like.
- examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, polyfluorene derivatives, and the like.
- examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives.
- the white color can be created by mixing the above blue, green and red colors.
- Examples of the dopant material include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squarylium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like.
- Electron transport materials include oxadiazole derivatives, anthraquinodimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyanoanthraquinodimethane or its derivatives, fluorenone derivatives, diphenyldicyanoethylene Alternatively, derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like can be given.
- a known electron injection material can be used for the electron injection layer 60.
- the electron injection material include alkali metals, alkaline earth metals, alloys containing at least one of alkali metals and alkaline earth metals, oxides of alkali metals or alkaline earth metals, halides, carbonates, or these And a mixture of these substances.
- the material of the cathode 70 is preferably a material having a low work function, easy electron injection into the light emitting layer, and high electrical conductivity. Further, in the organic EL element configured to extract light from the anode side, the material of the cathode 70 is preferably a material having a high visible light reflectance in order to reflect the light emitted from the light emitting layer to the anode side by the cathode.
- the cathode 70 for example, an alkali metal, an alkaline earth metal, a transition metal, a Group 13 metal of the periodic table, or the like can be used.
- a transparent conductive electrode made of a conductive metal oxide, a conductive organic material, or the like can be used as the cathode 70.
- the above layers and electrodes can be formed by a vapor deposition method or a coating method.
- Application methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, spray coating and Examples of the coating method include a nozzle coating method, and a coating method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method.
- pattern coating is required, it is preferably formed by a coating method capable of pattern coating, particularly by an ink jet printing method.
- the solvent of the ink (coating liquid) used in the coating method is not particularly limited as long as it dissolves each material.
- Chlorine solvents such as chloroform, methylene chloride and dichloroethane
- ether solvents such as tetrahydrofuran, toluene
- aromatic hydrocarbon solvents such as xylene
- ketone solvents such as acetone and methyl ethyl ketone
- ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, and water.
- a predetermined light emission pattern such as a character or a picture is formed by changing the light emission color for each of the light emitting regions 51 and 52 in the light emitting layer 50, so that the electrode 20 , 70 may be formed together, and it is not necessary to form the electrodes 20, 70 in a light emitting pattern.
- the present invention does not exclude a method using a mask as the light emitting layer forming method.
- the light emitting layer 50 is also formed by a technique that does not use a mask, in other words, unless a technique that forms a barrier (bank) or the like using a mask at the boundary between adjacent light emitting regions 51 and 52 is used. If the light emitting layer 50 is formed so that the light emitting layer in the light emitting region 51 and the light emitting layer in the light emitting region 52 are in contact with each other at the boundary between the adjacent light emitting regions 51 and 52, the productivity can be further simplified and reduced. Pricing is possible. [Second Embodiment]
- FIG. 3 is a view of an organic EL element according to the second embodiment of the present invention viewed from the light emitting surface side
- FIG. 4 is an enlarged cross-sectional view taken along line IV-IV of the organic EL element shown in FIG. .
- the organic EL element 1 includes a light emitting layer 50A instead of the light emitting layer 50 in the organic EL element 1.
- the light emitting layer 50A has two light emitting regions 51A and 52A, and the light emitting material of the light emitting layer in each light emitting region is different in the two light emitting regions 51A and 52A. As a result, the light emission colors of the two light emitting areas 51A and 52A are different.
- the light emitting region 51 ⁇ / b> A contains a red light emitting material like the light emitting region 51
- the light emitting region 52 ⁇ / b> A contains a blue light emitting material like the light emitting region 52.
- an ink containing a red light emitting material is applied to the light emitting area 51A, and then an ink containing a blue light emitting material is applied to the light emitting area 52A.
- the ink of each light emitting area is designed and applied so as to overlap with a predetermined width by a design value.
- the predetermined width is, for example, 0.05 mm to 15 mm, preferably 0.1 mm to 2.0 mm, and more preferably 0.2 mm to 0.5 mm.
- the light emitting layer 50A has a boundary region 53A between the adjacent light emitting regions 51A and 52A.
- the boundary region 53A includes the light emitting material of the light emitting layer in the light emitting region 51A and the light emission of the light emitting layer in the light emitting region 52A. Material.
- the light emitting material of the light emitting region 51A and the light emitting material of the light emitting region 52A may be mixed, or the light emitting material of the light emitting region 51A and the light emitting region 52A may be mixed depending on the viscosity of the ink.
- the light emitting material may be laminated in two layers. Further, the thickness of the light emitting layer in the boundary region 53A may be larger than the thickness of the light emitting layer in the light emitting region 51A and the thickness of the light emitting layer in the light emitting region 52A.
- the boundary between adjacent light emitting regions may be blurred due to wet spreading of ink (coating liquid).
- ink coating liquid
- the inventors of the present application apply the inks of the respective light emitting areas so as to overlap each other at the boundaries of these light emitting areas. It has been found that blurring can be suppressed and visibility can be improved. This is because the light emitting layer at the boundary between adjacent light emitting regions is thickened to form a contour with reduced light emission luminance, or the light emitting color is dark due to the light emitting color composition at the boundary between adjacent light emitting regions. This is considered to be due to the fact that these boundaries appear sharp when the contour is formed.
- the boundary region 53A between the adjacent light emitting regions 51A and 52A includes both light emitting materials of the light emitting regions 51A and 52A. Therefore, blurring at the boundary between these light emitting areas 51A and 52A can be suppressed, and visibility can be improved.
- FIG. 5 is a view of an organic EL device according to the third embodiment of the present invention viewed from the light emitting surface side
- FIG. 6 is an enlarged cross-sectional view taken along line VI-VI of the organic EL device shown in FIG. .
- the organic EL element 1B includes a light emitting layer 50B in place of the light emitting layer 50 in the organic EL element 1.
- the light emitting layer 50B has two light emitting regions 51B and 52B, and the light emitting material of the light emitting layer in each light emitting region is different in the two light emitting regions 51B and 52B. Thereby, the light emission colors are different between the two light emitting regions 51B and 52B.
- the light emitting region 51 ⁇ / b> B includes a red light emitting material similarly to the light emitting region 51
- the light emitting region 52 ⁇ / b> B includes a blue light emitting material similar to the light emitting region 52.
- an ink containing a red light emitting material is applied to the light emitting area 51B, and then an ink containing a blue light emitting material is applied to the light emitting area 52B. At this time, the ink is applied so as to shift the light emitting region 51B in the direction along the light emitting surface with respect to the light emitting region 52B.
- one of the two light emitting areas 51B and 52B is arranged so that one light emitting area 51B is surrounded by the other light emitting area 52B.
- ink corresponding to one light emitting region 51B is applied so as to shift in the direction along the light emitting surface, for example, the first light emitting region and one light emitting region 51B and the other light emitting region on one side in the shift direction.
- 52B can be overlapped, a gap is formed between one light emitting region 51B and the other light emitting region 52B on the other side in the shift direction.
- the ink in each light emitting region is applied so as to overlap at the boundary between the light emitting region 51B and the light emitting region 52B in the direction in which the light emitting region 51B is shifted with respect to the light emitting region 52B.
- the ink in each light emitting area is not applied by design. It is possible that a thin film is formed by flow.
- the light emitting layer 50B has a boundary region 53B between the adjacent light emitting regions 51B and 52B.
- the boundary region 53B is a light emitting material of the light emitting layer in the light emitting region 51B and light emission of the light emitting layer in the light emitting region 52B. Material.
- the light emitting layer 50B has a boundary region 54B between the adjacent light emitting regions 51B and 52B.
- the thickness of the light emitting layer in the boundary region 54B is the same as the light emitting layer in the light emitting region 51B and the light emitting layer in the light emitting region 52B. It is even thinner than the thinner one.
- the thickness of the light emitting layer in the boundary region 54B is preferably 0.7 times or less, more preferably 0.5 times or less of the average value of the thickness of the light emitting layer in the light emitting region 51B and the thickness of the light emitting layer in the light emitting region 52B. preferable.
- the light emitting material of the light emitting region 51B and the light emitting material of the light emitting region 52B may be mixed or the light emitting material of the light emitting region 51B and the light emitting region 52B may be mixed depending on the viscosity of the ink.
- the light emitting material may be laminated in two layers.
- the thickness of the light emitting layer in the boundary region 53B may be larger than the thickness of the light emitting layer in the light emitting region 51B and the thickness of the light emitting layer in the light emitting region 52B.
- the light emitting material of the light emitting region 51B and the light emitting material of the light emitting region 52B do not exist, and an electron injection layer and a cathode may exist, or the light emitting region 51B.
- the light emitting material and the light emitting material of the light emitting region 52B may be thinly present.
- a three-dimensional visual effect can be obtained by shifting a predetermined light emission pattern with respect to the surrounding light emission pattern. This is, (I) On one side of the shift direction, as described above, the light emitting layer at the boundary between adjacent light emitting regions is thickened, thereby forming a contour with reduced light emission luminance, or the boundary between adjacent light emitting regions. The light emission color synthesis in to form a dark outline of the light emission color; and (Ii) On the other side in the shift direction, on the contrary, the light emitting layer at the boundary between adjacent light emitting regions is thinned to form a contour with high light emission luminance, or the light emission color at the boundary between adjacent light emitting regions. By synthesizing a bright color outline, It is considered that a three-dimensional visual effect can be obtained.
- the shift amount is, for example, 0.05 mm to 15 mm, preferably 0.1 mm to 2.0 mm, and more preferably 0.2 mm to 0.5 mm.
- the boundary region 53B between the adjacent light emitting regions 51B and 52B includes both light emitting materials of the light emitting regions 51B and 52B. Therefore, since the boundary region 54B between the adjacent light emitting regions 51B and 52B is thinner than the thickness of both the light emitting layers 51B and 52B, a three-dimensional effect can be obtained.
- FIG. 7 is a view of an organic EL device according to the fourth embodiment of the present invention viewed from the light emitting surface side
- FIG. 8 is an enlarged cross-sectional view taken along line VIII-VIII of the organic EL device shown in FIG. .
- the organic EL element 1C shown in FIG. 7 and FIG. 8 includes a light emitting layer 50C in place of the light emitting layer 50 in the organic EL element 1.
- the light emitting layer 50C has two light emitting regions 51C and 52C, and the thickness of the light emitting layer in each light emitting region is different in the two light emitting regions 51C and 52C. Thereby, the light emission luminance differs between the two light emitting regions 51C and 52C.
- the light emitting region 52C is thicker than the light emitting region 51C. The thicker the light emitting layer, the higher the electrical resistance and the less the current flows. Therefore, the light emission luminance in the light emitting region 52C is lower than that in the light emitting region 51C.
- a predetermined light emission pattern such as a character or a picture is formed by making the light emission luminance different for each of the light emitting regions 51C and 52C in the light emitting layer 50. Therefore, the electrode 20 , 70 may be formed together, and it is not necessary to form the electrodes 20, 70 in a light emitting pattern. As a result, it is not necessary to prepare a mask for electrode formation in accordance with the light emission pattern. Therefore, when forming a plurality of types of light emitting patterns, it is not necessary to prepare a mask for forming an electrode for each light emitting pattern, and the manufacturing method can be simplified and the cost can be reduced. [Fifth Embodiment]
- FIG. 9 is a view of an organic EL element according to the fifth embodiment of the present invention as viewed from the light emitting surface side
- FIG. 10 is an enlarged cross-sectional view along the line XX of the organic EL element shown in FIG.
- the organic EL element 1D shown in FIGS. 9 and 10 is different from the first embodiment in that the organic EL element 1 includes a hole transport layer 40D instead of the hole transport layer 40.
- the thicknesses of the hole transport layers corresponding to the two light emitting regions 51D and 52D are different.
- the light emission luminance is different between the two light emitting regions 51D and 52D.
- the light emitting region 52D is thicker than the light emitting region 51D.
- the thicker the thickness is, the larger the electric resistance becomes, and it becomes difficult for the current to flow. Therefore, the light emitting luminance in the light emitting region 52C is lower than that in the light emitting region 51C.
- the organic EL element 1D of the fifth embodiment has the same advantages as the organic EL element 1C of the fourth embodiment.
- FIG. 11 is a view of an organic EL device according to the sixth embodiment of the present invention as seen from the light emitting surface side
- FIG. 12 is a partially enlarged sectional view of the non-light emitting region shown in FIG.
- the organic EL element 1E shown in FIGS. 11 and 12 is different from the second embodiment in that the organic EL element 1A includes a light emitting layer 50E instead of the light emitting layer 50A.
- the light emitting layer 50E further includes a non-light emitting region 55 in addition to the two light emitting regions 51A and 52A and the boundary region 53A therebetween.
- the non-light emitting area 55 is formed by applying two types of inks 55a and 55b in an overlapping manner.
- the ink 55b is the same as the ink applied to the light emitting region 52A adjacent to the ink 55b.
- the ink 55a includes the same light emitting material (that is, the same color) as the ink 55b or a non-light emitting material, and has a larger viscosity than the ink 55b.
- the viscosity of the ink 55b is 1 cp to 20 cp, preferably 2 cp to 10 cp, and more preferably 2 cp to 5 cp.
- the thickness of the light emitting layer in the non-light emitting region 55 is thicker than the thickness of the light emitting layer in the light emitting region 52A adjacent to itself, and as a result, the light emission luminance of the non light emitting region 55 is very low.
- This non-light emitting area 55 is preferably used for black characters and the like.
- the ink 55a has a viscosity equal to that of the ink 55b and includes a light emitting material different from the light emitting material of the ink 55b (that is, different color, for example, the same color as the ink applied to the light emitting region 51).
- the thickness of the ink 55b is reduced at the edge portion A of the ink 55a.
- the periphery of the non-light emitting region 55 emits light in the color of the light emitting material contained in the ink 55a, and the flow of the ink. In some cases, a blur is not generated and a sharp non-light emitting region is not provided.
- the ink 55a in the non-light-emitting region 55 is the same color as the ink 55b in the light-emitting region 52A adjacent to itself or a non-light-emitting material. Even in this case, the color is black and the viscosity is higher than that of the ink 55b, so that the blur due to the flow of the ink can be eliminated and a sharp non-light emitting area can be provided.
- each layer is coated with a coating liquid to form a coating film. It is formed by drying and solidifying, but in the process of drying and solidifying the coating film, the film thickness of the peripheral part (edge part) varies with the film thickness of the central part (thickening / thinning) ) (Coffee stain phenomenon).
- the coating liquid on the peripheral portion 100 of the coating film that has spread after application is applied to the central portion 200 during the drying of the coating liquid as shown in FIG. 14 (b). It is considered that the outermost peripheral portion 101 of the peripheral portion 100 is thinned and the inner portion 102 is thickened. For example, it is considered that the thicker the coating solution is, the larger the width at which the coating solution shrinks from the peripheral portion 100 to the central portion 200 at the time of drying, and a large retreat from the end portion 103 at the coating position.
- the thinned portion 101 becomes a bright line and the thickened portion 102 becomes a dark line.
- the coating film coating liquid
- a coating liquid containing a light emitting material is applied to form a coating film having a thickness of 1 ⁇ m to 6 ⁇ m, and the light emitting layer is solidified by solidifying the coating film.
- the film thickness of the coating film at the time of coating the coating liquid (before the coating film is solidified) is reduced to 1 ⁇ m or more and 6 ⁇ m or less, as shown in FIG. It is possible to suppress the coating liquid from shrinking and to suppress the backward movement from the end of the coating position. Therefore, in the thin film after solidification, it is possible to suppress the film thickness variation (thickening / thinning) of the film thickness of the peripheral part (end part) with respect to the film thickness of the central part. As a result, the occurrence of bordering at the boundary between the two light emitting regions 51 and 52 can be suppressed, and the visibility can be improved.
- the idea of the present invention can also be applied to the functional layer.
- a coating film containing a material constituting the hole transport layer 40D is applied to form a coating film having a thickness of 1 ⁇ m or more and 6 ⁇ m or less. Even if the hole transport layer 40D is formed by forming and solidifying the coating film, as described above, in the process of drying and solidifying the coating film, the film thickness of the peripheral part (end part) is the central part.
- the film thickness of the coating film is focused.
- the viscosity of the coating liquid is focused.
- the coating liquid in the peripheral portion 100 of the coating film that has spread after application returns to the central portion 200 during drying of the coating solution, whereby the peripheral portion 101 of the peripheral portion 100 is thinned.
- the inner portion 102 is considered to be thicker.
- the lower the viscosity of the coating solution the larger the width of the coating solution that contracts from the peripheral portion 100 to the central portion 200 during drying, and the end portion 103 of the coating position. It is thought that it will greatly recede from. It is also considered that the swell (thickening) at the peripheral edge 100 is large.
- a coating film containing a light emitting material and having a viscosity of 7 cp to 20 cp is applied to form a coating film, and the coating film is solidified to form the light emitting layer.
- the idea of the present invention can also be applied to the functional layer.
- a coating film is formed by applying a coating solution having a viscosity of 7 cp or more and 20 cp or less including the material constituting the hole transport layer 40D.
- the film thickness of the peripheral portion (end portion) is larger than the film thickness of the central portion. Variation in film thickness (thickening / thinning) can be suppressed, and as a result, the occurrence of bordering at the boundary between the two light emitting regions 51D and 52D can be suppressed, and visibility can be improved. it can.
- the present invention is not limited to the above-described embodiment, and various modifications can be made.
- the mode in which the light emitting layer has two different light emitting regions is illustrated, but the light emitting layer may have three or more different light emitting regions.
- a light emitting region having a different light emission color and a light emitting region having a different light emission luminance may be mixed.
- anode / light emitting layer / cathode b) anode / hole injection layer / light emitting layer / cathode c) anode / hole injection layer / light emitting layer / electron injection layer / cathode d) anode / hole injection layer / light emitting layer / Electron transport layer / electron injection layer / cathode e) anode / hole injection layer / hole transport layer / light emitting layer / cathode f) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode g ) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode h) Anode / light emitting layer / electron injection layer / cathode i) Anode / light emitting layer / electron transport layer / electron injection Layer / cathode i)
- the organic EL element 1A of the second embodiment shown in FIGS. 3 and 4 the organic EL element 1B of the third embodiment shown in FIGS. 5 and 6, FIGS.
- the organic EL element 1C of the fourth embodiment shown in FIG. 8 was produced as follows. [Example 1] (Base process)
- a base substrate having an anode 20 formed on a glass substrate 10 was prepared. Specifically, after forming a transparent conductive film (thickness 150 nm) made of ITO on the glass substrate 10, a grid-like auxiliary electrode (line width 50 ⁇ m, A pitch of 300 ⁇ m) was formed. A protective insulating film made of polyimide (Toray Photo Nice) was formed on the grid-like auxiliary electrode.
- a hole injection layer composition (ink) was applied onto a base substrate with a protective insulating film using a spin coater and dried to form a hole injection layer 30 (film thickness 65 nm).
- the hole transport layer composition (ink) was applied with a spin coater, dried and fired at 10 Pa and 190 ° C. for 60 minutes in a vacuum dryer, and the hole transport layer 40 (film thickness 20 nm). Formed.
- the composition for the hole transport layer (ink) is such that the polymer for the hole transport layer is mixed with a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so that the solid content concentration becomes 0.5%. It is dissolved. (Light emitting layer process)
- a light emitting layer 50A was formed on the base.
- a polymer for light emission is used as a red ink in the light emitting region 51A (the cross section) on the base, and is applied to form a thin film by ink jet printing.
- the luminescent composition (red ink) is obtained by dissolving a luminescent polymer in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so as to have a solid concentration of 2.0%. .
- the light emitting composition (white ink) is obtained by dissolving a light emitting polymer in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so as to have a solid content concentration of 0.7%. .
- the electron injection layer 60 and the cathode 70 were formed on the light emitting layer 50.
- NaF / Mg / Al / Ag was deposited on the light emitting layer 50 by 2 nm / 2 nm / 200 nm / 100 nm. Thereafter, it was bonded to a counter substrate and divided.
- a light emitting layer 50B was formed on the base. Specifically, a polymer for light emission is used as a red ink in the light emitting region 51B (the cross section) on the base, and is applied to form a thin film by ink jet printing. For 5 minutes.
- the luminescent composition (red ink) is the same as in Example 1 above.
- a white light emitting polymer was used as the light emitting region 52B (background portion), and the thin film was applied by ink jet printing, followed by vacuum drying to 10 Pa and baking at 130 ° C. for 10 minutes.
- the luminescent composition (white ink) is the same as in Example 1 above.
- the light emitting layer 50C was formed on the base. Specifically, with respect to the base, after vacuum drying up to 10 Pa with an inkjet printing apparatus, the light emitting region 51C (I portion) is a thin film area of 40 nm and the light emitting region 52C (background portion) is a thin film area of 60 nm. Application was performed by ink jet printing, and baking was further performed at 130 ° C. for 10 minutes.
- the light-emitting composition (ink) is obtained by dissolving a light-emitting polymer in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so as to have a solid concentration of 1.4%. (Post-process)
- FIGS. 13 (a) to 13 (c) show the photographing results of the light emitting surfaces when light is emitted from Examples 1 to 3, respectively.
- the emission color is made different for each of the light emitting regions 51A and 51B (cross beam portion) and 52A and 52B (background portion) in the light emitting layer.
- a predetermined light emission pattern such as a character or a picture can be formed.
- predetermined light emission patterns such as a character and a picture, can be formed by varying light emission brightness
- Example 2 it can be seen that in Example 1, blurring at the boundary between the light emitting region 51A (cross beam portion) and the light emitting region 52A (background portion) could be suppressed. Moreover, according to FIG.13 (b), in Example 2, it turns out that the three-dimensional visual effect was acquired.
- Example 11 of the present invention the equivalent to the organic EL element 1 of the first embodiment shown in FIGS. 1 and 2 to which the light emitting layer forming method of the seventh embodiment is applied, that is, for the light emitting layer.
- the film thickness of the coating film is as thin as 1 ⁇ m or more and 6 ⁇ m or less, and the light emitting layer in the light emitting area 51 and the light emitting area 52 in the boundary between two adjacent light emitting areas 51 and 52.
- the organic EL device 1 equivalent to the light emitting layer was made as follows, and Reference Examples 11 and 12 were made as follows. In FIG.
- the constituent material of the light emitting layer 50 is shown as a red light emitting material and a blue light emitting material. However, in the following embodiments, the constituent material of the light emitting layer may be different from that of FIG. 2. is there. In the following, the ground process and the post-process are the same as those in the first embodiment, and the description thereof is omitted. [Example 11] (Light emitting layer process)
- the light emitting layer 50 was formed on the base. Specifically, after vacuum drying up to 10 Pa with the ink jet printing apparatus with respect to the base, a polymer yellow ink for light emission is used for the light emitting region 51 (round portion) and light emitting region 52 (background portion) is used for light emission. A polymer blue ink was used to form a thin film and baked at 130 ° C. for 10 minutes.
- the luminescent composition (yellow ink)
- a luminescent polymer is dissolved in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so as to have a solid content concentration of 0.7%. Used and the viscosity was 5 cp.
- the film thickness immediately after coating was 4.5 ⁇ m.
- the film thickness of the coating film immediately after application is a value obtained by back-calculating the numerical value obtained by measuring the film thickness after drying with a stylus by the solid content concentration (the same applies hereinafter).
- the light emitting polymer was dissolved in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so as to have a solid content concentration of 1.0%. Used, and the viscosity was 8 cp. The film thickness immediately after coating was 2.4 ⁇ m.
- Example 11 is the same as Example 11 except that the film thickness immediately after application of the yellow ink is 6.8 ⁇ m.
- Reference Example 12 [Reference Example 12]
- Example 11 is the same as Example 11 except that the film thickness immediately after application of the yellow ink is 9.1 ⁇ m and the film thickness immediately after application of the blue ink is 4.8 ⁇ m. [Evaluation]
- FIG. 15 shows a photographing result of the light emitting surface when Example 11 and Reference Examples 11 and 12 were caused to emit light.
- Reference Example 12 if the thickness of the coating film when the yellow ink is applied to the light emitting region 51 (round portion) (before the coating film is solidified) is as thick as 9.1 ⁇ m, a bright line appears at the boundary between the two light emitting regions 51 and 52. In contrast, in Reference Example 11, the thickness of the coating film at the time of application of yellow ink in the light emitting region 51 (round portion) (before solidification of the coating film) was observed.
- the two light emitting regions 51 and 52 are formed by reducing the coating film thickness to 4.5 ⁇ m when the yellow ink is applied to the light emitting region 51 (round portion) (before the coating film is solidified). It can be seen that the generation of bright lines and dark lines at the borders of the film is suppressed, and the visibility of the border is further suppressed.
- Example 21 the equivalent to the organic EL element 1 of the first embodiment shown in FIGS. 1 and 2 to which the light emitting layer forming method of the seventh embodiment is applied, that is, the light emitting layer.
- An organic EL element 1 equivalent to the light emitting layer 52 in contact with the light emitting layer was prepared as follows, and Reference Example 21 was prepared as follows. In addition, below, since a base
- the light emitting layer 50 was formed on the base. Specifically, after vacuum drying up to 10 Pa with an ink jet printing apparatus on the base, a polymer purple ink for light emission is used for the light emitting region 51 (spiral portion), and light emission is performed for the light emitting region 52 (background portion).
- the polymer red ink was used to form a thin film and baked at 130 ° C. for 10 minutes.
- the luminescent composition (purple ink) a luminescent polymer is dissolved in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so as to have a solid content concentration of 0.7%. Used and the viscosity was 5 cp. The film thickness immediately after application was 2.8 ⁇ m.
- the light emitting polymer was dissolved in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so as to have a solid content concentration of 0.7%.
- the viscosity was 5 cp.
- the film thickness immediately after coating was set to 3.8 ⁇ m.
- Example 21 is the same as Example 21 except that the film thickness immediately after application of the red ink is 5.1 ⁇ m. [Reference Example 21]
- Example 21 is the same as Example 21 except that the film thickness immediately after application of the red ink is 6.4 ⁇ m. [Evaluation]
- FIG. 16 shows the imaging results of the light emitting surface when Examples 21, 22 and Reference Example 21 were caused to emit light.
- Reference Example 21 when the thickness of the coating film when the red ink is applied to the light emitting region 52 (background portion) (before the coating film is solidified) is as thick as 6.4 ⁇ m, a bright line is formed at the boundary between the two light emitting regions 51 and 52. A dark line is generated and the border is visually recognized.
- the thickness of the coating film at the time of applying the red ink in the light emitting region 52 (background part) (before the coating film is solidified) is reduced to 5.1 ⁇ m and 3.8 ⁇ m, respectively.
- Example 31 the equivalent to the organic EL element 1 of the first embodiment shown in FIG. 1 and FIG. 2 to which the light emitting layer forming method of the seventh embodiment is applied, that is, the light emitting layer.
- the organic EL element 1 equivalent to which the light emitting layer in 52 is in contact was prepared as follows.
- the light emitting layer forming method of the eighth embodiment is also applied.
- substrate process and a post process are the same as the said Example 1, description is abbreviate
- the light emitting layer 50 was formed on the base. Specifically, after vacuum drying up to 10 Pa with the ink jet printing apparatus with respect to the above base, a light emitting polymer white ink is used for the light emitting region 51 (snow mark portion), and the light emitting region 52 (background portion) is used for light emission. A polymer blue ink was used to form a thin film and baked at 130 ° C. for 10 minutes.
- the luminescent composition (white ink), a luminescent polymer dissolved in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so as to have a solid content concentration of 0.7%. Used and the viscosity was 5 cp. The film thickness immediately after coating was 4.9 ⁇ m.
- a light emitting composition blue ink
- a light emitting polymer was dissolved in a mixed solvent of 4-methoxytoluene and cyclohexylbenzene (mixing ratio 2: 8) so as to have a solid concentration of 0.8%.
- the viscosity was 5 cp.
- the film thickness immediately after coating was 3.4 ⁇ m.
- Example 31 The same as Example 31, except that the density of the white ink was 1.4%, the viscosity was 11 cp, and the film thickness immediately after coating was 1.8 ⁇ m. [Evaluation]
- FIG. 17 shows a photographing result of the light emitting surface when Examples 31 and 32 were caused to emit light.
- the thickness of the coating film when the blue ink is applied to the light emitting region 52 (background portion) (before the coating film is solidified) is 3.4 ⁇ m, and the white ink is applied to the light emitting region 51 (snow mark portion).
- Example 31 a dark line, that is, a border is slightly visually recognized at the boundary between the two light emitting regions 51 and 52.
- Example 32 by further increasing the viscosity of the white ink in the light emitting area 51 (snow mark portion) to 11 cp, the generation of dark lines at the boundary between the two light emitting areas 51 and 52 is further suppressed, and the border is drawn. The visibility of was more suppressed.
- the present invention can be applied to organic EL elements capable of simplifying the manufacturing method and reducing the price, and uses of the organic EL element manufacturing method.
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Abstract
Description
(i)シフト方向の一方側では、上記したように、隣り合う発光領域の境界における発光層が厚くなることにより、発光輝度が低下した輪郭が形成されること、もしくは、隣り合う発光領域の境界における発光色合成により、発光色が暗い色の輪郭が形成されることにより、及び、
(ii)シフト方向の他方側では、反対に、隣り合う発光領域の境界における発光層が薄くなることにより、発光輝度が高い輪郭が形成されること、もしくは、隣り合う発光領域の境界における発光色合成により、発光色が明るい色の輪郭が形成されることにより、
3次元的な視認効果が得られるものと考える。
[第1の実施形態]
[第2の実施形態]
[第3の実施形態]
(i)シフト方向の一方側では、上記したように、隣り合う発光領域の境界における発光層が厚くなることにより、発光輝度が低下した輪郭が形成されること、もしくは、隣り合う発光領域の境界における発光色合成により、発光色が暗い色の輪郭が形成されることにより、及び、
(ii)シフト方向の他方側では、反対に、隣り合う発光領域の境界における発光層が薄くなることにより、発光輝度が高い輪郭が形成されること、もしくは、隣り合う発光領域の境界における発光色合成により、発光色が明るい色の輪郭が形成されることにより、
3次元的な視認効果が得られるものと考える。
[第4の実施形態]
[第5の実施形態]
[第6の実施形態]
[第7の実施形態]
[第8の実施形態]
a)陽極/発光層/陰極
b)陽極/正孔注入層/発光層/陰極
c)陽極/正孔注入層/発光層/電子注入層/陰極
d)陽極/正孔注入層/発光層/電子輸送層/電子注入層/陰極
e)陽極/正孔注入層/正孔輸送層/発光層/陰極
f)陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極
g)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
h)陽極/発光層/電子注入層/陰極
i)陽極/発光層/電子輸送層/電子注入層/陰極
ここで、記号「/」は、記号「/」を挟む各層が隣接して積層されていることを示す。
[実施例]
[実施例1]
(下地工程)
(発光層工程)
(後工程)
[実施例2]
(下地工程)
(発光層工程)
(後工程)
[実施例3]
(下地工程)
(発光層工程)
(後工程)
[評価]
[実施例11]
(発光層工程)
[参考例11]
[参考例12]
[評価]
[実施例21]
(発光層工程)
[実施例22]
[参考例21]
[評価]
[実施例31]
(発光層工程)
[実施例32]
[評価]
Claims (21)
- ひとつらなりの第1の電極と、ひとつらなりの第2の電極と、前記第1の電極と前記第2の電極との間に配置される発光層とを備える有機EL素子であって、
前記発光層は、複数の発光領域を有し、
前記複数の発光領域のうちの少なくとも2つの発光領域では、発光色および発光輝度のうちの少なくとも一方が異なる、
有機EL素子。 - 前記複数の発光領域のうちの少なくとも2つの発光領域では、それぞれの発光領域における発光層に含まれる発光材料が異なる、請求項1に記載の有機EL素子。
- 前記複数の発光領域のうちの隣り合う発光領域の間の境界領域における発光層が、前記隣り合う発光領域のうちの一方の発光領域における発光層に含まれる発光材料と、前記隣り合う発光領域のうちの他方の発光領域における発光層に含まれる発光材料とを含む、請求項1又は2に記載の有機EL素子。
- 前記複数の発光領域のうちの隣り合う発光領域の間の境界領域における発光層は、前記隣り合う発光領域のうちの一方の発光領域における発光層と、前記隣り合う発光領域のうちの他方の発光領域における発光層とのうちで厚みの薄い発光層よりも、更にその厚みが薄い、請求項1~3のいずれか1項に記載の有機EL素子。
- 前記複数の発光領域のうちの少なくとも2つの発光領域では、それぞれの発光領域における発光層の厚みが異なる、請求項1~4のいずれか1項に記載の有機EL素子。
- 前記第1の電極と前記第2の電極との間に配置され、前記発光層とは異なる機能層をさらに備え、
前記複数の発光領域のうちの少なくとも2つの発光領域では、それぞれの発光領域に対応する機能層の厚みが異なる、請求項1~5のいずれか1項に記載の有機EL素子。 - 前記発光層は、非発光領域をさらに有し、
前記非発光領域は、2種の塗布液を塗布することによって形成されており、
前記2種の塗布液の一方は、前記複数の発光領域のうちの自身に隣接する発光領域における発光層のための塗布液と同一であり、
前記2種の塗布液の他方は、前記自身に隣接する発光領域における発光層のための塗布液の発光材料と同一の発光材料を含むか、もしくは、非発光材料を含んでおり、前記自身に隣接する発光領域における発光層のための塗布液よりも大きい粘度を有する、
請求項1~6のいずれか1項に記載の有機EL素子。 - 前記複数の発光領域のうちの隣り合う発光領域の間の境界領域では、前記隣り合う発光領域のうちの一方の発光領域における発光層と、前記隣り合う発光領域のうちの他方の発光領域における発光層とが当接する、請求項1~7のいずれか1項に記載の有機EL素子。
- 請求項1に記載の有機EL素子の製造方法であって、
ひとつらなりの第1の電極を形成する工程と、
複数の発光領域を有する発光層であって、前記複数の発光領域のうちの少なくとも2つの発光領域では、発光色および発光輝度のうちの少なくとも一方が異なる前記発光層を形成する工程と、
ひとつらなりの第2の電極を形成する工程と、
を有する、有機EL素子の製造方法。 - 前記発光層を形成する工程では、前記複数の発光領域のうちの少なくとも2つの発光領域に関して、それぞれ異なる発光材料を含む塗布液を各発光領域にそれぞれパターン塗布して塗布膜をパターン形成し、当該塗布膜を固化することによって各発光領域の発光層を形成する、請求項9に記載の有機EL素子の製造方法。
- 前記発光層を形成する工程において、前記複数の発光領域のうちの隣り合う発光領域の間の境界領域では、前記隣り合う発光領域のうちの一方の発光領域における発光層の発光材料を含む塗布液を塗布するとともに、前記隣り合う発光領域のうちの他方の発光領域における発光層の発光材料を含む塗布液を塗布する、請求項9または10に記載の有機EL素子の製造方法。
- 前記発光層を形成する工程において、前記複数の発光領域のうちの隣り合う発光領域の間の境界領域では、発光材料を含む塗布液を塗布しない、請求項9または10に記載の有機EL素子の製造方法。
- 前記発光層を形成する工程では、前記複数の発光領域のうちの少なくとも2つの発光領域に関して、それぞれの発光領域における発光層の厚みを異ならせるように、発光材料を含む塗布液の塗布量を異ならせて当該塗布液を塗布する、請求項9に記載の有機EL素子の製造方法。
- 前記第1の電極と前記第2の電極との間に、前記発光層とは異なる機能層を形成する工程をさらに有し、
前記機能層を形成する工程では、前記複数の発光領域のうちの少なくとも2つの発光領域に関し、それぞれの発光領域に対応する機能層の厚みを異ならせるように、前記機能層を構成する材料を含む塗布液の塗布量を異ならせて当該塗布液を塗布して塗布膜を形成し、当該塗布膜を固化して前記機能層を形成する、請求項9に記載の有機EL素子の製造方法。 - 前記発光層を形成する工程では、前記発光層に非発光領域を形成するサブ工程を含み、
前記非発光領域を形成するサブ工程では、前記複数の発光領域のうちの自身に隣接する発光領域における発光層のための塗布液の発光材料と同一の発光材料を含むか、もしくは、非発光材料を含んでおり、前記自身に隣接する発光領域における発光層のための塗布液よりも大きい粘度を有する塗布液を塗布した後に、前記自身に隣接する発光領域における発光層のための塗布液と同一の塗布液を塗布する、請求項9に記載の有機EL素子の製造方法。 - 前記発光層を形成する工程では、前記複数の発光領域のうちの隣り合う発光領域の間の境界領域に関し、前記隣り合う発光領域のうちの一方の発光領域における発光層と、前記隣り合う発光領域のうちの他方の発光領域における発光層とが当接するように、塗布液を塗布する、請求項9に記載の有機EL素子の製造方法。
- 前記発光層を形成する工程では、発光材料を含む塗布液を塗布して膜厚1μm以上6μm以下の塗布膜を形成し、当該塗布膜を固化することによって前記発光層を形成する、請求項9に記載の有機EL素子の製造方法。
- 前記発光層を形成する工程では、発光材料を含む粘度7cp以上20cp以下の塗布液を塗布して塗布膜を形成し、当該塗布膜を固化することによって前記発光層を形成する、請求項9に記載の有機EL素子の製造方法。
- 前記機能層を形成する工程では、前記機能層を構成する材料を含む塗布液を塗布して膜厚1μm以上6μm以下の塗布膜を形成し、当該塗布膜を固化することによって前記機能層を形成する、請求項14に記載の有機EL素子の製造方法。
- 前記機能層を形成する工程では、前記機能層を構成する材料を含む粘度7cp以上20cp以下の塗布液を塗布して塗布膜を形成し、当該塗布膜を固化することによって前記機能層を形成する、請求項14に記載の有機EL素子の製造方法。
- 前記塗布液を塗布する方法がインクジェットプリント法である、請求項9から20のいずれか1項に記載の有機EL素子の製造方法。
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KR20200004288A (ko) * | 2017-02-24 | 2020-01-13 | 쌩뜨레 나티오날 데 라 르세르쉬 생띠끄 (씨. 엔. 알. 에스) | 복수의 광활성 재료들을 포함하는 다색 광전자 장치를 제조하는 방법 및 이에 의해 제조된 광전자 장치 |
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KR20220099147A (ko) * | 2021-01-04 | 2022-07-13 | 삼성디스플레이 주식회사 | 발광 소자, 이를 포함하는 표시 장치, 그 발광 소자의 제조 방법 |
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US20160141541A1 (en) | 2016-05-19 |
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